1 s2.0 S0926860X21004816 Main

Applied Catalysis A, General 630 (2022) 118467
Contents lists available at ScienceDirect
Applied Catalysis A, General

journal homepage: www.elsevier.com/locate/apcata
Synthesis, characterization and application of Fe-zeolite: A review

Jie Zhang a, Xiaolong Tang a, b, Honghong Yi a, b, Qingjun Yu a, b, *, Yuanyuan Zhang a,
Jinghui Wei a, Yuting Yuan a
a
Department of Environmental Science and Engineering, School of Energy and Environmental Engineering, University of Science and Technology Beijing, Beijing 100083,
China
b
Beijing Key Laboratory of Resource-Oriented Treatment of Industrial Pollutants, Beijing 100083, China
A R T I C L E I N F O A B S T R A C T
Keywords: Fe-zeolites are widely applied in petrochemical, fine chemical, environmental protection, and other catalytic
Fe-zeolite fields because of the zeolitic properties as well as the redox properties endowed by the introduction of Fe species.
Fe species After being introduced into the zeolitic framework, the poor properties of traditional aluminosilicate zeolites, i.
Iron valence state
e., lack of active sites, low catalytic activity, poor anti-coking performance, etc., could be effectively improved.
Properties
The state of Fe species in zeolite, which significantly affects the properties (stability, acidity, redox properties,
Application
etc.) of Fe-zeolite, was determined by both the introduction methods/conditions and the properties (porosity /
acidity, etc.) of zeolite. From this point of view, a clear understanding of the structure-activity relationship of Fe-
zeolite is an important prerequisite for designing functional materials as necessary. Therefore, in this review,
recent developments on the synthesis, properties as well as the application of Fe-based zeolites were briefly
summarized. In detail, the factors affecting the recognition of types as well as the distribution of Fe species in Fe-
zeolites and the effects of the introduction of Fe on the physicochemical properties & catalytic performance of
zeolites are systematically clarified. Then, the applications of Fe-zeolite in chemical industry and environmental
engineering were reviewed and outlooked. This review is expected to provide theoretical reference for the
structural design and application of Fe-based zeolites in the future.
1. Introduction bond (average bond length 1.61 Å), Al-O bond (average bond length
1.75 Å) and P-O bond (average bond length 1.54 Å). Traditional zeolite
Zeolites, as a kind of inorganic microbes (pore size ＜ 2 nm) crystal is a three-dimensional reticular crystal connected by [AlO4] tetrahedron
materials [1] with regular pore structure connected by TO4 tetrahedron and [SiO4] tetrahedron via a common oxygen bridge, and its structure
through shared vertices, exhibit excellent properties such as thermal and follows the Lowenstein rule [2]. As the primary structural units of the
hydrothermal stability (700–1300 ◦ C), acidity, diffusion and adsorption, zeolite skeleton, these [SiO4] and [AlO4] tetrahedrons will connect with
shape selectivity, catalytic activity and ion exchange performance each other by sharing oxygen atoms to form multiple rings as the sec
because of their unique pore structure and highly crystalline framework. ondary structural units, which will be connected to each other in
The superior properties make zeolites widely applied in the fields of three-dimensional space to form a zeolite cage structure. Through
adsorption and separation, ion exchange and catalysis, such as petro further interconnection and regular arrangement, zeolite crystals with
leum processing, coal chemical industry, fine chemical industry, and three-dimensional framework are formed. The substitution of Al3+ iso
environmental protection, etc. morphs for Si4+ in the zeolite framework results in a negative charge in
Zeolite framework T atom usually refers to Si, Al, or P atoms (the the zeolite lattice, so the aluminosilicate zeolite composed of [SiO4]- and
silicoaluminate zeolite contains silicon & aluminum element, while [AlO4]- tetrahedron presents negative charge. To keep the framework
aluminophosphates zeolite contains phosphorus & aluminum element), structure electrically neutral, cations i.e., Na+, H+, K+, Ca2+, etc.) are
and appears in the form of high valence oxidation state. Through sp3 needed to balance negative charges [3]. When hydrogen proton presents
hybrid orbital, T atom could combine with oxygen atom to form Si-O as equilibrium cations in the framework of zeolites, Brønsted acid sites
* Corresponding author at: Department of Environmental Science and Engineering, School of Energy and Environmental Engineering, University of Science and
Technology Beijing, Beijing 100083, China.
E-mail address: [email protected] (Q. Yu).
https://doi.org/10.1016/j.apcata.2021.118467
Received 17 August 2021; Received in revised form 1 December 2021; Accepted 16 December 2021
Available online 18 December 2021
0926-860X/© 2021 Elsevier B.V. All rights reserved.
J. Zhang et al. Applied Catalysis A, General 630 (2022) 118467
will be formed, which make zeolites widely used as solid acid catalysts in 2. Overview of Fe-zeolites
various reactions [4].
The traditional aluminosilicate zeolite has the characteristics of Fe-zeolites refer to the introduction of iron element with variable
strong acidity and hydrophilicity, which limit its application in weak valence characteristics into the aluminosilicate or phosphoaluminate
acidity and humid environment. For example, for the reactions that do framework of zeolite to partially replace Si or Al or P, aiming to create
not require strong acid sites, such as in the conversion of methanol to a new catalytically active sites, regulate and improve catalytic perfor
mixture of ethylene, propylene and butene, the strong inherent acidity mance. Some main microporous zeolites are reviewed in this paper.
endowed by aluminum-related protons leads to both poor catalytic ac Such as FAU [14–20], *BEA [21–24], FER [22,25–27], MFI [22,28–34],
tivity and selectivity to the desired product [5,6]. In addition, the MEL [9,11,35], etc. (All 3-letter codes of Zeolites are available on this
bridged Si-OH-Al group related to the framework Al can strongly bind to website: http://www.iza-online.org/). The Fe species could exist in the
water, while the Si-OH group located on the external surface of the forms of single atom (only Fe [36]), double heteroatom (bimetal doping
zeolite as well as that connected with the extra framework Al can adsorb of Fe and other metals [37]), triheteroatom (co-doping of Fe and other
any polar compounds (i.e., methanol, methyl ethyl ketone and water) two metals [38]), etc. Generally, after being introduced into zeolite with
[7]. microporous porosity, the geometric position of different Fe species in
In order to overcome the disadvantages brought by traditional different zeolite supports is variable with the introduction methods
aluminosilicate zeolite, heteroatom isomorphism is usually used to (Table 1), including tetrahedral or octahedral coordinated isolated iron
replace the framework elements (Si, Al) of zeolites to modify zeolite, ions in the zeolite skeleton, small oligomeric iron oxide clusters or iso
which is also considered to be an effective way for the modification of lated iron ions in the channels, unsaturated iron species or octahedral
zeolites, which is also considered to be an effective way to improve the coordinated isolated iron ions on the outer skeleton, and iron oxide
hydrophobic adsorption and catalytic performance of zeolites [8]. The nanoparticles on the outer surface (Fe2O3, FeOx, etc.). Except for the
heteroatoms that can be introduced into the zeolite framework include introducing methods, the loading amount of iron, the structure &
the main group metals with variable valence (As, Ga, Sn, etc.), non properties of zeolite, the preparation parameters and calcination con
metals (B, C, etc.) and transition metals (Ti, Fe, Cu, Mn, W, etc.). Among ditions, etc., will also affect the existence state and distribution of iron
them, oxides formed by transition metal elements have become sub species in zeolite, which will affects the physical and chemical proper
stitutes for precious metal catalysts because of their halogen resistance, ties of Fe-zeolites, i.e., crystal morphology, pore properties, acidity,
low cost, high catalytic activity, and selectivity. Therefore, the intro hydrophobicity, thermal stability and redox properties, and these finally
duction of transition metal elements into zeolites can give them catalytic result in the variation of adsorption and catalytic performance of
oxidation properties in addition to their inherent properties provided by Fe-zeolites in various reactions.
the zeolitic framework. Compared with Mn, V, Cu, Co, Ni and other
transition metal elements, Fe has been proved to be more easily involved 3. Distribution and identification of Fe species
in zeolite framework [9,10]. Especially using + 3 valence Fe source, it
was found that Fe3+ could behave similarly to Al3+, and therefore As was summarized above, for most Fe-zeolites, the iron species in
disperse into the zeolite framework relatively well [11]. In addition, the zeolites are mainly present in the form of isolated iron species (mono
substitution of Fe to Al in zeolitic framework also endows MEL zeolite nuclear or binuclear oxygen-bridged iron species), oligomeric iron oxide
better hydrophobicity and catalytic oxidation performance, which clusters (Fe2O3, FeOx) and iron oxide nanoparticles (Fe2O3, Fe3O4, etc.)
makes it a potential adsorption-catalytic oxidation bifunctional material [33], which generally locate in the framework, pores, extra framework
for the purification of complex VOCs in wet environment (i.e., VOCs and external surfaces of zeolites. For each type of Fe species, there are
from Cooking Oil Fumes). Zhang et al. [12] also introduced Fe, K, Ga, several different structures. For example, there are mainly four different
Mg, Ni and other metals into ZSM-5 via a traditional wet impregnation structures of the isolated Fe species(Fig. 1), including framework Fe
method. It was found that the Fe-modified ZSM-5 exhibited both high species (I), extra framework Fe(II) species bounded to ‘silicon hydroxyl
olefin yield (2.7 wt%) and high aromatics yield compared with other nests’, mononuclear Fe species coordinated with extra framework Al
metal-modified ZSM-5 in the rapid pyrolysis of biomass to produce (III) and Fe species (IV) at cation exchange sites [39].
renewable aromatics and olefins. Maurya et al. [13] encapsulated Cr The existence state as well as distribution of Fe species in zeolite
(III), Fe(III), Bi(III), Ni(II) and Zn(II) complexes in Y-zeolite by flexible needs to be identified via a series of characteristic techniques, i.e., X-ray
ligand method, in which Fe(III) showed significantly higher yield of powder diffraction analysis (XRD), Fourier-Transform Infrared Spec
catechol (16.5%) and hydroquinone (6.5%) than the other elements in troscopy (FTIR), Scanning Electron Microscopy (SEM), Scanning trans
phenol hydroxylation. All these studies showed that as Fe could be more mission electron microscopy (STEM), Nitrogen adsorption-desorption
easily involved in the zeolitic crystallization process compared with experiments (BET), Thermogravimetric and differential thermal analysis
other transition metal elements, and the finally formed framework Fe (TG-DTA), Mössbauer spectroscopy, Electron Paramagnetic Resonance
and extra-framework Fe endow the zeolite with good hydrophobicity, (EPR), Ultraviolet–visible spectroscopy (UV–vis), X-Ray photoelectron
acidity and redox properties, exhibiting excellent performance in many spectroscopy (XPS), Temperature-programmed reduction of H2 (H2-
reactions. TPR), Ammonia temperature-programmed desorption (NH3-TPD) etc.
It is worth noting that parameters such as introduction methods, The characterization methods and their function in characterizing &
metal sources as well as the incorporated conditions directly affect the recognizing the Fe species in zeolites were summarized and listed in
type, distribution and existing forms of Fe species in zeolites, all of Table 2.
which will influence the hydrophobicity, acidity and catalytic oxidation
performance of zeolites. Clarifying these factors is an important pre 3.1. Structural analysis of Fe-zeolite
requisite for the precision design of Fe-based catalytic materials with
high performance as required. Hence, this review paper covers the XRD characterization technique is commonly applied to determine
structure, properties and the influencing factors affecting Fe species and analyze the crystalline phase, composition, crystallinity, and peak
distributed in zeolite crystals. Beyond these contents, the recent ad offset of synthesized zeolite product [68]. For the detection of Fe species,
vances of Fe-zeolite applied in chemical industry and pollutants abate only when Fe loads were greater than 5 wt%, the diffraction peaks of
ment were also summarized. α-Fe2O3 species can be observed at 2θ of 33.2◦ and 35.5◦ [44]. When Fe
loading was less than 5 wt%, which was below the detection limit for
powder X-ray diffraction analysis (load ＜ 5%) [40,41], no diffraction
peaks of α-Fe2O3 species were observed. In addition, if iron oxide
2
Table 1
Summary of the distribution of Fe species in various zeolite via different introduction methods & the application.
Fe- Introduction methods Existence state/distribution of Fe species Application
zeolite
Fe-X Wet impregnation method 2–6 wt%: Iron oxide clusters & isolated iron ions / uniform distribution Complete oxidation of dioxane [14]
> 6 wt%: Large iron oxide species / surface
Ion exchange method Fe(II) ions / zeolite pores Construction of electrochemical sensor based on iron-
doped carbon paste electrode (CPE) [15]
Fe-Y Wet impregnation method Fe(II) and Fe(III) species / surface or internal pores Catalytic degradation of Acid Red B (ARB), an Azo Dye in
Fe(II) and Fe(III) nanoparticles / surface Water [17]
Ion exchange method Isolated Fe(III) / framework Catalytic degradation of Acid Red B (ARB), an Azo Dye in
Octahedral coordination Fe(III) ions / framework Water [19]
Oligomeric Fe(III)xOy clusters & Fe2O3 species / surface Photocatalytic decolorization of Methyl Green [18]
Fe(II) ions / zeolite pores Catalytic decomposition of N2O [20]
Polypyridine ligand method Large metal complexes & a small amount of uncoordinated Fe(III) / Catalytic oxidation of styrene, cyclohexene, limonene
(flexible ligand method) super cage and α-pinene [16]
Uncoordinated ligands & complexes / surface
Fe- Wet impregnation method Most isolated Fe(II) ions / extra framework site Catalytic decomposition of N2O [22]
*BEA Fe(III) and Fe(II) iron oxide particles / surface Advanced oxidation process (AOPs) [21]
Small Fe2O3 clusters & octahedral coordinated Fe(III) species / extra-
framework
Two-step post-synthesis method Tetrahedral coordinated or octahedral coordinated Fe(III) species /
framework
Iron oxide species / extra-framework
Incipient wetness impregnation Tetrahedral or octahedral coordinated Fe(III) ions / framework Oxidation reactions of toluene [23]
Fe(III)xOy clusters / non framework
Fe2O3 particles / non framework
Ion exchange method Tetrahedral or octahedral coordinated Fe(III) ions / framework Oxidation reactions of hydrocarbons (methane, toluene
Isolated Fe(II) ions / coordinated to the zeolite framework and ethanol) [24]
Fe(III)-oxo species (dinuclear, polynuclear, larger oligomers)
FexOy oligomers
Fe-FER Wet impregnation method Isolated Fe(II) ions / extra-framework Catalytic decomposition of N2O [22]
Iron oxide particles (Fe(III) and Fe(II)) / surface
Incipient wetness impregnation Small Fe & FeOx clusters / extra-framework Oxidation reactions of hydrocarbons [25]
method Fe(III) ions / framework
Oligomeric Fe clusters / extra-framework
(FeOx) clusters / extra-framework
Liquid ion exchange method Isolated Fe(III) ions / framework Oxidation of methane with N2O [26]
Isolated & oligomeric Fe species / extra-framework
FexOy clusters & large Fe2O3 particles
Hydrothermal synthesis Tetrahedral coordinated Fe(III) ions / framework Hydroxylation of phenol with hydrogen peroxide [27]
Fe(III) & Fe(II) ions / extra-framework
Fe-MFI Wet impregnation method Fe(III) and Fe(II) iron oxide particles / surface Oxidative dehydrogenation of glycerol to acrolein and
Isolated Fe(II) ions & octahedral coordinated isolated Fe(III) ions & acrylic acid [28]
iron oxide species / extra-framework
Incipient-wetness impregnation Isolated Fe(III) ions coordinated by tetrahedron or octahedron / Selective liquid phase dehydration of 1-phenylethanol
method framework (PHE) [33]
Hydrothermal synthesis Isolated Fe(III) ions coordinated by tetrahedron or octahedron /
framework
Small oligomeric iron oxide clusters / channel FeOx nanometer
particles / surface
Tetrahedral coordinated isolated Fe(III) ions / framework Oxidative dehydrogenation of glycerol to acrolein and
A small amount of octahedral coordinated Fe(III) ions / extra- acrylic acid [28]
framework
Post-synthesis treatment in Tetrahedral coordinated isolated Fe(III) ions / framework
fluorinated medium A small amount of octahedral coordinated Fe(III) ions /extra-
framework
Ion exchange method Octahedral coordinated isolated Fe(III) ions and iron oxide species / Oxidative dehydrogenation of propane with nitrous
extra-framework oxide [32]
Isolated Fe ions coordinated by tetrahedron or octahedron oligomeric
iron oxide clusters Fe2O3 nanometer particles / surface
Dry gel conversion method (DGC) Isolated Fe ions & Oligomeric FexOy clusters & Fe2O3 nanometer Catalytic hydroxylation of phenol [31]
particles
Hydrothermal synthesis Tetrahedral coordinated isolated Fe(III) ions / framework Catalytic hydroxylation of phenol [30]
Tetrahedral coordinated isolated Fe(III) ions / channel Photocatalytic hydroxylation of phenol [29]
Small oligomeric FexOy clusters (Fe2O3) / surface
Chemical vapour infiltration (CVI) Mono & di-Fe species / extra-framework Oxidation reactions of hydrocarbons [34]
Iron oxide clusters
Tetrahedral coordinated isolated Fe(III) ions / framework
Fe-MEL Ion exchange method Tetrahedral coordinated isolated Fe(III) ions / framework Methylation of mxylene with methanol [35]
Crystallization process control Tetrahedral coordinated isolated Fe(III) ions / framework VOCs removal from
method Iron oxides species / surface cooking oil fumes by either adsorption method or
catalytic oxidation [9,11]
3
Fig. 1. The schematical illustration of four various isolated Fe species in Fe- zeolite [39].
microcrystals possess very small particle size less than 4 nm [14,72] or morphology, grain size, thickness and so on [86]. Galina et al. [86]
in high dispersion state in the zeolite carrier [40,42,43], the XRD peak described the morphological characteristics of fresh and aged Fe-FER
signals about Fe species are also missing and no conclusions could be zeolites prepared by wet impregnation by SEM characterization. Both
drawn. fresh and aged Fe-FER zeolites showed the same typical flake
FT-IR is generally used to characterize the structure of adsorbed morphology, with an average particle size of 500 nm and a thickness of
species, adsorbent-adsorbent interaction, reaction mechanism and about 20 nm ~ 30 nm, indicating that the aging process does not change
acidic property by detecting the bond type and connection mode be the morphology characteristics. The morphology changes of Fe-zeolite
tween various functional groups or atoms [45,46]. When iron is incor compared with conventional aluminosilicate zeolite could also provide
porated into silicate framework, the bands at 660 and 960 cm− 1 are evidence for the incorporation of Fe into the zeolite framework. Adel
attributed to Fe-O-Si species. With the increase of iron content, the et al. [29] characterized MFI, Fe-MFI, Fe-Al-MFI (0.5) and Fe-Al-MFI (1)
adsorption peak in 960 cm− 1 caused by the stretching vibration of zeolites synthesized by one-step hydrothermal method (the amount of
Si-O-groups on the surface gradually disappears, the adsorption peak of Fe2O3 in the gel composition is 0.5, 1 mol). Compared with the MFI with
about 1080 cm− 1 gradually broadens, indicating the formation of homogeneous microcrystal diameter of 0.5–0.7 µm & nanocrystals of
Fe–O–Si bond, which is mainly due to the fact that the distance of Fe-O 25–100 nm, Fe-MFI shows the non-uniform microcrystal size of
bands (1.84 Å) is longer than that of Si–O bonds(1.61 Å), indicating Fe 0.9–1.3 µm composed of circular nanocrystals with rectangular pris
is located at zeolite framework sites. In the stretching region of OH matic. In addition, different from the Fe-Al-MFI (0.5) with microcrystal
group, compared with the position (3620–3600 cm− 1) of the broader diameter of 0.6–0.8 µm & nanocrystals of 30–150 nm, Fe-Al-MFI (1)
lower band corresponding to acid bridged Si-OH-Al in the internal presents spherical and layered nanocrystals with size of 180–240 nm
cavities [85], the position of the band corresponding to the bridged Si (Fig. 3).
(OH)Fe group as Brønsted sites is at 3630 cm− 1 [49], and the intensity of The STEM carries out raster scanning imaging the sample by focusing
the infrared adsorption peak corresponding to the Bronsted acid hy probe [46]. It is a very powerful tool to qualitatively characterize the
droxyl group is obviously reduced, which indicates most of the protons microstructure and nanostructure of materials and their morphological
in the Brønsted acid hydroxyl group are replaced by cationic iron [32], characteristics and element distribution, as well as the particle size
and the Brønsted acid sites related to framework iron atoms are essen distribution of metal nanoparticles and local chemical composition [9,
tially weaker than those related to Al atoms [49]. Also, when NO2 was 11]. Sebastiano et al. [87] used HRTEM and HAADF-STEM microscopy
introduced, the band at 3675 cm− 1 was attributed to the OH group combined with Energy-dispersive X-ray spectra (EDX) to investigate the
connected to the ion-exchanged Fe3+(Fe-OH). The band decreases in the morphology and structure of Fe-ZSM-5 prepared by ionic exchange (I.
process of NO2 adsorption, but disappears after high temperature E.), denoted as Fe/ZSM5IE. HRTEM shows that the Fe/ZSM5IE catalyst
emptying or H2 treatment [47]. In addition, the interaction between has a defined shape of zeolite microcrystals with a grain size of about
ion-exchanged Fe3+ and some adsorbates derived from NO2 or NO2 will 0.3–3 µm. The HAADF-STEM/EDX element diagram shows that the iron
change the oxidation state of iron or the coordination structure around atoms are highly uniformly dispersed with the presence of silicon and
the iron center, resulting in a lower frequency shift of the perturbed aluminum atoms in the zeolite support, which indicates that the loaded
band from 920 to 905 cm− 1 [47]. Xiao et al. [60] characterized the iron is adsorbed within the zeolite pores (Fig. 4). STEM can also be used
coordination unsaturated Fe species on the extra framework of Fe-MFI to measure the particle size distribution of metal nanoparticles in zeo
with different Si/Fe ratios, designated as FSDx (x = Si/Fe), synthesized lites. For Fe nanoparticles impregnated with hollow zeolites, STEM
by direct hydrothermal synthesis by means of NO adsorbed FT-IR characterization technology can determine whether Fe nanoparticles are
technique. It was found that the bands are mainly centered at located at the cavity or surface of zeolites [46].
1867 cm− 1, which are mainly attributed to Fe2+(NO) and Fe3+(NO)
complexes. With the increase of NO pressure, new bands appeared at
1915 and 1809 cm− 1 & at 1840 and 1765 cm− 1, which were assigned to 3.3. Textural properties analysis of Fe-zeolite
Fe2+(NO)3 and Fe2+(NO)2 species, respectively (Fig. 2).
The introduction of Fe into zeolite often causes the variation of
textural properties, such as porosity, pore type, micropore surface area
3.2. Morphology and Fe distribution analysis and micropore volume of zeolite, which can be characterized by low
temperature N2 adsorption-desorption experiment [39]. Zhang et al.
The morphology of zeolites can be shown via SEM images. SEM is an [33] calculated the specific surface area (SBET) and micropore volume
instrument 84, that uses electrons instead of light waves to produce a (VMicro) of a series of Fe-MFI zeolites with different Fe/Si molar ratio by
large number of magnified images, which is used to characterize micro- N2 adsorption-desorption isotherms. Compared with the MFI with SBET
4
Table 2
Various characterization methods & function in recognizing Fe species in zeolite.
Characterization Function Characteristic peak/signal of species
technology
Species Characteristic peak/signal
XRD Crystalline phase/composition/crystallinity/structures [14, > 5 wt% Fe: α-Fe2O3 [40,44] 2θ = 33.2◦ , 35.5◦
40–43]
FTIR Structure of adsorbed species/adsorbate-adsorbent interaction/ Fe-OH 3675 cm− 1 [47]
reaction mechanism/acidity properties [45–48] Bridged Si(OH)Fe 3630 cm− 1 [49]
Perturbed band of the internal 920–905 cm− 1 [47,48]
asymmetric T-O-T by Fe
1
Fe-O-Si 660 and 960 cm−
STEM Microstructure and nanostructure /morphology /element Thicker/heavier metal nanoparticles of Darker areas
distribution /particle size distribution of metal nanoparticles the catalyst.
/local chemical composition [9,11,46] Light beams can pass through. Shallower areas
N2 adsorption and Porosity/pore type/micropore area/total pore volume/average Micropores 107＜P/P0＜102 adsorption
desorption pore diameter/specific surface area [11,39] Mesoporous/macroporous P/P0 = 0.4–1.0 adsorption
Characteristics of micropore structure Type I isotherm
Characteristics of mesoporous structure Type IV isotherm with hysteresis loop
TG-DTA Decomposition temperature of zeolite template/framework TG Loss of surface water to judge < 200 ◦ C weightlessness
thermal stability [9,11] curve hydrophobicity.
Decomposition of zeolite 350–550 ◦ C weightlessness
organic template.
Collapse of zeolite framework. 550–700 ◦ C weightlessness
DTA Decomposition of template Strong exothermic peak at 350 ◦ C~ 550 ◦ C
curve molecules in zeolite
micropores.
Incorporated metal oxidation Extra peak at 400 ◦ C
state
Mössbauer Valence/phase/spin configuration/coordination environment Fe(III) ions with tetrahedral 0.1 ≤IS≤ 0.3 mm/s &
of iron [50–55] coordination 0.87 ≤QS≤ 1.24 mm/s
Framework substituted Fe(III) 0.25 <IS< 0.27 mm/s & QS (1.2–1.5 mm/s)
Small FexOy nanoparticles in the 0.3 ≤IS≤ 0.37 mm/s &
Octahedral coordination with 0.65 ≤QS≤ 1.06 mm/s
superparamagnetism
Intervalent states of dinuclear Fe-O-Fe IS< 1.0 mm/s
pairs.
α-Fe(II) (Fe(II) located in cationic δ = 0.89 mm/s&∣ΔEQ∣= 0.55 mm/s
positions α or β)
N2O-ligated high-spin Fe(II) δ = 1.09 mm/s&∣ΔEQ∣= 1.53 mm/s
Fe(II) ions 0.7 ≤IS≤ 1.4 mm/s
EPR Free radicals/coordination environment /iron species of Highly symmetrical isolated Fe(III) ions g′ ≈ 2.0 [32,57]
different coordination geometries and aggregation degrees [46, and / or small FexOy oligomers with
56] weak dipole coupling
Tetrahedral coordinated ferric ions g′ ≈ 4.3 [58,59]
UV–vis Coordination of ions with surface oxygen/quantification of Isolated Fe(III) & Fe(II) ions with 200–300 nm [64,65]
oxidation states of metal ions/distribution of metal ions in different coordination states
zeolites [60–63] Tetrahedral coordinated isolated < 250 nm [59]
framework Fe(III) ions
Isolated Fe(III) and oligomeric Fe species 250–350 nm [60]
on the extra framework
Isolated Fe(III) ions with Octahedral 285 nm [65]
coordination
Oligomeric FexOy clusters 300–450 nm [66]
Inner surface oligomeric Fe(III)xOy 335 nm [66]
clusters
Outer surface oligomeric Fe(III)xOy 385 nm [66]
clusters
Large FeOx particles > 450 nm [65,66]
External surface Fe2O3 nanoparticles 460 nm and 550 nm [67]
(~1 nm)
XPS Chemical composition and state/coordination relationship Fe(III) ions Fe 2p1/2: around 725 eV [68–71]
between metals and zeolites/qualitative analysis of iron species Fe(II) ions Fe 2p3/2: around 711 eV [68–70]
[68–71] Pure iron oxide Fe 2p3/2 peak: around 710.8 eV & Fe 2p1/2
peak: around 724.2 eV [69,71]
Fe2O3 phase Main Fe 2p3/2 peak: 710.6 ~ 711.2 eV &
satellite Fe 2p3/2 peak: 718.6 ~ 719.2 eV
[71]
Fe3O4 phase Fe2p3/2 peak: 710.6 eV(S.D.=0.05) &
Fe2p1/2 peak: 724.1 eV (S.D.=0.07) [71]
H2-TPR Redox properties of iron species [72–74] Fe(III) (isolated Fe(III), FexOy, α-Fe2O3 327–377 ◦ C
nanoparticles) reduced to Fe(II) (in
cation or oxo-cations)
Extra-framework Fe(III) to Fe(II) 350–500 ◦ C
Framework Fe(III) to Fe(II) 500–640 ◦ C
FeO into Fe0 427–627 ◦ C
Fe(II) to Fe0 with collapse of the zeolite ＞827 ◦ C
framework
(continued on next page)
5
Table 2 (continued )
Characterization Function Characteristic peak/signal of species
technology
Species Characteristic peak/signal
NH3-TPD Acidic sites/strength/types of acid sites [75–80] Peak of Brønsted acid site ＞350 ◦ C [76,77]
Peak of Lewis acid site ＜200 ◦ C [78]
Weak acid site (Lewis acid sites and 100–200 ◦ C [79–81]
weakly physical adsorbed NH3)
Moderately strong acid site (Brønsted 350–400 ◦ C [80,82]
acid sites)
Strong acid site (Brønsted acid sites) 400–600 ◦ C [83,84]
paramagnetic resonance (EPR) spectroscopy, often referred to as elec

tron spin resonance (ESR), is another highly sensitive tool to charac
terize the environment of free radicals and transition metal ions in
zeolite zeolites [46]. The conclusions obtained are summarized in
Table 2. For Fe-zeolites, g′ = 2.0 EPR signals corresponds to highly
symmetrical isolated iron ions and/or small FexOy oligomers with weak
dipole coupling [57]. In the zeolite containing only isolated Fe, this
signal corresponds to a highly symmetrical position. g′ = 4.3 EPR cor
responds to tetrahedral coordinated isolated Fe3+ species. Gao et al. [88]
study the Fe/SSZ-13 catalysts with different iron loading (0.27 ~ 1.2 wt
% Fe) synthesized by ion exchange method by means of EPR charac
terization. It is found that there are g′ = 8.8, 6 and 4.3 at low-field, while
g′ = 2.3 and 2 at high field (Fig. 5), in which the g′ = 8.8, 6, 4.3 and 2.0
belong to isolated Fe3+ species, while the g′ = 2.3 attributed to the FexOy
clusters (Fig. 5 A). In addition, the linear shapes of EPR spectra with
different Fe loads are very similar, indicating that they have similar
active iron species distribution.
Fig. 2. FT-IR spectra of NO adsorbed on Fe-MFI: (a) FSD100, (b) FSD50, (c) The oxygen-metal charge transfer band in UV–vis can characterize
FSD25, (d) FSD15 [60]. the coordination state and aggregation degree of iron ions, which is a
direct method to characterize whether Fe was incorporated into the
of 458 m2/g & VMicro of 0.171 cm3/g, the larger SBET and smaller VMicro zeolitic framework or not [7]. In the UV–vis spectra of the Fe-zeolite,
are observed in Fe-MFI zeolites, which are 479 ~ 500 m2/g and 0.125 ~ generally, the bands at 200–300 nm assigned to the isolated attributed
0.135 cm3/g, respectively. Also, with the increase of Fe/Si ratio, from to Fe(III) or Fe(II) ions with different coordination states. Also, the bands
0.005 to 0.025, the specific surface area (SBET) of Fe-MFI gradually at 250–350 nm correspond to the isolated and oligomer iron species on
decreased, while the VMicro gradually increased. the extra-framework. In addition, the bands at 350–450 nm are attrib
uted to oligomeric iron oxide clusters, and the bands related to the bulk
3.4. Incorporation and state of Fe in zeolite iron oxide particles are above 450 nm, of which the bands at 460 and
550 nm are attributed to external surface Fe2O3 nanoparticles (~ 1 nm)
The existence state and distribution of Fe species in zeolite can be [89]. Fe-ZSM-5 and Fe-silicalite-1 zeolites with 0.5 wt% iron loading
determined by EPR, Mössbauer, UV–vis and so on. Electron and SiO2/Al2O3 molar ratio of 84 were synthesized by hydrothermal
Fig. 3. SEM images of MFI zeolite and its modified counterparts: (A) SEM images of MFI zeolite, (B) SEM images of Fe-MFI zeolite, (C) SEM images of Fe-Al-MFI(0.5)
zeolite, (D) SEM images of Fe-Al-MFI(1) zeolite [29].
6
Fig. 4. STEM measurements of Fe-ZSM-5IE: HAADF image of a catalyst grain (left side). STEM-EDX element mapping (right side) of the catalyst showing the silicon
(blue), aluminum(green) and Fe (red) maps [87]. (For interpretation of the references to colour in this figure, the reader is referred to the web version of this article.)
Fig. 5. (A) EPR spectra of Fe/SSZ-13 with different Fe loadings at125 K. Effective g factors are marked adjacent to the spectra [88]. (B) UV–vis spectra for 0.5Fe-s
ilicalite-1(84) (blue/solid) and 0.5 Fe-ZSM-5 (84) (red/dashed) both calcined at 550 ◦ C in air 90. (C) Mössbauer spectra of the ambient 57Fe/SSZ-13 samples
measured at 8 K, and are displayed with different colors. Spectra are shifted vertically [88]. (D) Peak fitting results of the Fe 0.27% 57Fe/SSZ-13 sample. Percentages
of Fe(II)-P, Fe(III)-P, and Fe(III)-M are also displayed [88].
synthesis, recorded as 0.5 Fe-ZSM-5 (84) and 0.5 Fe-silicalite-1 (84) the same identical activation process (550 ◦ C, 3 h in air), indicating that
[90]. It is found that, compared with 0.5 Fe-silicalite-1, the absorbance more extensive Fe3+ species migration has taken place in 0.5 Fe-ZSM-5
above the wavelengths of 250 nm in 0.5 Fe-ZSM-5 (84) increases after (84) (Fig. 5B). UV–vis characterization technique can be used to
7
characterize not only the coordination state of iron species but also the pyramidal, high-spin Fe(IV)), which is characterized by δ = 0.30 mm/s
aggregation degree of iron species. Miyake et al. [6] synthesized Fe-MFI and quadrupole splitting |ΔEQ | = 0.5 mm/s. And they also evaluated
with a crystal size less than 100 nm by dry gel transformation (DGC) the α-Fe and α-O species in detail and described α-Fe catalyzes the cycle
method. It was found that there were sharp adsorption peaks at 200 ~ for benzene hydroxylation to phenol catalysed by α-Fe using Mössbauer
300 nm at 6 h, 12 h and 24 h in the UV–vis spectra of the Fe-MFI, which spectroscopy (Fig. 6). It was found that α-O converts nearly quantita
was attributed to the transformation of Fe species from Fe-O-Fe extra- tively into a high spin (S = 2) Fe(II) site (α-C6H6, blue species in Fig. 6)
framework to isolated dispersed structure within the MFI framework that is distinct from α-Fe(II). The phenol product is released from the
after 6 h. active site over the course of single turnover, regenerating α-Fe, and
Mössbauer is an effective technique for the study of metal-zeolites by closing the catalytic cycle [53].
measuring the hyperfine interaction between nuclear moments and When quantifying iron species in Fe-zeolite by means of Mössbauer
electromagnetic fields [51], which is used to distinguish the forms of and UV–vis spectroscopy, UV–vis is sensitive to dispersed structure,
iron species and to provide reliable information on the environment while Mössbauer spectrum is sensitive to large aggregates. Masaoki et al.
where iron ions exist [50], which is helpful to identify active centers, [48] found that α-Fe2O3 is the main species in Mössbauer results, while it
characterize mesophase and study the relationship between catalyst is the secondary in UV–vis results. The reason for this difference is
structure and catalytic performance [53]. Pál et al. [91] determined the because the surface sensitivity of large α-Fe2O3 particles leads to the
oxidation state and iron environment of iron species in Fe-ZSM-5 zeo underestimation of their effects by UV–vis spectra. On the other hand,
lites prepared by sol-gel synthesis by in situ 57Fe Mössbauer spectros Mössbauer spectra tends to overestimate α-Fe2O3, because the Debye
copy characterization. The appearance of Fe components with 0.1 ≤ IS temperature of α-Fe2O3 particles is significantly higher than that of
≤ 0.3 mm/s and 0.87 ≤QS ≤ 1.24 mm/s is assigned for the presence of oxo-Fe3+ and oligomers, resulting in a decrease in the proportion of
tetrahedral coordination Fe(III) ions. Also, the other tetrahedral non-recoil adsorption. Therefore, to avoid drawing wrong conclusions
component with 0.25 < IS < 0.27 mm/s and QS (1.2–1.5 mm/s) is due to differences in the sensitivity of characteristic techniques, it is
assigned to framework substituted iron ions. Meanwhile, the Fe(II) ions necessary to combine various spectra to get the rational analysis of
component with 0.7 ≤IS≤ 1.4 mm/s value indicates intervalent states of materials.
dinuclear Fe-O-Fe pairs. In order to facilitate Mössbauer spectrum
measurement, Gao et al. [88] synthesized zeolites with 0.27 wt% iron 3.5. Redox properties of Fe-zeolite
loading using Fe-57 labelled FeSO4, which can be used to quantify all
possible iron species in Fe/SSZ-13 samples. It is found that in the The redox properties of zeolites can be characterized by XPS and H2-
unmodeled spectra of 557Fe/SSZ-13 samples (Fig. 5 C), although the TPR techniques. The chemical composition and chemical state of zeo
loads are different, the spectra are similar in properties, which are lites, the coordination relationship between metal species and zeolite,
mainly different from the relative contents of the doublet state (para and the qualitatively analysis of the redox iron species on the zeolite
magnetic state, P state) and the sextet state (magnetic state, M state). In crystal surface could be obtained by XPS analysis [68]. In the Fe 2p XPS
the fitting spectrum of the sample loaded with 0.27% Fe based on the spectra of Fe-zeolite, the peaks of Fe 2p1/2 and Fe 2p3/2 depend on the
Voigt fitting model, there are three Fe components: two doublets and a ion state of Fe. The satellite peak position is also very sensitive to the
sextet. And the components whose CS is about 1.4 mm/s can be assigned oxidation state, which can be used to qualitatively determine the ion
to Fe(II), while the other two components of CS ≈ 0.5 mm/s can be state of iron. In the same Fe-zeolite, Fe 2p binding energies increase with
assigned to Fe(III). According to their magnetism (P or M), the three the increase of iron loading, which makes the interaction between iron
components are named Fe(II)-P, Fe(III)-P and Fe(III)-M, and their per species and support stronger. The binding energy of the peak of Fe 2p1/2
centages are 35.2%, 15.4%, 49.4%, respectively (Fig. 5D). (around 725 eV) indicate the presence of Fe(III) ions, while the binding
The original definition of α- Fe(II) sites was defined by Panov et al.: energy of the peak of Fe 2p3/2 (around 711 eV) indicate the presence of
Fe capable of forming an active oxygen that oxidizes benzene (and Fe(II) ions [68–71]. When irons were incorporated into the silica
methane) at room temperature [92]. Panov et al. suggested under framework, the pure iron oxide (Fe 2p3/2 peak: around 710.8 eV & Fe
high-temperature calcination, iron released from the aluminosilicates 2p1/2 peak: around 724.2 eV) had a shift of about 0.8–1 eV, which may
and ferrisilicates framework of the ZSM-5 structure to the extraframe be attributed to the higher electronegativity of silicon than Fe [69,71].
work sites, resulting in the formation of Fe-related α-centers. Wichter Amel et al. [68] identified the chemical composition of three kinds of
lova et al. [64] determined the presence of extraframework Fe species at iron-based zeolites (Fe-Y, Fe-Omega, Fe-ZSM-5) prepared by hydro
cationic sites was indicated by perturbation of framework T-O-T bonds thermal method and the coordination relationship between Fe and ze
(the bands present in the region 1000–880 cm− 1) due to divalent cation olites by XPS spectra. The results showed that the binding energies
coordination. These extraframework dinuclear Fe species, formed by around 711 eV and around 725 eV correspond to Fe 2p3/2 and Fe 2p1/2,
high-temperature calcination, and bearing bridging oxygens are the which are related to Fe(II) ions and Fe(III) ions respectively (Fig. 7A). In
active sites for benzene hydroxylation with nitrous oxide and can cap addition, the different framework properties of zeolites with different
ture the atomic oxygen formed by N2O decomposition and transfer it to structures modified by iron lead to the change of the environment of Fe
benzene molecules significantly, resulting in improving the activity of species, which makes them have different binding energies. The binding
zeolite in the hydroxylation of benzene to phenol by Mössbauer spec energies of Fe-Y, Fe-Omega and Fe-ZSM-5 zeolites are around 710.9 eV,
troscopy by Panov et al.[53,93–96]. In addition, iron-exchanged zeolites 710.1 eV and 709.8 eV, respectively. The binding energy is mainly
stabilize an S = 2 square planar Fe(II) site (α-Fe(II)) that activates N2O, attributed to Fe(II) ions, which confirms the reduction of Fe(III) to Fe(II).
forming a highly reactive Fe(IV) = O intermediate (α-O) that is active in H2-TPR technique can be used to characterize the redox property of
the low-temperature hydroxylation of inert C–H bonds (for example, iron species and the existence of reducible iron species is revealed in
methane and benzene) [97]. Max L. Bols et al. [54] adopted Mössbauer some cases [47,73,98]. The hydrogen consumption in the temperature
spectroscopy to identify the N2O ligand α-Fe(II) complexes in Fe-*BEA range from 350 ~ 500 ◦ C is attributed to the reduction of extra frame
when tracking the state changes of α-Fe(II) active sites during N2O work Fe(III) to Fe(II) [73]. While the hydrogen consumption in the
binding intermediates and activation. The isomer shift of δ = 0.89 mm/s temperature range from 500 ~ 640 ◦ C is attributed to the reduction of
and quadrupole splitting |ΔEQ | = 0.55 mm/s is attributed to α-Fe(II) framework Fe(III) to Fe(II). In addition, the hydrogen consumption in
(mononuclear high-spin Fe(II)) site. When exposed to N2O, a single new the temperature range from 427 to 627 ◦ C is attributed to FeO reduction
component appears with an isomer shift of δ = 1.09 mm/s and quad to metallic iron (Fe0) in nanoparticles [72]. The hydrogen consumption
rupole splitting |ΔEQ | = 1.53 mm/s, characteristic of high spin (S = 2) in the temperature range > 827 ◦ C is attributed to the reduction of Fe(II)
Fe(II). After 30 min at 433 K, it is completely converted to α-O (square to metallic iron (Fe0) in isolated or oligomeric clusters with collapse of
8
Fig. 6. Cycle for benzene hydroxylation to phenol catalysed by α-Fe. The product of single turnover, α-C6H6, is indicated in blue. The phenol-ate poisoned active site,
generated in small quantities during single turn-over, is indicated in red [53]. (For interpretation of the references to colour in this figure, the reader is referred to the
web version of this article.)
Fig. 7. (A) XPS spectra of Fe modified zeolites: Fe 2p [68]. (B) H2-TPR of Fe-SSZ-13 zeolite [99].
the zeolite framework [20]. Niu et al. [99] characterized the existing high temperature peaks between 400 and 600 ◦ C are corresponding to
form and state of iron in Fe-SSZ-13 synthesized by hydrothermal method the strong acid center [83]. Thus the medium and strong acid sites can
by H2-TPR technique. From the intensity and area of H2 consumption be designated as Brønsted acid sites, and weak acid sites can be desig
peak (Fig. 7B), it can be seen that Fe-SSZ-13 has higher monomer and nated as Lewis acid sites and weakly physical adsorbed NH3.
oligomeric FexOy cluster content.
4. Factors affecting the species and distribution of Fe
3.6. Acidity of Fe-zeolite
4.1. Effect of introduction methods
NH3-TPD technology is usually used to characterize the acidic sites,
The methods of introducing Fe into zeolites include hydrothermal
acid strength and types of acid sites in zeolites [75]. The concentration
synthesis and post-treatment. The former mainly refers to the intro
of the acid site is expressed by the amount of ammonia desorbed in a
duction of Fe species before or during the formation of zeolite frame
given temperature range, and the temperature range with the largest
works, including the hydrothermal synthesis [101,102] dry-gel
amount of desorbed ammonia indicates the acid strength distribution.
conversion method (DGC) [6], etc. The post-treatment method means
The desorption of NH3 bound to Brønsted acid sites occurred above
that Fe was introduced into the well crystallized zeolite via impregna
350 ◦ C, while peaks at low temperature below 200 ◦ C are corresponding
tion method [103], ion exchange method [104], chemical vapor depo
to the desorption of weak binding NH3 on Lewis acid sites and weakly
sition method [48,105], etc. The dispersion of Fe on the zeolite support
physical adsorbed NH3 in the Fe-zeolite [3,47,78,100]. Generally, the
or into the specific position of the zeolite channel could be realized by
peaks in the temperature range of 100–200 ◦ C are corresponding to the
controlling the conditions of the treatment process. Except for the con
weak acid center [79]. The peaks in the temperature range of
ventional methods, in recent years, researchers have successively
350–400 ◦ C are assigned to the moderately strong acid center [80]. The
9
developed new methods such as green synthesis methods (including hydrothermal synthesis is one of the simplest and most common
using low-toxicity, cheap organic templates synthesis [99], free organic methods for the preparation of iron-based molecular sieves. Also, this
templates synthesis [106,107]), improved solvent-free synthesis [108], method has the advantages of fast reaction speed, high efficiency and
ion thermal synthesis [109], microwave-assisted synthesis [110], adjustable particle size of nano-sized catalysts. However, the hydro
two-step mechanochemical assisted synthesis [111], etc. The advan thermal synthesis of Fe-zeolites is usually carried out under alkaline
tages and disadvantages of the above introduction methods are sum conditions, so it is easy to form transition metal hydroxide precipitation,
marized and shown in Table 3. resulting in the uneven distribution of heteroatom species on the surface
Different synthesis methods will have a direct impact on the species or pores of zeolites. Generally, there are several different states of Fe in
and distribution of Fe species, which will affect the physicochemical zeolite by the direct hydrothermal synthesis, including isolated iron ions
properties and catalytic performance of the materials. Direct with tetrahedral or octahedral coordination in the zeolite frameworks,
small oligomeric iron oxide clusters or tetrahedral coordinated isolated
Table 3 iron ions in the channels, unsaturated iron species or octahedral coor
Comparison of various preparation methods of Fe-zeolites. dinated isolated iron ions on the extra-framework, and iron oxide
nanoparticles (Fe2O3, FeOx, etc.) on the surface [28–30,33,112–114].
Method Advantages Disadvantages Improvement
Required For instance, Zhang et al. [124] synthesized Fe-MFI by direct hydro
thermal method, denoted as Fe-S-1. And then prepared the hierarchical
Hydrothermal Fast reaction Harsh synthesis Shorten
synthesis speed. conditions. crystallization time. zeolites by post-treatment with tetrapropyl ammonium hydroxide
[28–30,33, High efficiency. Easy to form large Develop green (TPAOH), denoted as Fe-S-1-P (Fig. 8 A). It was found that all Fe-zeolites
112–114] Simple crystal domain and synthesis route. had isolated tetrahedral ferric ions at framework sites and isolated and
operation. extra-framework oligonuclear extra-framework iron clusters in the zeolite channels by
Adjustable species.
means of UV–vis characterization. However, compared with the
crystal size. Easily form
precipitates and Fe-S-1-P obtained by post-treatment (Fig. 8C), the Fe-S-1 had larger
impurities. extra-framework Fe cluster (Fig. 8B). Therefore, the percentages of
Long framework Fe in Fe-S-1-P (70.5%) is much higher than that in Fe-S-1
crystallization
(45.1%) calculated for the deconvolution of UV-Vis absorbance
time.
Impregnation Adjustable In the subsequent Cooperate with the spectra. Namely, more iron ions occupy the center of the Fe-S-1-P zeolite
methods [10, heteroatom treatment, the high corresponding framework, resulting in an increase of the content of Brønsted acid sites,
14,17,22,28, content on active iron species atmosphere which are mainly the active site of Fe-zeolites in PHE dehydration re
115–118] demand. may be treatment action. Specifically, the concentration of Brønsted acid sites in Fe-S-1 is
High loading. transformed into technologies (such as
15.886 μmol/g, while that of Fe-S-1-P is 36.431 μmol/g, so Fe-S-1-P with
low active iron NTP, microwave,
species. thermal field, etc.). more Brønsted acid sites showed higher reactivity in PHE dehydration
Poor dispersion. reaction.
Tedious operation. The impregnation method is a post-synthesis method, including wet
High cost.
impregnation and incipient-wetness impregnation method generally.
Ion exchange High dispersion. Poor load Optimize the
method [15, Uniformly controllability. preparation steps.
Compared with the direct synthesis method, the impregnation method
19,20,32,35, distributed. Limited iron Regulation the can more effectively incorporate iron atoms with larger radius than Si
119] Low cost. content. amount of metal and Al atoms into the zeolite framework, resulting in obtaining Fe-
Low repeatability. introduced. zeolites with higher iron loading [2]. Fe-zeolite obtained by impregna
Tedious operation. Improve the
tion method, and Fe generally exists in the form of in the form of iron
exchange degree and
exchange rate. oxide (Fe2O3, Fe3O4, etc.) nanoparticles on the surface or inside chan
Chemical vapor Reduce the use High cost. Optimize the nels of zeolites. However, compared with Fe-zeolites prepared by wet
deposition of organic Not easily realize preparation steps. impregnation, Fe-zeolites prepared by incipient-wetness impregnation
[48,105,120, templates. industrialization. Reduce the cost of
method have relatively smaller grain size and more dispersed distribu
121] Increase the High energy preparation.
yield of zeolites. consumption.
tion, most of the crystalline grain enter the channels of the zeolites, and
Improve atomic Produce corrosive there are isolated Fe(II) ions and octahedral coordination Fe(III) ions in
economy. HCl gas. the extra-framework [10,115–117]. While the crystalline grains size of
High dispersion. Fe-zeolites prepared by wet impregnation are larger, and the phenom
Solvent-free Avoid the Harsh synthesis Shorten
enon of particle agglomeration is more serious, most of which exist
method generation of conditions. crystallization time.
[6108] liquid waste. Higher Lower crystallization outside the channels. Namely, more particles exist on the surface of the
Eliminate crystallization temperature. zeolites, and only part of the crystalline grains enter the channels of the
completely the temperature. zeolites [10,14,17,22,28,115–118]. Jíša et al. [22] prepared Fe-FER,
safety risks Longer the Fe-MFI and Fe-*BEA by impregnation method and investigated the dif
related to high crystallization
pressure. time.
ference of catalytic performance of the three zeolites in the decompo
Enhance sition of nitrous oxide (N2O). It is found that although the three zeolites
crystallization have the same iron species and considerable Fe(II) content in the
rate. cationic position of the zeolites, the catalytic activity of Fe-FER is
Ion thermal Accelerate High pressure with Reduce the
significantly better than that of Fe-*BEA and Fe-MFI in the decomposi
method [110, crystallization low boiling point consumption of
111,122,123] rate. solvents. templates by tion reaction of N2O, which is mainly attributed to the unique spatial
Improve Not easily to realize introducing of local structure of Fe-FER. This structure contains two closely coordi
efficiency with industrialization. crystal seed or nated Fe(II) cations located at the β sites of two adjacent unit cells, and
microwave- mechanochemical- the length of Fe∙∙∙ Fe is 7–7.5 Å. Therefore, N2O is easily decomposed
assistance. guided synthesis.
Shorten
under the interaction of two adjacent ferrite ions. Ramakrishna et al.
crystallization time [14] prepared Fe/13X with different iron loading by impregnation
Reduce consumption method. It is found that under low loading conditions (2–6 wt%Fe), iron
of eutectic mixed exists on zeolite-13X support uniformly in the form of highly dispersed
solution.
iron oxide clusters or isolated iron ions. Under higher loading (＞ 6 wt%
10
Fig. 8. (A) Synthesis scheme of hierarchical Fe-MFI by direct hydrothermal method. UV-Vis spectra of the catalysts: (B) Fe-S-1, (C) Fe-S-1-P [124].
Fe), the iron oxide species with larger size were formed and the particles hydrothermal synthesis method, the crystal size of Fe-zeolites prepared
gather on the surface to form dense irregular shapes and clusters, and by DGC is much smaller, and with the extension of crystallization time,
the iron species are unevenly distributed, which reduces the specific the extra-framework Fe-O-Fe species can be transformed into isolated
surface area and catalytic activity of the catalyst. and dispersed in the framework. Koji Miyake et al. [6] synthesized MFI
Ion exchange method was mainly applied to obtain highly dispersed ferrisilicate nanocrystals (Fe-MFI-DGC) with a crystal size smaller than
active iron species, thus giving play to the excellent catalytic perfor 100 nm using a single template (tetrapropylammonium hydroxide) by
mance of zeolites. Also, ion exchange methods can easily exchange dry gel conversion method (DGC). The crystal size, structure and cata
active metals into the support through electrostatic adsorption, so that lytic performance of Fe-MFI-DGC were compared with the sample
the active species can be dispersed and fixed in the channels of the ze (Fe-MFI-HTS) prepared by traditional hydrothermal synthesis method.
olites. Therefore, this method can even be extended to synthesize the Compared with Fe-MFI-HTS synthesized by hydrothermal method, the
isolated centers of precious metals in the micropores of zeolites. zeolite synthesized by DGC had higher nucleation density in the early
Compared with the impregnation method, the ion exchange method has stage and slower crystal growth after nucleation. Therefore, the crys
higher dispersion and catalytic activity. By ion exchange, Fe could be tallization rate of Fe-MFI-DGC is significantly slower than that of
mainly deposited in the ion-exchange positions in the form of isolated Fe-MFI-HTS and its crystal particle size (< 100 nm) is also much smaller
iron ions or oxygen-bridged binuclear iron species. Besides, small clus than that of Fe-MFI-HTS (about 1 mm). In addition, the morphology of
ters of iron species in the pores, as coordinated unsaturated iron species Fe-MFI-DGC framework iron species was tracked and analyzed by
on the extra-framework and as large agglomerates of iron oxides on the UV–vis spectroscopy, and it was found that with the crystallization time
external surface could also be found [15,19,20,32,35,119]. Long et al. extended to 6 h, a sharp adsorption peak appeared at 200 ~ 300 nm,
[125] prepared different Fe-ZSM-5 zeolites by improved aqueous indicating that the Fe species changed from the Fe-O-Fe in the
ion-exchange (IA), and solid-state ion-exchange (SS) technology, deno extra-framework to the isolated and dispersed form in the MFI frame
ted as Fe-ZSM-5 (IA), Fe-ZSM-5 (SS). Different preparation methods lead work. Due to the decreased crystal size of Fe-MFI-DGC zeolite, the
to different forms of iron ions in Fe-ZSM-5. According to the ESR char diffusion path was shortened and the diffusion resistance was decreased,
acterization, most of the iron species in Fe-ZSM-5 (IA) are Fe3+ ions, a resulting in the improved catalytic performance in methanol conversion
few extra-framework α-Fe2O3 and Fe3O4 species and octahedral sym to olefin (MTO). Besides, the introduction of Fe into zeolite causes the
metrical Fe3+ complexes. However, the iron species of Fe-ZSM-5 (SS) formation of weak Brønsted acid strength and this inhibits the side re
mainly exist in the form of extra-framework α-Fe2O3 and Fe3O4 species. action or coke formation in the aromatic cycle, thus obtaining higher
Because the active center of SCR reaction is Fe3+ ions, and almost all Fe propylene-ethylene ratio (P/E) and lower light chain alkanes yield and
species in Fe-ZSM-5 (IA) exist in the form of Fe3+ ions, so the catalytic prolonging the service life of the catalyst. The CVD method can improve
activity of Fe-ZSM-5 (IA) is better than that of Fe-ZSM-5 (SS). atomic economy and highly disperse active iron species on the surface of
In addition to the conventional hydrothermal synthesis and post- support, so the Fe-zeolites prepared by CVD have better catalytic per
treatment method, some other methods, such as, dry gel conversion formance, but this method has higher equipment cost and high energy
method (DGC), reducing solid state ion exchange method (RSIE) and consumption [126]. Masaoki et al. [48] compared the Fe/ZSM-5 cata
chemical vapor deposition method (CVD). Compared with the lysts prepared by impregnation method (Imp), reducing solid state ion
11
exchange method (RSIE) and chemical vapor deposition method (CVD) ions, while the iron species in iron silicate zeolites maintain their
in terms of iron species, relative concentration and catalytic perfor oxygenated state. Aluminized iron zeolite is more inclined to activate
mance of selective catalytic reduction of NO by NH3 (NH3-SCR). The nitrous oxide, which is an important step in the selective conversion of
characterization methods of XRD, UV–vis and Mössbauer proved that benzene to phenol with N2O as oxidant. The great difference between
there were three types of iron species in the prepared Fe/ZSM-5 cata [Fe]MFI and [Fe, Al]MFI should not be attributed to the high density of
lysts-aggregated α-Fe2O3 particles, FexOy oligomer, and ion-exchanged [Fe, Al]MFI active centers, but to the chemical difference of iron in Fe-O-
oxo-Fe3+. Among them, the relative concentrations of FexOy oligomer Al and Fe-O-Fe adducts.
and oxo-Fe3+ species are as follows: CVD > RSIE > Imp. Therefore, the The shape selection effect of silicon aluminum zeolites in catalytic
SCR activity order of Fe/ZSM-5 catalyst obtained by three different reaction is reflected by the reactivity of B acid center in different pore
preparation methods follows the sequence of CVD > RSIE > Imp. structures. The distribution of acid protons in different pores will affect
the reactants, intermediate transition states and the spatial confinement,
4.2. Effect of Si/Al ratio and Al distribution on zeolites and then change the reaction activity and selectivity of the whole cat
alytic reaction. The distribution of framework aluminum, the aggrega
zeolites can be divided into total silicon (e.g. type Silicalite-1, type tion degree of acid center and the strength of acid center will lead to the
Silicalite-2), high silicon (Si/Al = 10 ~ 100) (e.g. type ZSM-5, type ZSM- difference of catalytic reaction, which also directly determines the
11), medium silicon (Si/Al = 2.0 ~ 5.0) (e.g. type X, type Y) and low complexity and specificity of zeolite structure design and preparation
silicon (Si/Al = 1.0 ~ 1.5) (e.g. type A) according to the ratio of silicon process required in a specific reaction. At the same time, on the premise
to aluminium of zeolitic framework. The framework Si/Al ratio has a of clarifying the structure-activity relationship between catalytic reac
significant impact on the incorporation of Fe into zeolite crystals, which tion and zeolite structure, the position and type of T atom of zeolite
finally affects the iron content, the size and distribution of iron species, framework are carefully regulated for specific reaction.
acid sites, interaction of metal carriers, thermal stability, hydrophobic
ity and catalytic performance of zeolites. For the preparation of Fe- 4.3. Effect of Fe incorporation amount
zeolite by post-treatment (i.e., impregnation, ion exchange, etc.),
zeolite with low Si/Al ration is usually selected as the support. It has With the variation of Fe loading, the presence and distribution of Fe
been well acknowledged that the dispersion of Fe depends on the on the zeolite will also change, further affecting the hydrothermal sta
number of ion sites provided in the zeolite framework. The lower the Si/ bility and catalytic performance of Fe-zeolites. Under the condition of
Al ratio of the framework, the more ionic sites provided, and the better excessive metal loading, the iron species incorporated into the zeolite
the dispersion of Fe as well as more amount of Fe species at the ionic framework are prone to migration and aggregation due to their insta
sites. Hu et al. prepared 5%Fe-ZSM-5 zeolites with different SiO2/Al2O3 bility under strict reaction conditions, and eventually form metal oxide
molar ratios (SiO2/Al2O3 = 28, 43, 80, 260) by impregnation method. It particles, resulting in the loss of catalyst activity [128,129]. In contrary,
is found that the Fe species on ZSM-5 zeolite with a SiO2/Al2O3 ratio of if the metal content is too low, the number of active sites is insufficient,
28 presents the smallest particle size (6.9 ± 1.3 nm). Besides, nanoscale which cannot ensure an effective catalytic reaction. Some studies have
particles were observed to be associated with the zeolite channel to shown that the metal ions located at the ion exchange sites have a
make the high dispersion of Fe in the support. Both XPS and H2-TPR certain protective effect on the framework structure of zeolites under
show that with the decrease of SiO2/Al2O3 ratio, the Fe 2p XPS peaks hydrothermal conditions. Therefore, adjusting the appropriate amount
move to a lower binding energy, and the reduction temperature of Fe/ of active metal loading can improve the hydrothermal stability and
ZSM-5 increases, suggesting the interaction between metal and sup catalytic oxidation performance of zeolites [130]. Andonova et al. [130]
port becomes stronger, which enhances the dispersion and stability of prepared Fe/SAPO-34 with different Fe content (0.27 wt%, 0.47 wt%,
metal/metal oxide on the carrier and prevents the sintering of metal 1.03 wt% Fe) by one-pot hydrothermal synthesis method, and studied
contained particles in the decomposition reaction of NH3. In addition, the relationship between crystal structure, hydrothermal stability and
the NH3-TPD results show there is a good linear relationship between the the catalytic performance of selective catalytic reduction of NOx by
acidity of Fe/ZSM-5 and H2 formation rate in ammonia decomposition ammonia. It is found that the crystallinity of Fe/SAPO-34 (1.03 wt% Fe)
process. Correspondingly, 5%Fe/ZSM-5(28) with high acidity can pro decreases obviously due to the cell size expansion caused by the high
mote the decomposition of NH3 by increasing the concentration of NH3 content of iron in the framework of SAPO-34 zeolite, which may lead to
near the iron active center, thus showing the highest catalytic activity, the instability and easy migration and aggregation of iron species in the
which can achieve the conversion of 99% NH3 at 650 ◦ C. Zhang et al. framework during hydrothermal treatment, forming FexOy aggregates
[127] loaded 5 wt% Fe in ZSM-5 zeolites with different SiO2/Al2O3 with almost no SCR catalytic activity, and finally leads to the decrease of
molar ratios (SiO2/Al2O3 = 30, 107) by impregnation method which SCR activity. While the active iron species increased via hydrothermal
was applied in the catalytic combustion of chloromethane (CH3Cl). treatment at high temperature, which is beneficial for the SCR catalytic
According to NH3-TPD characterization, the intensity of weak acid and activity improvement. Therefore, there was a best matching relationship
strong acid peak of Fe/ZSM-5 decreased slightly compared with that of between Fe content and catalytic activity and hydrothermal stability.
support ZSM-5, but the acidity of zeolite lattice increased significantly Zhang et al. [131] prepared Fe/ZSM-5 with different iron loads of 0.5, 1,
with the introduction of more aluminum, that is, the number of acid sites 2, 4 and 8 wt% Fe by impregnation method, and applied them in the
increased with the decrease of SiO2/Al2O3 ratio. Therefore, compared catalytic pyrolysis performance of rice husk. It was found that the
with 5% Fe/ZSM-5(107), 5% Fe/ZSM-5(30) shows stronger NH3 peaks dispersion of active metal components on the surface or pores of zeolite
at weak and strong acids. 5% Fe/ZSM(30) with higher acidity shows resulted in the blocking of micropores. With the increase of Fe loading,
good catalytic performance in the catalytic combustion of chloro the specific surface area (SBET), total pore volume (Vt), micropore vol
methane (CH3Cl). Seen from all the studies above, it could be concluded ume (Vmic) and micropore area (Smic) of the zeolite all presented a
that the selection of appropriate SiO2/Al2O3 molar ratio is of great sig decreasing trend. At the same time, in the catalytic pyrolysis of bio-oil,
nificance to the size and distribution of iron species, the acidity of ze the relative content of hydrocarbons increased obviously from 44.14%
olites as well as the interaction between metal and supports, all of which in the presence of ZSM-5 without iron to 49.97% in the presence of 4%
greatly contribute to the change of materials’ catalytic performance. Fe/ZSM-5. When the loading capacity of Fe was further increased to 8%
The distribution of aluminum also has a certain impact on the Fe Fe/ZSM-5, the relative content of hydrocarbons had no significant
speciation in Fe-zeolites. The reducibility of iron species in Fe-Si zeolite change. This was because Fe overload reduced the surface area of the
is obviously different from that in Fe-Al zeolite. In Fe-zeolites containing zeolite, which resulted in the increase of mass transfer resistance, thus
aluminum silicate, a considerable part of iron species is reduced to Fe(II) affecting the yield of bio-oil refining. Therefore, the optimal dosage of Fe
12
modified ZSM-5 zeolite catalyst was 4% Fe/ZSM-5. form of hexagonal layered stacking, and the adsorption performance
decreases slightly. Therefore, in the synthesis of zeolite, the optimal
molar ratio should be selected.
4.4. Effect of preparation parameters Yang et al. [133] prepared Fe, Co or Ni heteroatomic EU-1 zeolites by
hydrothermal synthesis at various temperatures. The effects of the
The preparation parameters (such as crystallization conditions, introduction of Fe and the crystallization temperature on the nuclei
template amount, Fe source types, calcination temperature, etc.) also formation of zeolites were also investigated. It was found that the
play a significant role in affecting morphology, microstructure, iron presence of Fe, Co or Ni in the synthesis system could promote the for
types and distribution, acid properties and redox properties of Fe- mation of the nucleus of EU-1 zeolite. The reason of accelerating
zeolites. Crystallization conditions mainly affect the nucleation and nucleation is related to the cation of oxyacid salt. Fe, Co or Ni have the
growth of zeolite crystals, which also will influence the properties of existence center of empty d orbital. The metal silicon oxygen structures
product zeolite. Li et al. [132] prepared FeAlPO-5 zeolite by coordinated by tetrahedron will be formed first in the amorphous
fluorine-free microwave hydrothermal synthesis using TEA as template samples that are incomplete crystallization. These structures accelerate
and studied the effect of template amount on the synthesis of FeAlPO-5. the nucleation and growth of crystals in the process of crystallization.
According to XRD (Fig. 9 A), the diffraction peak of the sample syn With the progress of crystallization, the gradually growing crystal nu
thesized with the addition of TEA in the range of 1.0–3.5 corresponds to cleus form tetrahedral coordinated metal silica structures. These units
the characteristic peak of AlPO-5 zeolite, which is a pure phase of AFI are transformed into tetrahedral coordinated framework species.
topological structure. However, when the amount of TEA is small Therefore, Fe, Co and Ni accelerate the crystal growth by accelerating
(TEA/P2O5 =0.7), two other diffraction peaks appear at 2θ = 20.3◦ and the formation of oligomer silicon, significantly shortening the nucle
21.4◦ , which are mainly related to the crystal phase of FeAl2( ation time and reducing the apparent activation energy. In addition, the
PO4)2(OH)2. In addition, under the condition of the same amount of iron apparent nucleation activation energy En of Fe, Co or Ni atom-doped
source, the iron content in the zeolite products decreased with the in EU-1 zeolites are larger than the apparent growth activation energy
crease of the amount of TEA (Fig. 9B). This is because the increase of Eg, indicating that the nucleation process is a rate-controlling step, so
TEA content will enhance the basicity of the reaction solution, resulting higher crystallization temperature is beneficial to the nucleation of EU-1
in the hydrolysis of Fe3+ into Fe(OH)3 colloid and cannot enter the zeolites containing Fe and can accelerate the crystal growth process.
molecular sieve framework. At the same time, the adsorption properties Nevertheless, the crystallization time should be shortened properly with
of molecular sieves decrease with the increase of TEA (Fig. 9B) and are the increase of temperature to prevent the appearance of stray grains.
related to the morphology of molecular sieves (Fig. 9C). When the molar Different Fe sources also have different effects on the incorporation
ratio of TEA/P2O5 increases from 0.7 to 2.0, the crystal structure of the of Fe into the zeolite framework. Yu et al. [9] used ferric sulfate and
product is gradually improved, and the crystallinity increases. When the ferrous sulfate as Fe sources to prepare Fe-MEL zeolites by in-situ
molar ratio of TEA/P2O5 reaches 2, the product is a perfect hexagonal feeding method, that is, introducing Fe sources at the end of
prism. At this time, the adsorption performance is the best. with the low-temperature crystallization (nucleation) stage and after
further increase of the molar ratio, the grain size of the FeAlPO-5 be high-temperature crystallization. The purpose of the process control
comes shorter, the cross-sectional area increases, the zeolite grows in the
Fig. 9. (A) XRD patterns of samples synthesized from different TEA/P2O5 ratio. (B) The composition and saturated adsorption capacity of samples synthesized from
different TEA/P2O5 ratio. (C) SEM images of samples synthesized from different TEA/P2O5 ratio [132].
13
method is to reduce the possibility of metal hydroxides or oxides for capacity of the zeolite support, which leads to the difference of catalytic
mation when Fe was introduced into the synthetic system. In the pre performance. Fe/H*BEA zeolite was synthesized by impregnation
vious studies of Yu et al. [134–136] the interaction between the method by Ma et al.[137]. The effects of calcination temperature on the
positively charged template TBA+ and negatively charged Si-Al frame physicochemical properties and catalytic performance of zeolite in
work fragments inhibits the aggregation of fragments and therefore, NH3-SCR reaction were investigated. It is found that the particle size of
promotes the formation of nanocrystal stacking morphology. After Fe/H*BEA-550, Fe/H*BEA-650 and Fe/H*BEA-750 is about 0.3 µm by
introducing Fe instead of aluminum into the synthesis system, the high resolution transmission electron microscope (HRTEM), while the
stacking morphology of nanocrystals were preserved in the product particle size of Fe/H*BEA-850 increases gradually, and the particle size
Fe-MEL zeolites (Fig. 10A) [11] indicating that Fe could be involved in of Fe/H*BEA-950 increases to about 3 µm (Fig. 11c), indicating that
the formation of zeolite framework, which was also confirmed by UV-Vis Fe/H*BEA forms crystal clusters at high temperature, resulting in a
(Fig. 10B). Nevertheless, the distribution of Fe in zeolite crystals shows decrease in specific surface area and pore volume. The catalytic activity
an evident variation with valence states of Fe in the metal sources. Ac curve of Fe/H*BEA prepared at different calcination temperatures in
cording to the STEM image, the Fe in Sam-SiFe(III) is uniformly NH3-SCR reaction showed that Fe/H*BEA-550 showed high catalytic
dispersed in the crystal, while the Fe in Sam-SiFe(II) is unevenly activity and reached close to 100% NOX conversion at 350–500 ◦ C, but
distributed in the local area of the crystal (Fig. 10A). The interaction the NOx conversion decreased at this temperature after hydrothermal
between NH3 and Fe-Si framework is much weaker than that with Al-Si aging (800 ◦ C), about 80% (Fig. 11d). In contrast, the NOx conversion of
framework, so the total acidity and peak temperature decrease after Fe Fe/H*BEA-850 below 350 ◦ C is relatively low, and the NOx conversion
replaces Al into the zeolite framework. At the same time, the third peak of Fe/H*BEA-950 is the lowest in the whole temperature range
at high temperature can be used to observe the change of Brønsted acid (Fig. 11a). In addition, according to the N2O selectivity test results of
center after the introduction of Fe into zeolite. It can be seen that NH3-SCR (Fig. 11b), lower N2O yields were detected on three kinds of
Sam-SiFe(III) has more Brønsted acid than Sam-SiFe(II) (Fig. 10C). Fe/H*BEA calcined at low temperature (550,650,750 ◦ C), but the N2O
Meanwhile, the Brønsted acid site formed by the incorporation of Fe into content on Fe/H*BEA-850 and Fe/H*BEA-950 catalysts was much
silicalite framework can act as a promoter to improve the catalytic higher at low temperature (< 350 ◦ C), which indicated that the
oxidation ability of zeolite. Therefore, Sam-SiFe(III) with more Bronsted morphology of iron species changed during calcination, especially at
acid sites has better catalytic performance. higher calcination temperature (above 850 ◦ C), iron ions (the active
The calcination process plays an important role in removing the center of NH3-SCR reaction at low temperature) may migrate from the
template and stabilizing the metal species later loaded on the zeolite ion exchange center to the iron oxide clusters on the zeolite support. In
support. The calcination temperature has a significant effect on the addition, due to the kinetic limitation at lower temperature and ther
microstructure, iron species, redox ability and reactant adsorption modynamic limitation at higher temperature, the conversion rate of NO
Fig. 10. (A) SEM images of different MEL samples (a) Sam-SiAl, (b) Sam-SiFe(III), (c) Sam-SiFe(II), (a1-a2) are the STEM-mapping of different areas of Sam-SiAl, (b1-
b2) are the STEM-mapping of different areas of Sam-SiFe(III), (c1-c2) are the STEM-mapping of different areas of Sam-SiFe(II). (B) UV-Vis spectra of different MEL
samples (a) Sam-SiAl, (b) Sam-SiFe(III), (c) Sam-SiFe(II), NH3-TPD original curves (C) and individual Gaussian bands of the curve simulation (D) of different MEL
samples (a) Sam-SiAl, (b) Sam-SiFe(III), (c) Sam-SiFe(II) [11].
14
Fig. 11. Catalytic performance for SCR of NOx with ammonia on different Fe/H*BEA catalysts. Reaction conditions: 0.1 g catalyst, 500 ppm NO, 500 ppm NH3, 5%
O2, balance N2, and GHSV = 160,000 h− 1. (a) NOx conversion on different catalysts. (b) N2O selectivity on different catalysts. (c) HRTEM pictures of different Fe/
H*BEA catalysts. (d) NOx conversions of fresh and aged Fe/H*BEA catalysts calcined at 550 ◦ C. Hydrothermal aging condition: Fe/H*BEA catalyst was made at
800 ◦ C for 10 h with 500 mL/min mixture gases consisting of 5% H2O (N2balance). (e) Oxidation activity of NO to NO2 by O2 over different Fe/H*BEA catalysts.
Reaction conditions: 0.1 g catalyst, 500 ppm NO, 5% O2, and balance N2, GHSV = 160,000 h− 1 [137].
on Fe/H*BEA prepared at different calcination temperatures showed a Different calcination atmosphere also has an important influence on
trend of first increase and then decline (Fig. 11e). Fan prepared 0.6 wt% the existence of Fe species. It is found that after calcination in air, the
Fe-ZSM-5 by incipient-wetness impregnation method and calcined at catalyst only contained iron species, most of which were hexagonal iron
different temperatures (T = 550, 600, 700, 800, 900 ◦ C) to obtain a species, and a small part of iron species belonged to large α-Fe2O3 par
series of Fe-ZSM-5 zeolites. The effects of different calcination temper ticles. However, after calcination in helium, some of the six-coordinated
atures on the structure of zeolites, the morphology of iron species and Fe3+ in the catalyst will undergo autoreduction reaction to form a stable
the catalytic performance of N2O oxidation of CH4 to methanol and α-site (mononuclear or binuclear divalent iron), and its content in
other oxygen-containing organic compounds were investigated. It is creases with the increase of calcination temperature. Therefore, the
found that when the calcination temperature is ≤ 700 ◦ C, the framework methane conversion increased at first and then decreased with the in
of the zeolite exists stably. When the calcination temperature is crease of calcination temperature. When the calcination temperature
≥ 800 ◦ C, the high temperature reduces the stability of the zeolite was 800 ◦ C, the methane conversion was the highest (1.01%), while the
framework, a large amount of framework aluminum is removed, and the selectivity and yield of oxygenated organic compounds increased with
zeolite framework is destroyed to a certain extent, and part of the mi the increase of calcination temperature. When the calcination temper
cropores will collapse, resulting in the decrease of micropore volume ature is 900 ◦ C, the selectivity (13.3%) and yield (0.12%) of oxygenated
and specific surface area as well as the decrease of crystallinity. In organic compounds of the catalyst are the highest.
addition, with the increase of calcination temperature (600 ◦ C→900 ◦ C)
in inert atmosphere, the content of six-coordinated Fe3+ gradually 5. Effect of Fe incorporation on the structure and properties of
decreased (76.0%→32.5%), and the content of α-site (mononuclear Fe2+ zeolites
and binonuclear Fe2+-O-Fe2+) gradually increased (1.6%→19.2%). The
content of α-Fe2O3 in large particles also gradually increased (22.4%→ The introduction of Fe will induce various changes in the pore
48.3%). Therefore, the high calcination temperature under inert atmo properties, stability, acid properties, hydrophobicity and redox proper
sphere (the calcination temperature is ≥700 ◦ C) will promote the ties of zeolites. Aluminosilicate microporous zeolites is a material with
autoreduction reaction of iron, and a part of six-coordinated Fe3+ will be high specific surface area with microporosity. When iron is incorporated
converted to the α-site of divalent irons, and the higher the temperature into zeolites, its specific surface area and micropore volume are reduced,
is, the more the conversion is. At the same time, high temperature while for Beta-zeolites, the addition of iron increases its specific surface
calcination also causes a large amount of six-coordinated Fe3+ to area and micropore volume. Sebastiano et al. [87] explored the changes
migrate and reunite, forming large α-Fe2O3 particles, and with the of specific surface area and micropore volume when iron was mixed into
aggravation of agglomeration, α-Fe2O3 will form different sizes. carrier ZSM-5 and Beta zeolites respectively by ion exchange method.
15
According to the N2 desorption schedule characterization, the specific iron covers the acid sites in the zeolite and affects the total acidity in
surface area (Fig. 12A) and micropore volume (Fig. 12B) of ZSM-5 different ways.
decreased with the addition of iron, which was mainly due to the par When irons are incorporated into aluminosilicate zeolites, the hy
tial blockage of ZSM-5 micropores. On the contrary, the introduction of drophobicity of zeolites will be improved. This is because the substitu
iron increases the specific surface area (Fig. 12C) and micropore volume tion of Al by Fe avoids the formation of Si-OH-Al groups, which has
(Fig. 12D) of Beta zeolites, which may be due to the formation of strong affinity to H2O in zeolite, resulting in effectively improving the
Fe-aggregates. Rache et al. [19] characterized the Y-Fe-zeolite prepared hydrophobicity of zeolites [9,11]. Yu et al. [11] characterized the
by ion exchange method by low temperature N2 adsorption and Fe-MEL(Sam-SiFe(III), Sam-SiFe(II)), Al-MEL(Sam-SiAl) synthesized by
desorption (BET) technique. The results showed that the introduction of in-situ feeding method by means of TG-DTA, and explored the influence
Fe reduced the pore volume from 0.24 to 0.10 cm3/g and the specific of the introduction of Fe on the hydrophobicity and thermal stability of
surface area from 432 to 259 m2/g. the zeolite. Compared with Al-MEL zeolites, weight loss of water below
For iron-free silica-zeolites, there are no Brønsted and Lewis acid 200 ◦ C is smaller in Fe-MEL zeolites, indicating that Fe-MEL zeolites had
sites. While iron was incorporated into the framework of silica-zeolites, better hydrophobicity. Besides, through the TG-DTA curve (Fig. 13A), it
Brønsted and Lewis acid sites are also introduced into zeolites. is known that compared with the Al-MEL zeolites, the larger ion radius
Compared with iron-free silica support, iron-zeolites contain both of Fe3+ makes its charge/radius smaller, and the interaction between
Brønsted and Lewis acid sites. However, for aluminosilicate zeolites, due TBA+ and the negative charge caused by the incorporation of the zeolite
to the existence of Al, aluminosilicate zeolites have strong acidic sites. frameworks much weaker than that of the Al framework. Therefore,
After Fe was incorporated into zeolite framework, the amount of Sam-SiFe(III) shows a double exothermic peak temperature similar to
Brønsted acid sites will be in a distinct decrease due to replacement of that of Al-MEL zeolite, but a significantly lower exothermic peak tem
protons or Al by cationic iron species in Brønsted acid hydroxyl groups perature (main peak temperature: ~ 416 ◦ C/Sam-SiFe(III), ~
[32]. Hosseinpour et al. [75] characterized Fe-ZSM-5 zeolites with 445 ◦ C/Al-MEL. shoulder peak temperature: ~ 435 ◦ C Sam-SiFe(III), ~
different iron concentrations prepared by one-pot immobilization 463 ◦ C /Al-MEL). Different from Sam-SiFe(III), Sam-SiFe(II) has a single
method and hot compression impregnation method, denoised as exothermic peak (~ 425 ◦ C). The authors believe that Fe2+ can only be
Fe-Z-xM(x = 0.05, 0.1, 0.2, 0.3, 0.5 mol/L) and Fe-Z-IMP by NH3-TPD partially incorporated into the framework of zeolite, and FeOx clusters
method. The results show that there are two main peaks of desorption may be formed in the process of crystallization. In addition, according to
near 160 ◦ C and 340 ◦ C, both of which are attributed to the adsorption of the H2O adsorption isotherms (Fig. 13B), the order of water adsorption
NH3 on the Brønsted acid center. At the same time, with the increase of capacity of different zeolites is Sam-SiAl > Sam-SiFe(III) > Sam-SiFe(II),
iron load, the second peak associated with the Brønsted acid center which proves that Fe-Si zeolite has good hydrophobicity. And Fe-Si ze
tended to decrease, which may be the reason for the destruction of the olites have good hydrophobicity mainly due to the lack of Si-OH-Al
Brønsted acid center. Compared with H-ZSM-5, the incorporation of Fe group. In addition, Sam-SiFe(II) has better hydrophobicity, which may
reduces the acidity of the catalyst, especially in the catalyst prepared be due to the fact that Fe is easier to incorporate into Sam-SiFe(III)
from the highest amount of iron nitrate precursor (Fe-Z-0.5 M), because framework, resulting in the formation of more Si-OH-Fe groups in
Fig. 12. N2 adsorption and desorption on bare and Fe-loaded zeolites: surface area and pore size distribution of ZSM-5 zeolite (A) and Fe-ZSM-5(B), and of Beta
zeolite (C) and Fe/Beta(D), respectively [87].
16
Fig. 13. TG-DTA curves of different MEL samples (A). (a) Sam-SiAl, (b) Sam-SiFe(III), (c) Sam-SiFe(II), (d) silicalite-2. H2O sorption isotherms of different MEL
samples (B). (a) Sam-SiAl, (b) Sam-SiFe(III), (c) Sam-SiFe(II) [11].
Sam-SiFe(III). Therefore, its hydrophobicity is weaker than that of The effect of water on the adsorption and catalytic process of Fe-zeolites
Sam-SiFe(II). is related to the spatial position of water and reactants in the adsorption
Because of its high polarity, water will first be adsorbed by the center of Fe-zeolites. In other words, the effect of water on the adsorp
adsorbent in the adsorption catalytic reaction, which hinders the tion and catalytic process is related to the structure of zeolites. Bal’Z
adsorption of the adsorbent to the target reactants, and then affects the hinimaev et al. [7] carried out a breakthrough study on the adsorption of
subsequent catalytic reaction. The Lewis acid sites, hydroxyl groups, toluene on high silica MFI and FAU zeolites under anhydrous and
surface cations and silyl alcohol groups of zeolites all adsorb water to a aqueous conditions (Fig. 14). It is found that according to the FTIR
certain extent, of which the most stable water molecules bind with spectroscopy technology of adsorption probe molecules (CO, quinoline),
surface cations, followed by hydrogen binding with coordination water, the Lewis acid sites, hydroxyl groups and cations that can adsorb water
and silanol groups binding with free water [138]. The water contact are located on the outer surface of MFI, while the adsorption sites of
angle can directly reflect the hydrophilicity or hydrophobicity of the toluene are located in the pores of MFI, so water will not hinder the
outer surface of zeolites. Different zeolites have different water contact adsorption of toluene. However, for FAU zeolites, the acid-base sites that
angle, the larger the water contact angle, the stronger the hydropho can adsorb water are distributed in the pore cavity and outer surface of
bicity; the larger the Si / Al ratio, the larger the contact angle, the the zeolite, so it will seriously affect the adsorption of toluene in the
stronger the hydrophobicity. For example, ZSM-5 zeolite is hydrophilic presence of water.
and its contact angle is 20.1◦ . When ZSM-5 is coated with siliceous When irons are incorporated into aluminosilicate zeolites, the redox
Silicalite-1, its hydrophobicity is obviously enhanced and has a higher properties of zeolites will be improved. Zhu et al. [139] investigated the
contact angle (the contact angle of the ZSM-5/Silicalite-1–75% is 36.4◦ ). redox performance of Fe-Beta and hierarchical Fe-Beta molecular sieves
Fig. 14. Toluene and water adsorption over different high zeolites. A) high silica MFI. B) high silica FAU [7].
17
prepared by ion exchange method by H2-TPR (Fig. 15). It was found that performance or photocatalytic activity were improved. Fe-zeolites show
there were two reduction peaks on Fe-Beta and hierarchical Fe-Beta, in excellent catalytic performance in fluid catalytic cracking (FCC), hy
which the overlapping reduction peak centered on 354 ◦ C (369 ◦ C) was drogenation cracking, toluene disproportionation, xylene isomerization,
attributed to the reduction of isolated Fe3+ to Fe2+, and the overlapping catalytic alkylation of benzene, catalytic hydroxylation of phenol,
reduction peak centered on 441 ◦ C (499 ◦ C) was attributed to oligomeric methanol to gasoline (MTG), methanol to olefins (MTO), methanol to
iron oxide species or the conversion of trace Fe2O3 to Fe3O4. Fe3+, aromatic hydrocarbon (MTA), low hydrocarbon catalytic pyrolysis
oligomeric iron oxide clusters and Fe2O3 coexist on Fe-Beta and hier propylene (OCC) and other chemical production, widely used in petro
archical Fe-Beta, but compared with Fe-Beta, the hydrogen consumption leum refining, petrochemical, fine chemical, coal chemical and other
of hierarchical Fe-Beta is higher than that of Fe-Beta, indicating that the chemical fields, especially the oxidation of benzene to phenol and the
enhanced activity of hierarchical Fe-Beta is mainly related to the high hydroxylation of phenol, as well as environmental protection fields such
dispersion of Fe active species, which may be due to the introduction of as air and water pollution treatment.
more defects in the layered structure, providing more ion exchange
centers for Fe species. In addition, when irons are incorporated into 6.1. Application of Fe-based zeolites in Chemical Industry
zeolites, Fe-Beta and hierarchical Fe-Beta showed higher SCR activity
than Beta and hierarchical Beta in the whole temperature range of Fe-zeolite is one of the most active catalysts in the direct conversion
150–500 ◦ C, and the reduction temperature of Fe species on hierarchical of benzene to phenol and phenol hydroxylation, especially Fe-ZSM-5.
Fe-Beta catalyst was lower than that of Fe-Beta catalyst, so hierarchical hydroxylating benzene catalytically with 95 + % selectivity for phenol
Fe-Beta had higher low temperature SCR activity. - even at high levels of conversion (30–45%), which is a key step in the
new Panov AlphOx process that emerged after the implementation of the
6. Application of Fe-based zeolites technology in the Solutia pilot plant [140]. Phenol hydroxylation is the
oxidation of phenol with hydrogen peroxide (H2O2) to produce catechol
As was mentioned, the introduction of Fe into zeolites has a signifi (CAT) and hydroquinone (HQ). The main products hydroquinone (HQ)
cant impact on the morphology, pore properties, acidity, hydrophobic and catechol (CAT) are indispensable raw materials or additives for the
ity, and catalytic performance of zeolites. The introduction of Fe does production of dyes, spices, drugs, rubber and so on. The patent pub
not lead to changes in the framework structure of the parent zeolite, but lished by Mobil Company in 1986 reported the hydroxylation of phenol
the introduction of Fe may be highly dispersed in the framework of the with 40% H2O2 on a modified ZSM-5 zeolite. After the reaction at 80 ℃
zeolite, or the agglomeration of iron oxides may lead to the blockage of for 1 h, the conversion of phenol was 30% and the selectivity of hy
micropores, resulting in changes in the crystal size of the zeolite and droquinone was 77% [141]. At present, Fe-zeolites such as Fe/H*BEA
corresponding changes in its microstructure characteristics. In addition, [142], Fe-HMS [143], FeAPO-5 [144] and Fe-MFI [29,108] have been
the hydrophobicity of the zeolites was significantly improved by the developed and applied to the hydroxylation of phenol with hydrogen
introduction of Fe instead of Al, and the acid properties were well pre peroxide and show good catalytic performance. Han et al. [108] syn
served. Nevertheless, compared with the Si-Al framework, the number thesized Fe-ZSM-5 zeolite by solvent-free method with Fenton reagent as
of Brønsted acid sites decreased due to the substitution of protons in the accelerator, and investigated the comparison of iron species, crystal
acidic hydroxyl group by cationic iron species. Therefore, the acidity of structure and catalytic performance for phenol hydroxylation between
Fe-zeolite is reduced. HP1.2-LT18-HT36 (HPx-LTy-HTz, where ‘HP’, ‘LT’ and ‘HT’ represent
In a word, the introduction of iron into the framework of alumino hydrogen peroxide, low temperature pretreatment and high tempera
silicate and phosphoaluminate zeolites modifies the physicochemical ture crystallization respectively; x, y and z are the molar ratio of
properties of traditional zeolites (acidity, particle size, pore structure, H2O2/Fe, low temperature crystallization time at 80 ◦ C and crystalli
pore performance). As a result, the pore adsorption performance, cata zation time at 180 ◦ C, respectively) treated with Fenton reagent and low
lytic performance, activity and selectivity of zeolites are changed, and temperature crystallization conditions and untreated HP0-LT0-HT48. It is
the shortcomings of hydrophilicity and insufficient catalytic ability of found that HP0-LT0-HT48 is composed of spherical nanoparticles with a
traditional zeolites are effectively overcome. The hydrogenation activ diameter of about 100 nm through the characterization of SEM and N2
ity, cracking activity, redox activity, oxidative dehydrogenation adsorption and desorption (BET), while HP1.2-LT18-HT36 is
Fig. 15. (A) H2-TPR results of the different Beta samples. (B) NOx conversion and N2 selectivity (inserted) results of Fe-Beta and Beta catalysts. Reaction conditions:
[NO] = [NH3] = 500 ppm, [O2] = 5 vol%, N2 balance and GHSV = 200,000 h− 1 [139].
18
agglomerated by crystals with a length of 5–10 µm, so HP1.2-LT18-HT36 6.2. Application of Fe-based zeolites in the field of environmental
has higher crystallinity (Fig. 16C). In addition, both HP1.2-LT18-HT36 protection
and HP0-LT0-HT48 have type I characteristic adsorption isotherms, and
obvious hysteresis loops appear at high relative pressure of the iso 6.2.1. Application of Fe-based zeolites in atmospheric field
therms (Fig. 16A), indicating that they are typical microporous mate Fe-zeolites have been widely used in various catalytic redox re
rials with a small amount of additional mesoporous or macropores. And actions in the atmospheric field, such as hydrocarbon and ammonia
compared with HP0-LT0-HT48, HP1.2-LT18-HT36 has a larger specific assisted selective catalytic reduction of NOx to N2 (HC-SCR and NH3-
surface area (302 m2/g) and a larger mesoporous volume (0.078 cm3/g) SCR) [48,65,145,146], decomposition and reduction of N2O [22,147],
(Fig. 16B), which means that the active iron species of HP1.2-LT18-HT36 catalytic oxidation of VOCs to CO2 and H2O [148], catalytic oxidation of
is more easily absorbed by the reactants. At the same time, the Chlorinated Volatile Organic Compounds (CVOCs) and so on [40],
adsorption capacity of HP1.2-LT18-HT36 for phenol was significantly which have attracted wide attention because of their remarkable cata
higher than that of HP0-LT0-HT48 (Fig. 16D). Although the isolated lytic activity and durability [65]. After being introduced into zeolite
tetrahedral coordinated Fe3+ is the active center of phenol hydroxyl with microporous porosity, Fe-zeolites will form different iron species,
ation, and HP0-LT0-HT48 contains more isolated tetrahedral coordinated including framework and extra-framework iron species. These iron
Fe3+ than HP1.2-LT18-HT36, HP1.2-LT18-HT36 has better catalytic activ species play different roles in different catalytic reactions. Masaoki et al.
ity, which indicates that the excellent performance of the catalyst pre [48] prepared a series of Fe/ZSM-5 catalysts by impregnation (Imp),
pared by this method is mainly due to the mesoporous volume, the large reductive solid-state ion exchange (RSIE) and chemical vapor deposition
specific surface area and the enhanced adsorption of phenol rather than (CVD), and compared the catalytic performance of Fe/ZSM-5 catalysts
just active iron species. Therefore, HP1.2-LT18-HT36 showed the better synthesized by three different preparation methods in the selective
catalytic performance in phenol hydroxylation. To sum up, the direct catalytic reduction (SCR) of NO by NH3. It was found that three types of
hydroxylation of phenol with hydrogen peroxide over Fe-zeolites is a Fe species coexist in Fe/ZSM-5 zeolites by XRD, UV-Vis and Mössbauer
promising green catalytic process. characterization: aggregated α-Fe2O3 particles, FexOy oligomer in the
extra-framework, and oxo-Fe3+ at ion-exchanged sites. Among them, the
relative concentrations of oxo-Fe3+ at ion-exchanged sites: CVD > RSIE
> Imp. In addition, because NO2-TPD has two NOx desorption peaks, its
high temperature peak correlated with the T-O-T perturbation peak in
FT-IR, indicating that the HT peak was due to desorption from
Fig. 16. (A) N2 adsorption/desorption isotherms of five representative Fe-ZSM-5 samples. (a) HP1.2-LT18-HT24, (b) HP1.2-LT18-HT28, (c) HP1.2-LT18-HT32, (d) HP1.2-
LT18-HT36 and (e) HP0-LT0-HT48. (B) pore size distribution curves of five representative Fe-ZSM-5 samples. (a) HP1.2-LT18-HT24, (b) HP1.2-LT18-HT28, (c) HP1.2-LT18-
HT32, (d) HP1.2-LT18-HT36 and (e) HP0-LT0-HT48. (C) SEM images of two representative Fe-ZSM-5 samples. (a-b) HP0-LT0-HT48, (c-d) HP1.2-LT18-HT36. (D) UV–visible
adsorption spectrum of phenol solution: untreated phenol solution (b) phenol solution treated by HP0-LT0-HT48, (c) phenol solution treated by HP1.2-LT18-
HT36 [108].
19
ion-exchanged oxo-Fe3+ sites. Meanwhile, since the HT peak had a adsorption on three configurations of Fe modified zeolites, the infrared
linear relationship with catalytic performance, the ion exchanged adsorption peak intensity of N2O by iron ions supported on Fe-Beta ze
oxo-Fe3+ sites should be the active sites for the NH3-SCR reaction, in olites is the highest, so the catalytic activity of Fe-Beta zeolites is obvi
other words, the activity order of Fe/ZSM-5 catalysts obtained by three ously higher than that of Fe-ZSM-5 and Fe-MCM-22 zeolites under the
different preparation methods is CVD > RSIE > Imp. Therefore, the condition of almost the same amount of iron loading.
Fe/ZSM-5 prepared by CVD method has better catalytic activity in the Chlorinated volatile organic compounds (CVOCs) are industrial
selective catalytic reduction of NO by NH3. Guo et al. [149,150] pre pollutants widely used in metal degreasing, dry cleaning, printing and as
pared Fe-ZSM-5, Fe-Beta and Fe-MCM-22 zeolites by ion exchange chemical intermediates. Due to the harmful effects of CVOCs, environ
method and analyzed the effect of zeolite configuration on the direct mental legislation has imposed more stringent restrictions on the
catalytic decomposition of N2O. The study showed that Fe3+ is mainly emission level of CVOCs in the atmosphere (the maximum allowable
loaded on the zeolite by replacing the proton H of the acid center, and it emission concentration is 36 mg/m3). Romero-Sáez et al. [40] prepared
is also the main active component in the catalytic decomposition of N2O a series of zeolites supported iron catalysts (2 wt% Fe-ZSM-5) by
by FT-IR, H2-TPR and NH3-TPD characterization techniques. According following different routes namely ion exchange from solution (IE),
to the FT-IR, H-ZSM-5 has two infrared absorption peaks at 3610 cm− 1 impregnation (IMP) and solid state ion exchange (SSIE) and investigated
and 3740 cm− 1, which belong to Al-OH and Al-Si-OH of Brønsted acid the catalytic performance of 2%Fe-ZSM-5 oxidative chlorination volatile
center of zeolites, respectively. When iron ions are introduced into organic compounds such as trichloroethylene (TCE) synthesized by
H-ZSM-5, a new infrared absorption peak appears at 3670 cm− 1, which different preparation methods (Fig. 17). It is found that through
corresponds to Fe-OH. With the increase of iron ions loading, the peak NH3-TPD characterization technology, the acidity of 2%Fe-ZSM-5 pre
intensity at 3610 cm− 1 (Al-OH of Brønsted acid center) decreases pared by ion exchange method has been greatly reduced by 30%, so the
gradually. This is because the iron ions as valence bond compensation acidity is low, which is due to the fact that iron species can be exchanged
cations replace the proton H at the Brønsted acid center on the surface of at α, β or γ sites, thus affecting the total acidity. In addition, through the
zeolites, resulting in the weakening of the infrared absorption peak in characterization techniques of EPR, UV–vis and TEM, it is known that
tensity at 3610 cm− 1. Meanwhile, Meloni and Dumitriu et al. [149] Fe2O3 nanoparticles are the active iron species for catalytic oxidation of
analyzed the valence state of iron ions on Fe-ZSM-5 by H2-TPR. The TCE, and there are a large amount of Fe2O3 nanoparticles and the
results show that the H2 reduction peak at 530 ◦ C corresponds to the highest dispersion in 2% Fe-ZSM-5 prepared by ion exchange method. At
valence bond compensation Fe3+ outside the zeolite framework, which the same time, the T50 and T90 values of IE samples are about 395 ◦ C and
undergo reduction reaction under the action of H2 to produce Fe2+. 460 ◦ C respectively, while those of IMP samples are 60 ◦ C higher than
Therefore, according to FTIR and H2-TPR, iron ions are mainly loaded on those of IE samples (455 ◦ C and 520 ◦ C), those of SSIE samples are 85 ◦ C
zeolites in the form of valence bond compensation cations. In addition, and 110 ◦ C higher than that of IE samples (480–570 ◦ C) (Fig. 17D). In
according to the in-situ diffuse reflection infrared spectroscopy of N2O addition, compared with H-ZSM-5 deactivation mechanism, Fe-ZSM-5
Fig. 17. TEM images of the Fe-ZSM-5 zeolites prepared by ion exchange (A), impregnation (B), and solid state ion exchange (C). (D) TCE oxidation light-off curves
over different Fe-ZSM-5 and H-ZSM-5 zeolite. (E) Conversion of TCE vs. time on stream over Fe-ZSM-5 prepared by IE (13.500 and 27.000 h− 1) and H-ZSM-5
(13.500 h− 1) [40].
20
did not lose its activity due to acid center coking and chlorine erosion of COFs, we can see that Fe-S2 (4.468 mmol/g) has better adsorption ca
zeolite, which indicates that the catalytic activity of Fe-zeolites is mainly pacity than Al-S2 (2.781 mmol/g) (Fig. 18B). Therefore, when applied to
due to the redox property caused by the change of valence of iron rather Non-methane Hydrocarbon (NMHC) removal from cooking oil fumes,
than acidity (Fig. 17E). To sum up, the 2%Fe-ZSM-5 prepared by ion Fe-MEL showed good adsorption and catalytic performance of NMHC
exchange method shows better activity and better stability in the cata (Fig. 18A). In order to further verify the adsorption and catalytic per
lytic oxidation of TCE. formance of Fe-zeolites with different valence states for NMHC, Yu et al.
Cooking oil fume (COFs), as a typical source of volatile organic [11] synthesized Fe-MEL (Sam-SiFe(III), Sam-SiFe(II)) and Al-MEL
compounds (VOCs), contains a variety of complex organic compounds (Sam-SiAl) zeolites by introducing different iron sources into MEL zeo
harmful to the environment and organisms, including hydrocarbons, lites framework via an in-situ feeding method, the results show that the
alcohols, aldehydes and polycyclic aromatic hydrocarbons (PAHs), etc. degree of Fe incorporated into silicalite framework is closely related to
COFs has become one of the important sources of urban air pollution. Yu the valence states of Fe in raw materials. Fe-MEL with good Fe disper
et al. [9] proposed a material with both good hydrophobic adsorption sion could be obtained and Fe3+ can be well incorporated into zeolite
and catalytic oxidation of non-methane hydrocarbon (NMHC) in cook framework. The Fe2+ can only be partially incorporated into the zeolitic
ing fume. Through the method of crystallization process control, diva framework, accompanied with the formation of FeOx clusters dispersed
lent metal ions (M2+=Fe2+, Mn2+, Cu2+) were introduced into MEL in zeolite crystals during crystallization. In addition, zeolite with Si-Fe
zeolites to investigate the doping, distribution, and existing forms of framework presents superior hydrophobicity due to the substitution of
different divalent metal ions in the framework of MEL zeolite, as well as Al by Fe avoiding the formation of hydrophilic Si-OH-Al groups. Because
the adsorption and catalytic oxidation properties of non-methane hy the doping degree of iron in the framework of Sam-SiFe(III) is higher
drocarbons (NMHC) in cooking fumes (Fig. 18). It is found that the peak than that of Sam-SiFe(II). Compared with Sam-SiFe(II), more Si-OH-Fe
intensity of samples containing Fe, Cu and Mn at 2θ 7.92◦ and 8.78◦ (low groups are formed in Sam-SiFe(III), resulting in weaker hydrophobici
angle) is evidently higher than that of Al samples by XRD, SEM, UV–vis ty than Sam-SiFe(II). This can be further confirmed by the adsorption
and other characterization techniques, which indicates that the substi curves of NMHC on different MEL zeolites (Fig. 18C). The NMHC
tution of divalent metal for Al is beneficial to improve the hydropho removal efficiency can be kept at ~80% for the longest period of
bicity of zeolite framework, and Fe2+ can be relatively well combined ~44 min over Sam-SiFe(II), then was followed by Sam-SiFe(III)
into the zeolite framework, and the interaction with TBA+ can effec (~36 min), and the correspondingly calculated adsorption capacity
tively induce the stacking morphology of nanorod crystals. Meanwhile, (average value) is 4.468, 3.659 mmol NMHC per gram zeolite, respec
from the adsorption-desorption curves of different metals to NMHC in tively. Therefore, Sam-SiFe(II) with best hydrophobicity displays the
Fig. 18. (A) Catalytic performance of NMHC in COFs over different metal-MEL zeolites. (B) Adsorption breakthrough curves of NMHC in COFs over different metal-
MEL zeolites. (C) The adsorption curves for NMHC over different MEL zeolites (a) and temperature-programmed desorption (TPD) of different MEL zeolites (b): (a)
Sam-SiAl, (b) Sam-SiFe(III), (c) Sam-SiFe(II). (D) NMHC removal efficiency curves with temperature over different MEL zeolites by catalytic oxidation method (a)
Sam-SiAl, (b) Sam-SiFe(III), (c) Sam-SiFe(II), (d) Blank [9,11].
21
best NMHC adsorption-desorption ability. In addition, the Fe species accordingly, which leads to the enhancement of catalytic activity, at the
that can participate in Fe3+/Fe2+redox cycles (framework Fe3+& moment, the particles are easy to agglomerate, resulting in poor self-
extra-framework FeOx) in Fe-MEL also endows the zeolite good catalytic stability and short life of zeolites. In addition, it is difficult for sup
oxidic properties (Fig. 18D), and the Brønsted acid sites formed by the ported iron-based zeolites to fundamentally solve the contradiction be
incorporation of Fe into zeolite framework can act as a promoter to tween particle dispersion and stability. In the process of catalytic
improve the catalytic oxidation ability of zeolites. When applied for the reaction, the loaded Fe heteroatoms can easily migrate to the outer
removal of NMHC from COFs, the Fe-MEL zeolites show excellent dual surface or pore channels of the zeolite, resulting in the blockage of the
functions of hydrophobic adsorption and catalytic oxidation. pore and the serious destruction of the ordered pore structure, in turn
leading to the deterioration of the thermal stability of the catalyst.
6.2.2. Application of Fe-based zeolites in water environment field In view of the above problems, the following aspects should be paid
With the increasing number of refractory organic pollutants in in attention to in future research: 1. New preparation methods should be
dustrial wastewater, the demand for clean water is increasing day by developed to ensure that Fe can be introduced controllably as needed
day. The advanced oxidation process (AOP) is based on highly reactive and distributed stably in the channels of zeolites for a long time, such as
species (mainly hydroxyl radicals [151]) and has the characteristics of anchoring or encapsulation technology, guest materials such as active
high efficiency and simplicity, so it is widely used in the treatment of iron species (such as Fe-Schiff base complexes) are encapsulated in
refractory organic pollutants in water [152]. In H2O2-based AOP, zeolite cavities, pores or cages, or zeolites can be directly designed as
treatment with Fenton reagent (dissolved Fe2++H2O2) is an effective hollow zeolites as packaging host materials to realize particular distri
and cheap method to degrade organic compounds in wastewater. Due to bution of metal species, resulting in improving the catalytic performance
the disadvantages of homogeneous catalyst, such as low yield, more and reusability of zeolites. In addition, iron-containing zeolites with
by-products, low selectivity, difficult separation of product and catalyst, hierarchical pore zeolite structure can also improve the narrow channel
complex catalyst recovery and high cost. Heterogeneous catalysts have defect of zeolites, which is beneficial to improve the diffusion of re
been gradually used in advanced oxidation processes. In recent years, actants and products, and thus improve the catalytic reaction perfor
Fe-based zeolites have been widely studied as catalysts for heteroge mance. Combining the properties of zeolites with other functional
neous Fenton-like advanced oxidation processes because of their ability components (Fe3O4 nanoparticles, Cu-Fe and other bimetallic or poly
to activate H2O2 to produce highly reactive oxidants in solutions close to metallic) can also broaden the application field of zeolites. 2. Fe-zeolites
neutral environmental conditions [153]. Gonzalez-Olmos et al. [154] should have the properties suitable for this application in different sit
prepared Fe-ZSM-5 (236) (SiO2/Al2O3 = 236) by ion exchange method uations. For example, the acidity caused by Si-Al framework may be
and investigated the adsorption and catalytic effect of zeolite on Methyl needed when it is used in various acid catalytic reactions in the chemical
Tert-Butyl Ether (MTBE) in water in heterogeneous Fenton-like industry. However, for the removal of air pollutants, such as the removal
advanced oxidation process. The results show that the zeolites with of VOCs, oxidation and hydrophobicity may be more needed, then Si-Fe
high SiO2/Al2O3 ratio (>200) were the most effective adsorbents, even can play its hydrophobic and redox role, while in the SCR reaction, both
superior to AC in the study of the adsorption of low MTBE concentra acidity and oxidation may be needed, and Si-Fe-Al may need to exist at
tions (Cfree = 0.01–1 mg L− 1) pollutants in water. In addition, the iron the same time. In addition, various factors such as different iron species,
speciation was studied by analyzing the UV–vis spectra of Fe-ZSM-5 Si/Al ratio, Si/Fe ratio and calcination temperature in Fe-zeolites also
(236), there are no iron-oxide particles and only a small fraction of have different effects on the properties of Fe-zeolites, which in turn
Fe(III)xOy clusters (3.5% of the total Fe spectral band) in Fe-ZSM-5. The affect their catalytic performance. Therefore, it is possible to select
dominant fraction consists of iron species of low nuclearity (isolated or suitable Fe-based zeolites and catalytic conditions for suitable catalytic
binuclear), which can be subdivided into Fe(III) in tetrahedral (band at reactions, which is of guiding significance in the fields of chemical in
λ ≈ 220 nm, 27.5%) and octahedral coordination (band at λ ≈ 285 nm, dustry, environmental protection, biomass conversion and so on.
69%), of which the isolated mononuclear and binuclear iron ions
attached to the acidic sites on the surface of zeolites are active species for
catalytic oxidation of MTBE. Meanwhile, the heterogeneous reaction has Declaration of Competing Interest
the advantages of working in near-neutral conditions together with the
possibility of recycling the Fe and avoiding the formation of sludge, The authors declare that they have no known competing financial
which is inevitable for homogeneous Fenton reactions. Even under interests or personal relationships that could have appeared to influence
nearly neutral conditions, Fe-ZSM5 (236) can produce active species the work reported in this paper.
from H2O2 and improve the activity of catalytic oxidation of MTBE.
Therefore, the hydrophobic Fe-ZSM-5 (236) zeolite can effectively Acknowledgements
adsorb and oxidize MTBE, so it is considered as a promising material for
MTBE removal from water. The authors greatly appreciated the finance Supported by the Pro
gram for Fundamental Research Funds for the Central Universities (No.
7. Concluding remarks and prospects FRF-AT-20-12), the Opening Fund of State Key Laboratory of Heavy Oil
Processing (No. SKLOP202002001), and National Natural Science
Iron-containing zeolites have been widely used in chemical industry, Foundation of China (No. U20A20130).
environmental protection, biomass conversion and other catalytic fields
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Applied Catalysis A, General

Synthesis, characterization and application of Fe-zeolite: A review

paramagnetic resonance (EPR) spectroscopy, often referred to as elec

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Applied Catalysis A, General 630 (2022) 118467

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Applied Catalysis A, General

Synthesis, characterization and application of Fe-zeolite: A review

paramagnetic resonance (EPR) spectroscopy, often referred to as elec­

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paramagnetic resonance (EPR) spectroscopy, often referred to as elec