Applied Catalysis B: Environmental 316 (2022) 121625

Contents lists available at ScienceDirect

Applied Catalysis B: Environmental

journal homepage: www.elsevier.com/locate/apcatb

Full utilization of lignocellulose through one-pot in-situ hydro-liquefaction

with versatile Pt/CeCrO2− x catalyst
Weichao Chou a, Dong Liu a, *, Weizhen Li b, Xin Chou c, Hua Liu d, Chongchong Wu e, Peng Wu b,
Zhuowu Men b, Zhiheng Li a
a
School of Chemistry and Chemical Engineering, China University of Petroleum, Qingdao 266580, China
b
National Institute of Clean-and-Low-Carbon Energy, Beijing 102211, China
c
Department of Occupational Disease, Shanghai Pulmonary Hospital affiliated Tongji University, Shanghai 200433, China
d
School of Geosciences, China University of Petroleum, Qingdao 266580, China
e
CNOOC Research Institute of Refining and Petrochemicals, Beijing 102200, China

A R T I C L E I N F O A B S T R A C T

Keywords: One-pot catalytic conversion of raw woody biomass into valuable chemicals and fuels is a promising strategy for
Pt/CeCrO2− x catalyst relieving energy depletion. Here, we proposed an efficient catalyst combining highly dispersed and ultrafine
Surface oxygen vacancy platinum nanoparticles on ceria doped with Cr, enabling nearly complete conversion, and obtaining value-added
Solid solution
chemicals and bio-fuel with high energy density. The key part of our approach lies on the flexible utilization of a
Bio-fuels
Full utilization
synergetic catalysis system consisting of a redox potential CeCrO2− x, balanced acid-base properties and strong
metal-support interaction. Abundant oxygen vacancies and enhanced wettability have been achieved by properly
doping of Cr. Under nitrogen atmosphere, the catalyst still shows excellent conversion performance, not only can
hydrogen transfer be achieved by using the “borrowed” hydrogen, but also the Guerbet reaction can suppress the
formation of intractable chars. Moreover, alcoholophilicity facilitates the dispersion of the catalyst particles in
ethanol, leading to higher mass transfer efficiency. The catalyst can be separated facilely and reused three times
without obvious deactivation.

1. Introduction compared with other methods[11–13]. In addition, a variety of metals

can act as catalysts for HTL, rendering the products with lower oxygen,
Lignocellulosic biomass, which is composed of cellulose (40–50 wt moisture content and higher H content, calorific value [6,14]. Finally, it
%), hemicellulose (16–33 wt%) and lignin (15–30 wt%), represents reduces the fixed and operating costs of processing equipment and
more than 90 wt% of all plant biomass and is one of the most abundant storage, allowing HTL technology more competitive for biomass to fuel
renewable carbon-neutral feedstocks with renewability [1–4]. However, conversion [15].
biomass as a solid material with a complex structure and notorious However, the conventional catalytic reactions for HTL only utilized a
resistance to chemical transformation, has a low direct utilization effi­ certain fraction of the lignocellulose, leaving large fraction unconverted
ciency and the current utilization methods exist huge challenges. To mixed with the catalyst [16,17]. To improve the conversion rate of
tackle these issues, the conversion of raw lignocellulosic biomass into lignocellulose, the pretreatment of biomass (including acids [18], bases
the liquid fuels and chemicals has been the focus of numerous studies in [19], ionic liquids [20], etc.) was attempted, and the intrinsic structure
recent years. [4–13]. of biomass is first properly disrupted before catalytic conversion.
The main technologies to convert lignocellulose to liquid fuel include Although it is beneficial to improve the conversion rate to a certain
pyrolysis [4], hydrothermal liquefaction (HTL) [8], gasification [9], and degree, the difficulties in separating subsequent products from ionic
enzymatic digestion [10], among which HTL is the most promising liquids and the unfriendliness of acids and bases to the environment
alternative technology. The HTL method is able to accommodate a wide make the pretreatment not feasible [19,21]. On the other hand, a
range of feedstocks (agricultural and forest residues, animal manure, two-step lignin first approach, in which lignin was converted to aromatic
food processing wastes and even wet microalgae) for fuels production alcohols under mild conditions firstly and the remaining lignin and

* Corresponding author.
E-mail address: [email protected] (D. Liu).

https://doi.org/10.1016/j.apcatb.2022.121625
Received 12 April 2022; Received in revised form 9 June 2022; Accepted 10 June 2022
Available online 14 June 2022
0926-3373/© 2022 Elsevier B.V. All rights reserved.
W. Chou et al. Applied Catalysis B: Environmental 316 (2022) 121625

unreacted cellulose subsequent converted to aliphatic in the second step Table 1

was reported to achieve the full utilization of lignocellulose [22–24]. Elements, chemical composition results of the sawdust.
Nevertheless, the two-step reaction requires different reaction condi­ Items Contents Items Contents
tions and even different catalysts, leading to a complex and
Elements C 46.22 Chemical Cellulose 45.62
energy-intensive process [25]. Therefore, it is critical to develop new (wt%) H 5.56 Composition (wt%) Hemicellulose 20.13
catalytic systems and innovative biorefining methods that can achieve Oa 47.86 [37] lignin 25.19
efficient recycling and the valorization of all lignocellulose constituents N 0.36 Ash 0.94
[26,27]. Extractive 8.12

To avoid the complexity and energy intensity of multi-step batch a

Calculated by difference between 100 wt% and the contents of C, H, N as
reactions, one-pot catalytic conversions seem to be more promising for well as other elements in the ash (e.g., Na, K, and et al.)
industrial applications [28] due to its facile operation and unnecessity of
pretreatment. A lot of research has focused on the development of from Sinopharm Chemical Reagent Co., Ltd. Ce(NO3)30.6 H2O, Cr(NO3)⋅
multifunctional catalysts to meet various requirements in the one-pot 9 H2O, Pt(NO3)2 were purchased from Sigma-Aldrich Corporation. All
system. In this regard, certain contributions have been made to the the reagents were used directly without further treatment.
design of an efficient combination of metal-catalyzed hydrogenation and
acid-catalyzed deoxygenation for highly selective hydrodeoxygenation
2.2. Catalyst synthesis
(HDO) of woody biomass into liquid fuels and chemicals (e.g., Cu-PMO
[25], Pd/NbOPO4 [26], Ni-W2C/AC [29], and Ni2Al3 alloy [30]). the
The CeO2 support was prepared by precipitation method. The sche­
above studies generally have the disadvantages of high catalyst dosage,
matic for the formation of the catalyst is illustrated in Scheme 1. In a
incomplete conversion, catalyst deactivation, which are usually ignored
typical synthesis procedure, Ce(NO3)30.6 H2O was dissolved in 100 mL
at the laboratory experiments. However, these aspects are likely to
of deionized water. An aqueous ammonia solution was added dropwise
become increasingly prominent as hydro-liquefaction processes move
into the solution of Ce(NO3)3 with continual stirring at 60 ℃ until the
towards industrial scale. Another important point is that most of the
precipitation was complete at pH = 10. The mixture was centrifuged to
exogenous “gray” hydrogen comes from non-renewable fossil fuels, and
collect the precipitate that was then washed thoroughly with distilled
its storage and transportation have great safety hazards[31]. In order to
deionized water. The solid was dried at 110 ◦ C overnight and then
address the above challenges for the one-step conversion of lignocellu­
calcined at 500 ◦ C for 4 h to obtain the CeO2 support. The Cr-doped CeO2
lose to high quality bio-oil, this work aims to develop a catalyst with
support, named Ce0.9Cr0.1O2− x, was prepared following similar pro­
three main properties. (i) water-tolerant and stability; (ii) high
cesses to the synthesis of the CeO2, with an initial molar Ce(NO3)3/Cr
char-suppressing potential; (iii) in-situ hydrogen supply; (Ⅳ) high HDO
(NO3)30.9 H2O ratio of 9/1.
efficiency. Highly oxophilic CeO2 has rarely been reported as a
The Pt/CeO2 and Pt/Ce0.9Cr0.1O2− x catalysts were prepared by
water-resistant Lewis acid-base support [32] which can effectively
incipient wetness impregnation with 2 wt% Pt loading. In detail, the
inhibit char-forming condensation reactions [33,34]. Nelson et al.
CeO2 or Ce0.9Cr0.1O2− x support was impregnated into the aqueous so­
investigated the activity of Pd supported on Na-modified CeO2 for the
lution of Pt(NO3)2. The mixture was evaporated in the water bath at
in-situ hydrogenation of phenol using 2-PrOH [35]. Pd/Ce-Na shows
70 ◦ C for 4 h under vigorous stirring and then further dried at 110 ◦ C
higher activity than Pd/CeO2 because the increased the number of
overnight. The obtained solids named PtO2/CeO2 and PtO2/
substrate adsorption and redox active sites. However, most of the cur­
Ce0.9Cr0.1O2− x were calcined at 500 ◦ C for 4 h in air. The schematic
rent studies have targeted model compounds, and the actual biomass is
formation of Pt/CeCrO2− x is illustrated in Scheme 1. Finally, the PtO2/
much more complex. Therefore, we conceived CeO2 as support, and
CeO2 and PtO2/Ce0.9Cr0.1O2− x samples were reduced in a 50 mL/min
modified the lattice of CeO2 to improve its surface properties to make it
10% H2/N2 gaseous mixture for 3 h at 350 ◦ C with a heating rate of
more suitable for raw biomass feedstocks [36].
5 ◦ C min− 1. The resulting catalysts were labelled as Pt/CeO2 and Pt/
Here, we reported a multifunctional Pt/CeCrO2− x catalyst consisting
CeCrO2− x catalysts.
of the ultrafine highly dispersed platinum and balanced acid-based sites,
which, due to the synergistic effect, can achieve near 100% conversions
of biomass. The catalyst can be separated and recycled by a facile 2.3. Activity test and product analysis
filtration. Interestingly, the Pt/CeCrO2− x also catalyzes Guerbet reaction
efficiently, the resulting “green” hydrogen provides the reducing The catalytic conversion of raw biomass was conducted in a 100 mL
equivalents necessary for the HDO reaction. The addition of Cr signifi­ Teflon-lined stainless-steel autoclave. Typically, feedstock (1 g), catalyst
cantly increased the concentration of oxygen vacancies, acidity on the (0.20 g) and ethanol (20 g) were added into the reactor. The reactor was
catalyst surface and the wettability of the catalyst, which promoted the purged with N2 for three times and charged to an initial pressure of
breakage of C-O bonds and the dispersion of the catalyst in the solvent. 5.0 MPa with H2. The reactor was then slowly heated to 300 ℃ and held
The strong metal-support interaction (SMSI) enhances the catalyst sta­ at this temperature for 10 h with a stirring speed of 600 rpm. After the
bility and maintains similar performance in repeated tests. Overall, this reaction, the reactor was cooled down to room temperature rapidly by
work will inspire the development of sustainable biorefineries that can cooling coils. And the pressure and temperature were recorded. The
increase biomass utilization, and gradually replace intermittent batch gaseous product was collected for analysis using gas bags. After
reactions, and promote the industrialization of continuous feeding slurry releasing the gas inside, the resulted production was thoroughly rinsed
reactor. out of the reactor with acetone. Then, the liquid/solid mixtures were
separated by a pre-weighed filter paper to obtain the filtrate and residue.
2. Experimental and methods The solid sample remaining on the filter paper was extracted with
acetone and dried in a vacuum oven at 110 ℃ for 12 h before weighing,
2.1. Chemicals and materials and the dried fraction was named as solid residue. The filtrate was dried
over anhydrous sodium sulfate (Na2SO4), filtered, and evaporated in a
Birch was obtained from an industrial wood factory in Qingdao, rotary evaporator to remove acetone and residual water. The remaining
China. Before usage, the sawdust was washed with deionized water for fraction was designated as bio-oil. The products in the liquid phase were
three times, dried at 105 ℃ for 12 h and then milled into particles qualitatively analyzed by Gas Chromatography-Mass Spectrometry
(210–325 µm). The characteristics of the sawdust is listed in Table 1. (GC–MS) and quantitatively analyzed by GC–flame ionisation detector
Ammonia solution tetrahydrate (NH3⋅H2O, 25%− 28%) were purchased equipped with a DB-5 column (30 m × 0.25 mm×0.25 µm). Helium was

2
W. Chou et al. Applied Catalysis B: Environmental 316 (2022) 121625

Scheme 1. Schematic for the formation of Pt/CeCrO2− x catalyst.

applied as the carrier gas (1.0 mL⋅min− 1) with a split ratio of 20:1. The mapping and element line scan were recorded on the Tecnai G2F20 S-
temperature was programmed to start at 60 ◦ C (holding for 5 min) and Twin. An elemental analyzer (Vario EL III, German) was applied to
then increased to 300 ◦ C with a heating rate of 10 ◦ C⋅min− 1 (holding for analyze the elemental contents of C, H, N and S in feedstocks and
20 min). products. The O content was calculated by difference. The combustion
The yields of bio-oil, solid residue, and gas were all expressed in wt heat of feedstocks and products is calculated by the higher heating value
%. The bio-oil and solid residue yields were calculated from: (HHV)[38]:

weightofinitiallignocellulose(g) − weightofrediduallignocellulose(g)
Conversion(wt.%) = ( ) × 100% (1)
weightofinitiallignocellulose(g)

/
HHV(MJ⋅kg− 1 ) = 0.3383 × C% + 1.422 × (H% − O% 8) (5)

Yieldofbio − oil(wt.%) = (
weightofbio − oil(g)
) × 100% (2) The chemical adsorption/reduction properties of catalyst surface are
weightofinitiallignocellulose(g) tested on the Micromeritics AutoChem II 2920 instrument. For H2
temperature programmed reduction (H2-TPR), 100 mg of calcined
weightofresidue(g) − weightofcatalyst(g) sample was loaded into a U-shaped quartz reactor. The sample was first
Yieldofsolid(wt.%) = ( ) × 100%
weightofinitiallignocellulose(g) treated in in Ar at 300 ◦ C for 1 h. Next, the sample was heated to 900 ◦ C
(3) in the 10 vol% H2/Ar mixed gas (30 mL⋅min− 1) at a rate of
15 ◦ C mL⋅min− 1. The outlet gas was analyzed by an online gas chro­
Yieldofgas(wt.%) = 100 − Yieldofbio − oil(wt.%) − Yieldofsolid(wt.%) (4)
matograph equipped with a thermal conductivity detector (TCD). The
temperature programmed desorption of ammonia (NH3-TPD) was con­
ducted on AutoChem II 2920 instrument. Approximately 100 mg cata­
2.4. Catalyst characterization
lyst were thermally treated at 450 ◦ C with flowing He for 1 h, at a
heating rate of 10 ◦ C⋅min− 1, then cooled to 40 ◦ C prior to adsorption. At
Powder X-ray diffraction (XRD) was conducted on X′ pert PRO MPD
40 ◦ C, a total of 10% NH3–He was passed over the catalysts for 30 min.
diffractometer with Cu Kα radiation (10 kV, 40 mA) with a scanning
After purging with pure He for 1 h at 40 ◦ C until the baseline was stable,
angle from 5◦ to 80◦ at a scan rate of 2.5◦ min− 1. N2 physisorption
the desorption profile was obtained using the thermal conductivity de­
(Micromeritics ASAP 2020) was used to characterize the pore volume
tector in He flow at a heating rate of 10 ◦ C⋅min− 1 to 650 ◦ C. The static
and diameters. All catalysts were degassed at 350 ◦ C for 6 h prior to
contact angle between catalyst and ethanol was measured using a
analysis. The surface areas were calculated by the Brunauer-Emmett-
German DAS30 contact angle measuring instrument. Nicolet 6700
Teller (BET) method, and the pore size distribution was calculated by
spectrometer in situ equipped with a cell was used recording Pyridine
the Barrett-Joyner-Halenda (BJH) method from the desorption
FT-IR spectrum. The samples were pressed into a self-supporting plate
branches. X-ray photoelectron spectroscopy (XPS, Thermo ESCA­
(8 mg, 13 mm diameter), placed in an IR cell, and then treated at 150 ◦ C
LAB250Xi) was performed to measure the composition and valence
under vacuum for 30 min. After the IR cell was cooled to room tem­
states of surface metals. Inductively coupled plasma-atomic emission
perature, pyridine vapor was introduced into the cell, adsorbed for
spectrometry (ICP-AES, VARIAN 720-ES) was used to obtain the Pt, Ce
20 min, and reached equilibrium for 30 min. Then, the cell was scanned
and Cr metal content. Samples (5 mg) were digested for 24 h in aqueous
after being vacuumed for 10 min and recorded at 200 ◦ C under vacuum.
HF and HCl solution (0.18 v/v % and 5 v/v % respectively). All the
absorbance-based experiments were carried out using a Shimadzu
3. Results and discussion
UV–visible spectrophotometer (UV-2600). SEM images were recorded
using a Genimi SEM 500 (Carl Zeiss Microscopy GmbH). The high-
3.1. Structure and morphology of Pt/CeCrO2− x catalyst
resolution transmission electron microscope (HR-TEM, Tecnai F20)
was used to investigate the morphology of the catalyst at a voltage of
The XRD patterns of the CeO2-based materials are shown in Fig. 1,
200 kV. High-angle annular dark-field scanning transmission electron
and all the catalysts exhibit typically CeO2 fluorite structure with the
microscopy (HAADF-STEM) images, energy dispersive X-ray (EDX)

3
W. Chou et al. Applied Catalysis B: Environmental 316 (2022) 121625

Fig. 1. XRD patterns of catalysts (fresh, reduced, reused three cycles) and partially enlarged profile.

space group of Fm3m [39,40]. The main peaks at 28.6◦ , 33.1◦ , 47.5◦ , clusters absorb between 300 and 500 nm [47]. Fig. S3 shows that
and 56.3◦ correspond to (111), (200), (220), and (311) crystal planes Pt/CeO2 has an absorption peak between 400 and 500 nm, which proves
according to the XRD database (CeO2 JCPDS card No. 34–0394). It is that Pt existing on this catalyst exists as a cluster, while Pt/CeCrO2− x
interesting to see that there are no obvious diffraction peaks for catalyst has no obvious absorption peak, and may exist in an isolated
Cr-related species due to their lower loading content and weak crystal­ state.
lization of Cr oxides. Moreover, the peak of Pt can not be detected,
suggesting that the Pt clusters, with relatively small size, may disperse
3.2. Catalytic performance
evenly over the surface of the CeCrO2− x support [41]. It is worth noting
that the XRD patterns of the same loading amount of Pt/CeO2 and
The Pt/CeCrO2− x catalyst was further applied to the hydro-
Pt/CeCrO2− x are different, as shown in Fig. S1. Besides, the diffraction
liquefaction system of raw sawdust to investigate its hydro-
peaks of the CeO2 support, and the three small peaks were also detected
liquefaction and HDO performance in comparison with the blank
at 39.5, 46.0◦ and 67.1◦ , corresponding to the diffraction of the (111),
agent. As shown in Fig. 3 and Table S1, the yields of the three-phase
(200) and (220) facets of Pt microcrystallites, respectively [42,43]. The
products under different conditions were summarized. Without cata­
reason is that the dispersion of metal Pt on CeO2 is not as good as that on
lyst, the conversion rate for lignocellulose is about 75 wt% under
CeCrO2− x, and this part will be analyzed in detail later.
hydrogen atmosphere for 5 h (Fig. 3a). In the case that the reaction time
The morphology of Pt/CeCrO2− x and Pt/CeO2 was further studied by
was extended to 10 h and above, a decrease of conversion rate was
HR-TEM, STEM-EDX and HAADF-STEM, as shown in Fig. 2. According
observed, which may be due to the fact that the depolymerization pro­
to the HR-TEM analysis (Fig. 2a), Pt particles are not visible in the TEM
cess generates many highly reactive oxygenated intermediates [33].
image with high magnification, indicating that Pt nanoparticles are
However, there is not enough H radicals in the system to stabilize these
highly dispersed on CeCrO2− x [39]. The diffraction surfaces of CeO2
intermediates, resulting in the repolymerization between them to form
(111) and (220) were detected on both materials, but not for any of the
heavier products, such as black char [48]. As shown in Fig. S4, the white
Cr-related species [36,44]. The Pt/CeCrO2− x shows the characteristic
sawdust gradually changed into loose brown residue, and finally, turned
spacings of 0.190 and 0.308 nm for the (220) and the (111) lattice
into black solid residue. However, after the introduction of the catalyst,
planes of CeO2, corresponding to the results shown in Fig. 2b [45].
the conversion rate for lignocellulose could reach as high as 98.6% in
However, in the HR-TEM image of conventional Pt/CeO2, as shown in
5 h. We also investigated the effect of temperature on the reaction
Fig. S2, a Pt (111) crystal plane with the interplanar spacing of 0.226 nm
(Fig. 3b), and found that the highest bio-oil yield of about 45.22% was
was observed, which further proves that the addition of Cr can promote
obtained at the reaction temperature of 300 ◦ C. In another word, higher
the degree of dispersion of Pt [46]. The HR-TEM results are in good
temperature result in lower bio-oil yield and higher gas yield [11].
agreement with the XRD results.
Under hydrogen atmosphere without catalysts, the yields of the gas,
To investigate the effect of Cr3+ doping on elemental distribution of
liquid and solid products for 5 h are 39.56 wt%, 34.78 wt% and
the catalyst surface, energy-dispersive X-ray (EDX) mapping was per­
25.66 wt%, respectively. The addition of Pt/CeCrO2− x catalyst is bene­
formed, and the spectra show that Pt, Cr and Ce were uniformly
ficial to generate less solid (1.42 wt%) as well as producing more gas
distributed over the Pt/CeCrO2− x sample (Fig. 2c). In the high angle
(44.22 wt%) and liquid products (56.26 wt%), as shown in Fig. 3c. The
annular dark-field scanning transmission electron microscopy (HAADF-
catalyst has good catalytic performance under hydrogen atmosphere,
STEM) image (Fig. 2d), the nanoparticles of ultrafine Pt with high
and similar performance under nitrogen atmosphere (Fig. 3d). In the
coverage and the size of 1.28 ± 0.2 nm can be observed, which are much
case that the reaction time was extended to 10 h, complete conversion of
smaller than that of Pt/CeO2. We also conducted UV− vis spectroscopy to
lignocellulose could be achieved regardless of the gas atmosphere. In
study the dispersion of Pt species. An absorption band of isolated Pt
obvious contrast, the conversion rate under nitrogen atmosphere
species appears below 300 nm, and aggregated Pt sheets or small
without the addition of catalyst was only 46.36%.

4
W. Chou et al. Applied Catalysis B: Environmental 316 (2022) 121625

Fig. 2. Morphology characterization of Pt/CeCrO2− x. (a) TEM and average particle size of particles image (b) HR-TEM image, (c) EDX elemental mapping, (d)
HAADF-STEM and average particle size of Pt.

We have designed the control experiments, as shown in the product paper is capable of obtaining extremely high conversion rate under both
distribution section (Fig. S5), in which only the catalyst and ethanol nitrogen and hydrogen atmosphere. Nevertheless, it takes longer route
were involved in the reaction under nitrogen atmosphere and the for woody biomass to convert under nitrogen atmosphere as it does not
hydrogen gas produced was quantified. Based on the above experi­ have external hydrogen sources, and needs one extra step to in-situ
mental results, we made a bold speculation that the catalyst relies on the generate hydrogen and then proceed to the following hydrogenolysis
dehydrogenation reaction of ethanol to induce the Guerbet reaction, and HDO reaction. On the other hand, the nitrogen atmosphere reaction
thus enhancing hydrogen transfer [49–51]. The possible mechanism and has the advantages of enhancing the hydrogen transfer reaction for in-
the subsequent isotope tracer methodology experiments are shown in situ hydrogen supply, exhibiting the potential of residue suppression.
Scheme 2. Ethanol is first dehydrogenated at Pt sites, producing acet­ The catalyst, at the completion of the reaction can be recovered by using
aldehyde and hydrogen atoms that spill over onto the Pt/CeCrO2− x ordinary filtration with a filter paper, and a high value-added n-butanol
catalysts. The active hydrogen produced in this process can be utilized in can be obtained.
catalytic conversion and further HDO reaction. As compared to the high
pressure reaction, the high local concentration of the hydrogen source in 3.3. Components analysis of liquid / gas products and catalyst reusability
situ generated on the catalyst surface led to easier hydrogen diffusion
and higher hydrogenolysis capacity [52,53]. These active H radicals can GC-MS measurements were conducted to analyze the volatile frac­
react with the reaction intermediates rapidly through catalytic transfer tion of HDO oil, and reflect the effect of Pt/CeCrO2− x catalyst on HDO in
hydrogenation, thereby allowing the reaction to proceed in a positive depth. Based on the complex chemical composition of bio-oil, the spe­
direction all the time. The application of this “borrowed” hydrogen cific spectra and main products in bio-fuel are shown in Fig. 4 and
strategy is a possible alternative technique for catalytic hydrogenation Table S2. The organic molecules with lower molar mass may be evap­
in biomass upgrading in terms of safety and easy control [54]. orated during the evaporation of water molecules. After 10 h reaction,
In general, the multifunctional Pt/CeCrO2− x catalyst designed in this large amounts of ethyl acetate, benzene, 1,3-dimethyl-, 1-Butanol, 2-

5
W. Chou et al. Applied Catalysis B: Environmental 316 (2022) 121625

Fig. 3. Measurement of the HDO products (a) Comparison of conversion with and without catalyst at the same reaction times (b) Effect of reaction temperature on
the yield of product fractions, (c) Product yields for hydro-liquefaction reactions under hydrogen. (d) Product yields for hydro-liquefaction reactions under nitrogen.
Reaction conditions: 300 ℃, 5 MPa H2 or 1 MPa N2, feedstock (1 g), catalyst (0.2 g), ethanol (20 g).

Scheme 2. Typical reaction networks for ethanol dehydrogenation.

Furanmethanol, tetrahydro-, Propylene Glycol, 1,2-Ethanediol, Phenol, component could also be converted into monophenols [16,29].
Phenol, 2-methoxy-4-methyl- as well as other undefined intermediates Furthermore, the products are classified according to functional groups
in the acetone phase were detected by GC-MS (Fig. 4a). Based on the as shown in Table 2, which are mainly composed of alcohols, phenols,
distribution of products, Pt/CeCrO2− x catalyst is capable of converting esters, hydrocarbons, ethers, aldehydes, acids and ketones [44]. Without
three components of lignocellulose (cellulose, hemicellulose, and catalyst (Table 2, Entry 1), the oxygenated compounds such as unsatu­
lignin). Cellulose and hemicellulose were selectively converted to al­ rated fatty acids, esters, aldehydes and ketones dominated the structures
cohols and diols with a yield approximately 45 wt%, whereas, the lignin of bio-oils. Subsequently, we investigated the effect of the support on the

6
W. Chou et al. Applied Catalysis B: Environmental 316 (2022) 121625

Fig. 4. Analysis of the liquid products. (a) Typical GC-MS spectra of the reaction effluent obtained from direct conversion of birch (b) volatile parts of product (blank,
Pt/CeO2, Pt/CeCrO2− x under H2 and N2, respectively) and (c) the stability test of Pt/CeCrO2− x catalyst. Reaction conditions: 300 ℃, 5 MPa H2, feedstock (1 g),
catalyst (0.2 g), ethanol (20 g).

HDO reaction and found that the addition of the CeCrO2− x had a certain HDO effect. It can be seen that Pt/CeCrO2− x catalyst has the best HDO
positive effect on the experiment (Table 2, Entry 2). The relative content performance (Fig. 4b and Table 2, Entry 5). The acid and aldehyde/
of the alcohols reached 25.69%, which may be due to the fact that ketone contents were reduced from 17.52% and 21.13–2.46% and
CeO2-based catalyst has a certain basicity, which can promote Guerbet 6.14%, respectively. With the increase of the reaction time, the degree of
reaction and retro-aldol condensation of glucose and xylose [50,55]. HDO is further enhanced [56], and the content of the oxygenated
Specifically, the catalytic performance of commercial Pt/SiO2 catalysts compounds in the bio-oil decreases, while that of the saturated hydro­
without basicity is inferior to that of CeO2 catalysts (Table 2, Entry 3), carbon increases (Table 2, Entry 6). In addition, we observed that the
and the catalytic performance was slightly worse than that of Pt/CeO2. Guerbet reaction of ethanol occurred in this experiment, leading to an
Furthermore, the Pt/CeCrO2− x catalyst can be used to promote the increase of the content of alcohols [51]. However, the Pt/CeCrO2− x

7
W. Chou et al. Applied Catalysis B: Environmental 316 (2022) 121625

Table 2
Component analysis of various catalysts.
Entrya Catalyst Relative content (%)

Esters Hydro carbons Acids/anhydride Ketones/Aldehyde Phenols Alcohols Ethers

1 —— 25.25 —— 17.52 21.13 15.29 14.33 6.48

2 CeCrO2− x 23.32 —— 11.68 15.87 14.86 24.69 5.83
3 Pt/SiO2 16.75 0.72 13.37 12.85 19.91 28.26 6.27
4 Pt/CeO2 17.64 2.67 10.57 9.82 18.05 35.57 5.10
5 Pt/CeCrO2− x 16.68 4.04 2.46 6.14 19.44 42.45 3.83
6b Pt/CeCrO2− x 16.95 5.23 1.86 4.43 21.14 48.32 2.02
7c Pt/CeCrO2− x 18.02 4.80 4.27 6.69 19.15 41.33 4.54
a
The reactions were conducted at 300 ℃, 5 MPa H2, feedstock (1 g), catalyst (0.2 g), ethanol (20 g), 600 rpm, 5 h;
b
10 h;
c
1 MPa N2, 10 h.

catalyzed Guerbet and esterification reactions are rarely discussed. diffraction peaks [60]. However, the results obtained from present
Huang suggested that Guerbet and esterification reactions can suppress experiment was in the opposite direction. ICP-AES results of
the repolymerization reactions of larger fragments, which is consistent Pt/CeCrO2− x catalyst after three cycles were listed in Table S4. Though
with the results obtained in this paper [57]. According to the reaction we speculate that the catalyst has good anti-sintering ability and high
mechanism in Scheme 2, ethanol first undergoes dehydrogenation re­ stability, certain degree of leaching and loss of catalyst is inevitable after
action, and the H radicals removed in the above dehydrogenation re­ long-term reaction.
action, to a certain extent, can take the place of the external source of Moreover, the morphology of the spent catalysts was characterized
hydrogen. In addition, the acetaldehyde originated from ethanol can be by using HAADF-STEM, STEM-EDX elemental mapping, and SEM to
further converted to high-carbon alcohols such as n-butanol by aldol visualize the morphology, metal distribution, and elemental composi­
condensation [58]. The application value of n-butanol is much higher tion of the catalysts as shown in Fig. S7 and, Fig. S8. It can be seen from
than that of ethanol, and the former has higher energy and blending the figure that the distribution of metal Pt is still uniform. There is no
ratios as well as similar octane numbers to gasoline [59]. We have large-scale agglomeration, and the particle size of Pt is increased from
demonstrated, through the control experiments listed in Table S3, that 1.2 nm to 3.86 nm, which may be attributed to the addition of Cr to
hydrogenation product n-butanol and its (acetal and esterification re­ improve the SMSI. In summary, after the catalyst reaction, there is a
action) derivatives occupy an appreciable portion of the liquid phase. certain degree of particle size growth and metal loss, which may explain
The results also showed that the insufficient hydrogenation would in­ the reduction of the activity [47]. As can be seen from the SEM image
crease the selectivity of esters, but the excessive hydrogenation would shown in Fig. S8, no residual sawdust was visible after 5 h, and there was
lead to more alcohols. The difference between the hydrogenation no major difference in the morphology of the catalyst before and after
amounts may be transferred to the lignocellulosic hydro-liquefaction the reaction. The above results are in agreement with the XRD patterns
reaction. However, the trade-off is not the focus of this paper, which, of the sawdust (orange) and the remaining solid (green) presented in
instead, only plays a role in in-situ hydrogen production. We will spe­ Fig. 1.
cifically investigate the hydrogen transfer process in our future work. To further evaluate the HDO efficiency of the Pt/CeCrO2− x catalyst,
The composition of the gaseous phase after the reaction was quan­ efforts were made to compare the elemental distribution in the feed­
tified by using tandem gas chromatography (GC) with thermal con­ stocks and biofuels. As shown in Table 3, the weight averages of C, H
ductivity detector (TCD) and flame-ionization detector (FID). As and, O in the feedstocks are 46.42 wt%, 5.56 wt%, and 48.02 wt%,
expected, seen from the GC spectrum of Fig. S6, a considerable amount respectively, which include a high oxygen content and a low HHV value.
of hydrogen is generated, i.e., about 41.26 mmol. In addition, there are Due to the hydrodeoxygenation reaction, the abundance of hydrogen is
some decarbonylation and decarboxylation products, such as CO and increased from 5.56 wt% to 9.51 wt%, while that of oxygen is decreased
CO2. Using ethanol as the solvent in the catalytic system, the generation from 48.02 wt% to 19.55 wt%. Besides, the degree of HDO is increased
of a small amount of ethylene and acetylene in the product is inevitable with the increase of reaction time. As expected, a considerable increase
[58]. Based on better HDO performance of the Pt/CeCrO2− x catalyst, the in the high heating value (HHV) of bio-oil from 15.1 MJ⋅kg− 1 to
gas phase product contains high content of CH4 probably originated
from the hydrogenation of CO and CO2 in the presence of H radicals.
Generally speaking, hydrogenation reactions, especially in the presence Table 3
of Pt/CeCrO2− x catalysts, can facilitate the removal of excess oxygen Elemental analysis of feedstocks and products for Pt/CeCrO2− x participated
atoms from the system. Compared with the fact that NiAl alloy catalysts HDO system.
enables nearly complete conversion of lignocellulose to natural gas, this Sample Element content
catalytic system converts half of the solid biomass into natural gas and
C (wt H (wt O (wt H/C O/C HHV
the other half into fuel, achieving complete conversion without gener­ %) %) %)a (MJ⋅kg− 1)b
ating coke, which is more valuable for applications [30].
lignocellulose 46.42 5.56 48.02 1.44 0.78 15.1
To investigate the stability of the Pt/CeCrO2− x catalyst, three Pt/CeCrO2− x 64.46 8.67 26.87 1.63 0.31 30.5
sequential batch experiments were conducted under the same conditions 5 hc
(Fig. 4c). After three cycles of experiments with the catalyst, the con­ Pt/CeCrO2− x 70.94 9.51 19.55 1.61 0.21 34.2
version rate and HDO capacity were reduced to certain extent. To figure 10 hc
Pt/CeCrO2− x 65.3 7.88 26.82 1.45 0.31 29.6
out whether the structure of the used catalyst was altered, XRD char­ 5 hd
acterization was performed as shown in Fig. 1. Crystalline fluorite Pt/CeCrO2− x 68.86 8.37 22.87 1.44 0.25 31.1
structure of ceria was exhibited. It is interesting to see that the height of 10 hd
the XRD diffraction peaks of used catalysts is generally reduced a
calculated by difference between 100 wt%;
compared with fresh catalysts. To our best knowledge, after a few b
calculated according to Eq1.
rounds of reaction of the catalyst, the metals are very likely to c
5 MPa H2
agglomerate or sinter, leading to an increase of the height of the d
1 MPa N2

8
W. Chou et al. Applied Catalysis B: Environmental 316 (2022) 121625

approximately 34.2 MJ⋅kg− 1 was observed by using the Pt/CeCrO2− x CeO2 crystal lattice to form a solid solution structure. Compared with the
catalyst for 10 h, which is in agreement with the GC–MS result that undoped CeO2, it increases the dispersion of Pt on the surface of the
liquefaction bio-oil contained less oxygenated products[61]. In this case, catalyst, which is also confirmed by DRUV− vis and STEM-EDX. In the
the Pt/CeCrO2− x catalyst may have good HDO performance in bio-fuels, previous catalyst screening studies, we also examined the nature of
which, at the same time, also shows promising catalytic performance catalysts with different ratios between ceria and chromium, as shown in
under nitrogen atmosphere. However, it may be due to the relatively low Fig S9.
autogenous pressure of the system in a sealed autoclave, a lower degree
of hydrodeoxygenation than that of external hydrogen is obtained. Even 4.1. Effect of solid solution on hydrogen activation
so, the in-situ hydrogen transfer process of lignocellulose into high en­
ergy density bio-fuel is still of significant research value [54]. It can be inferred from the above TEM and UV− vis spectroscopy that
In addition to the HHV results, a Van Krevelen diagram is used to the solid solution has a significant effect on the particle size of Pt. Many
compare the molar ratios of O/C versus H/C for the HDO bio-oil [62]. literatures have shown that the particle size of the active metal Pt has an
With the introduction of catalyst, the O/C ratio is decreased by reducing important influence on the hydrogenation reaction [65,66]. The for­
the oxygen content in liquefaction bio-oil. It can be seen from Table 3 mation of solid solution is substantially beneficial to the improvement of
and Fig. 5 that with the decrease of O/C ratio, high HHV value is the dispersion of the catalyst, which may be related to the interaction
markedly increased. The lowest O/C values and highest H/C values were between the metal and support [67]. H2-TPR experiments were con­
observed for the bio-oil produced with Pt/CeCrO2− x catalyst in 10 h, ducted to analyze the redox properties and the metal-support in­
which are much lower than our prior results obtained without catalyst. teractions of catalysts [68]. The TPR profiles (Fig. 6) illustrate that the
As can be seen from the illustration, the final liquid products obtained samples presented different redox characteristics. For pure CeO2, there
exhibits a yellowish color due to the inability to remove all the oxygen is no obvious reduction peak, and the peak at 491 ℃ could be attributed
[63]. to the surface reduction of cerium atoms or surface oxygen [36]. The
reduction peak at above 700 ℃ is considered to be the bulk reduction of
4. Investigation of structure-activity relationship and CeO2 to Ce2O3 [39]. Focusing on the reduction peak of the CeCrO2− x
depolymerization mechanism support below 500 ◦ C, the formation of a solid solution greatly increased
the amount and mobility of reactive surface oxygen. For the Pt/CeO2
An interesting phenomenon in Fig. 1 is that the 2θ value of the and Pt/CeCrO2− x sample, the new multiple peaks below ~250 ◦ C can be
strongest (111) peak increased, and the interplanar distances of CeO2 assigned to the mixed reduction of PtO to metallic Pt and the reactive
decreased slightly (Table 4). There is a high probability that Cr3+ cations surface oxygen of the supports [40].
were dissolved in the CeO2 lattice, forming a solid solution structure Compared with Pt/CeO2, the peak of Pt/CeCrO2− x inclines to the
[43]. In the pure CeO2, the Ce4+ cation has a coordination number (CN) high temperature. It is probably because that the SMSI is enhanced after
of 8 and ionic radius of 0.97 Å. Assuming that Cr dissolves into the the substitution of Cr3+ for Ce4+, which can effectively anchor and
lattice of CeO2, Cr and Ce should have the same CN, i.e., 8 for both [39]. improve the dispersion of the active metal, thereby inhibiting the
Generally speaking, the ionic radius of Cr3+ at CN 6 is 0.62 Å, which is migration and agglomeration of atoms or small clusters [39,69]. The
smaller than that of 0.87 Å for Ce4+ at CN 6. Through analogy, the radius latest literature shows that too strong interaction can trigger Ostwald
of the Cr3+ ion with CN 8 is also smaller than that of the Ce4+ ion with ripening, whereas too weak interaction stimulates particle migration
CN 8. Therefore, with Cr3+ replacing portion of Ce4+ in the support, the and coalescence [60]. It can be seen that the doping of Cr enhances the
crystal lattice shrinks, and the size of the crystal lattice decreases [39]. SMSI of the conventional Pt/CeO2 catalyst, thus improving the stability
The comparison between Fig. 2 and Fig. S2 shows that the inter­ of the catalyst. At the same time, it avoids the problem that the metal is
planar spacings in Pt/CeCrO2− x are slightly smaller than those in Pt/ difficult to be reduced.
CeO2, which provides an additional evidence to the formation of a solid
solution in Pt/CeCrO2− x [64]. To sum up, the XRD and HRTEM results 4.2. Effect of solid solution on acid sites
show that in the Pt/CeCrO2− x catalyst, Cr3+ ions are inserted into the
The solid solution forms many new acidic sites and the catalyst
surface acidity plays an important role in lignocellulose hydro-
liquefaction and HDO reaction, which in turn affects the reaction
properties related to the acidic sites [70]. Therefore, NH3-TPD was first
employed to compare the acidities of the catalysts (Fig. 7a, Table S5),
and the results shows a significant increase in NH3 adsorption over the
CeCrO2− x and Pt/CeCrO2− x catalyst. For pure CeO2 or Pt/CeO2 catalyst,
the surface acidities were relatively weak [36]. It can be seen from the
resulted NH3-TPD profile that CeCrO2− x has a broad peak centering at
ca.110–250 ℃, which can be assigned to the desorption from weak to
medium acid sites [61]. When loaded with metal Pt, the amount of
medium strength acid decreases, while that weak acid increases signif­
icantly, indicating that new acid sites were generated by metal incor­
poration. Taking a comprehensive consideration of the previous studies,
we inferred that one of the main reasons for the high catalytic activity of
Pt/CeCrO2− x lies on its balanced acidity, leading to an effective dehy­
dration (sufficient acidity) and a low degree of condensation coking
reaction (not too high acid strength) [39,48]. Too weak acidity, leads to
a low degree of depolymerization of lignocellulose, and the failure of the
complete proceeding of the reaction. On the other hand, if the acidity is
too strong, the degree of dehydration is drastic, and the intermediate
Fig. 5. Van Krevelen diagram measurement. Relationship between O/C and H/ tends to carbonize and coke [33].
C of the lignocellulose and HDO oil, and the illustration is the product of To determine the type of acid in Pt/CeCrO2− x catalyst, in-situ Pyri­
this experiment. dine-FTIR experiments were conducted with the parameters shown in

9
W. Chou et al. Applied Catalysis B: Environmental 316 (2022) 121625

Table 4
Physicochemical properties of the reduced catalysts and the supports.
Catalysts CeO2 crystallite size CeO2 particle size Pt cluster size Interplanar distances CeO2 surface area pore volume pore size
(nm)a (nm)b (nm)b (111) (nm)b (m2⋅g− 1) (cm3⋅g− 1) (nm)

CeO2 11.5 14.5 52 0.13 7.2

CeCrO2− x 10.4 10.6 55 0.17 9.8
Pt/CeO2 11.7 14.8 22.1 0.311 38 0.13 8.4
Pt/ 10.2 10.6 1.28 0.308 43 0.15 9.5
CeCrO2− x

a
XRD results for the CeO2 phase in the samples.
b
HRTEM results for the CeO2 phase in the samples.

shows a contact angle of 51.0◦ . The decrease of the contact angle of the
catalyst may be related to the change of surface energy due to the fact
that the dopped Cr. The wettability of the catalyst facilitates the
enrichment of substrates around the catalytic site, and plays a crucial
role in the activity and selectivity of catalysts [75]. Improved dispersion
of the catalyst in ethanol increases the mass transfer efficiency, thereby
greatly improving the depolymerization of lignocellulose. This is one of
the reasons for achieving full utilization of biomass in this experiment.
This property will greatly improve the catalyst dispersion in the system,
more in line with the characteristics of slurry hydrogenation process,
which will promote the industrial continuous feeding reaction of
biomass.

4.3. Effect of solid solution on oxygen vacancy

A certain amount of literature has been published, which use Roman

spectra and Electron Paramagnetic Resonance (EPR) to demonstrate that
Cr doping leads to the formation of more surface oxygen vacancies [7,
39,43]. Therefore, we conducted XPS spectra to investigate the effect of
Cr3+ doping on the surface composition (Fig. 8), and quantify the oxy­
Fig. 6. H2-TPR profiles of the as-prepared catalysts.
gen vacancy concentration, as summarized in Table 5. For the Ce 3d
spectra (Fig. 8a), each catalyst was deconvoluted into ten peaks. The six
Fig. 7b and Table S6. The band at 1490 cm− 1 can be attributed to the peaks at 916.4 eV (u′′′ ), 907.5 eV (u′′ ), 900.6 eV (u), (898.3 eV) (v′′′ ),
adsorption of pyridine at Brønsted and Lewis acid sites at the same time 888.2 eV (v′′ ), and 882.4 eV (v), are assigned to surface Ce4+, and the
[26]. The band at 1450 cm− 1 and 1610 cm− 1 corresponds to the other four peaks at 903.7 eV (u′ ), 898.8 eV (u0), 884.9 eV (v′ ), and
adsorption of pyridine at the Lewis acid sites, and that at 1540 cm− 1 and 881.1 eV (v0) are assigned to surface Ce3+. The presence of Ce3+ ions in
1647 cm− 1 has the characteristic of the adsorption of pyridine at ceria lattice can maintain electrostatic equilibrium, and generate oxygen
Brønsted acid sites, indicating that Pt/CeCrO2− x possesses both Brønsted vacancies [39]. To quantify the relative surface Ce3+ amount, the
and Lewis acid sites. Many previous literatures have shown that CeO2 Ce3+/(Ce3+ + Ce4+) ratios were calculated by using the sum of the in­
has only a small amount of Lewis acid[36]. However, when being tegrated areas of the Ce3+ peaks divided by the sum of the integrated
modified with a small amount of Cr, a larger amount of Brønsted acid areas of the U and V peaks [44]. As can be seen from the quantitative
appeared, and we calculated the remaining charge of the system based results of the experiments, the doping of Cr increased the content of Ce3+
on the theory proposed by Kozo Tanabe [71]. The specific details are from 22.7% to 32.62% compared with the undoped catalyst.
shown in Supplementary Note S1. The excess of negative charge requires In addition, CeO2 has unique surface characteristics such as rich
a positive charge to balance the frontal electroneutrality of the system, oxygen vacancies (Vö) and strong oxygen affinity, which has a strong
so that Brønsted acid is formed on the Cr atom. Lewis acid sites were adsorption and activation effect on oxygen-containing biomass raw
mainly derived from the Ce4+ cations with surface oxygen defects and materials [76]. This is an obvious advantage over other catalysts in
some of the unsaturated Cr cations, whereas Brønsted acid sites were biomass conversion. Therefore, to provide direct evidence for the effect
related to Cr-OH and [Ce4+]-OH formed on different Cr species [72]. of oxygen vacancies, the asymmetric O 1 s spectra of the two Pt catalysts
Nelson [73] also proposed the mechanism of HDO at the bifunctional (Fig. 8b) were analyzed, which were deconvoluted into two peaks
Ru/TiO2, and H2 is activated on Ru particles and heterolytical interface considering that the samples were subjected to H2 reduction, and XPS
dissociates across the interface to protonate a bridging hydroxyl group experiments were performed in a very short time. The low binding en­
on TiO2, generating a Brønsted acid site. ergy peak of about 528–531 eV can be the attributed to lattice oxygen
Combined with the above analysis, it is speculated that Brønsted acid (Olatt). While the high binding energy peak at about 531.6 eV can be
has more abundant bridged surface hydroxyl groups, thereby improving attributed to a mixture of surface adsorbed oxygen species (Oads),
the surface energy and wettability of the catalyst as well as the disper­ including surface OH and carbonate (CO2- 3 ) groups. As previously re­
sion in ethanol solution [74]. The photograph of the catalyst particles ported, the approximately same CO2− 3 molar ratio on both Pt/CeO2 and
highly dispersed in ethanol is shown in Fig. S10. With the addition of Pt/CrCeO2− x indicates the same amount of CO2− 3 on both catalysts [39].
Pt/CeCrO2− x catalyst into the solution, it is immediately dispersed in Therefore, combining the experimental results and those obtained from
ethanol, showing a turbid state. In contrast, the Pt/CeO2 catalyst just the previous studies, it can be concluded that the addition of Cr can
settles on the bottom of the autoclave without the occurrence of the significantly increase the concentration of oxygen vacancies and Ce3+ in
aforementioned dispersion phenomenon. The effect of Cr doping on the the catalyst. Other characterizations of this catalyst, such as Raman and
alcoholophilicity of the catalyst is shown in Fig. 7c and d. The Pt/CeO2 EPR, have been reported elsewhere with similar results [7,39,76,77].
catalyst has a contact angle of 132.8◦ , while, the Pt/CeCrO2− x catalyst The easily reversible redox cycle of cerium ions (Ce3+/Ce4+) redox pairs

10
W. Chou et al. Applied Catalysis B: Environmental 316 (2022) 121625

Fig. 7. (a) NH3-TPD profiles of catalysts, (b) In-situ Pyridine-FTIR spectra of Pt/CeCrO2− x obtained after evacuation at different temperatures, (c) Image of contact
angles on Pt/CeO2. (d) Image of contact angles on Pt/CeCrO2− x.

and the existence of oxygen vacancies lead to the production of non­ 4.4. Effect of solid solution on pore structure
stoichiometric CeO2− x nanomaterials, offering ceria redox properties
and special Lewis acid-base active sites, which may be one of the key To investigate the influence of Cr3+ cations on the textural proper­
reasons for gaining a better catalytic activity [36]. ties, the samples were analyzed by using N2 sorption. The data of surface
According to the Pt content determined by XPS and ICP-AES, as area, pore volume and average pore diameter are summarized in
shown in Table 5, the amount of surface Pt in Pt/CrCeO2− x was higher Table 4. All the samples showed a typical IV isotherm with an H3-type
than that in Pt/CeO2, further verifying that the incorporation of Cr3+ hysteresis loop (Fig. S12), showing a structure with mesopores [78]. The
facilitated Pt dispersion. The Pt 4 f peaks could be resolved to two surface area, pore volume, and pore size of Pt/CeCrO2− x were
components at BEs of 71.4 and 72.2 eV, which are assigned to Pt0 and 43 m2⋅g− 1, 0.15 cm3⋅g− 1, and 9.5 nm, respectively. While the BET sur­
Pt2+, respectively. In addition, based on the shift of binding energy, it is face area and pore size of Pt/CeCrO2− x are a litter bit larger than that of
speculated that the metal of Cr provides electrons to the system and Pt, Pt/CeO2. There are many excellent literatures reporting that the trend of
and Ce accepts electrons. The Pt in metallic state is generally considered oil yield was positively correlated with the average pore size of the
as the active center for catalytic hydrogenation reactions. In the case catalyst. It suggests that larger pore size of catalyst may allow larger
that Pt receives electrons, it can better maintain the metallic state, thus species to fit in and undergo consecutive reaction during lignocellulose
facilitating the activity of hydrogenation reaction and the H-Spillover depolymerization reaction. Of course, it is not necessarily to have a
effect when Pt and oxide are combined (Fig. S11a). For the Cr 2p spectra, larger size catalysts for small and medium molecules. The catalysts with
the peaks at ~576 and~586 eV correspond to 2p1/2 and 2p3/2 of Cr3+ large pores and surface area tend to adsorb larger and complex in­
cations, verifying that Cr cations were doped in the CeO2 lattice as Cr3+( termediates, making it difficult to decompose and form carbon deposits
Fig. S11b). In the meantime, more Ce3+ is accompanied by the genera­ [79]. Therefore, combined with the results obtained in this experiment,
tion of high concentration of oxygen vacancies. The synergistic effect of in a complex raw woody biomass hydro-liquefaction system, a medium
both metal and oxygen vacancies is more conducive to the breaking of surface area and pore size may be available to avoid coke and carbon
chemical bonds, thereby avoiding the formation and condensation of deposition.
macromolecules [66]. The transfer of electrons indicates the existence of
metal-support interaction. 5. Proposed reactions routes and depolymerization mechanism

Based experimental data, Scheme 3 showed a proposed mechanism

of the main tandem and parallel reaction pathways occurring in the

11
W. Chou et al. Applied Catalysis B: Environmental 316 (2022) 121625

Fig. 8. XPS spectrum of catalysts: (a) Ce 3d, (b) O 1 s.

Table 5
XPS and ICP-AES results of catalysts.
Samples XPS ICP-AES

Ce3+/ (Ce3+ + Ce4+) molar ratio (%) Oads/ (Oads + Olatt) molar ratio (%) Pt (wt%) Cr/ (Cr+Ce) molar ratio (%) Pt (wt%)

CeO2 22.85
CeCrO2− x 29.37 11.10
Pt/CeO2 22.70 22.31 2.6 1.73
Pt/ CeCrO2− x 32.62 40.14 2.9 12.03 1.85

Scheme 3. proposed reactions routes for the valorization of lignocellulosic biomass.

12
W. Chou et al. Applied Catalysis B: Environmental 316 (2022) 121625

catalytic liquefaction and HDO of lignocellulose. First, birch could be the wettability and dispersion rate of the catalyst in ethanol are signif­
fragmented into smaller oligomeric compounds by breaking β-1,4 icantly improved, providing intimate contact between diverse sites for
glucosidic bonds and β-O-4 ether bonds, which is followed by the the HDO reaction, which has been rarely reported in other literature. It
hydrogenolysis of the generated compounds into monomeric in­ is evident that this scheme is feasible to be accomplished at large scale
termediates [1,61]. A catalyst with sufficient strength and density of with both environmental and economic benefits. Moreover, this catalyst
acid, especially protonic acid, can be used to effectively enhance the can efficiently catalyze the Guerbet reaction at the same time. We
cracking of lignin-derived oligomers [21,71]. The essence of complete anticipate that it will be applied to more interdisciplinary subjects, thus
conversion without residue lies in the balance between the rate of bringing more opportunities for further development.
depolymerization and stabilization [48]. In this in-situ generated
hydrogen system, Pt/CeCrO2− x catalyst can be used to promote the CRediT authorship contribution statement
depolymerization of lignin, and quench radicals and unstable in­
termediates formed during depolymerization. This suppression of coke Dong Liu, Weichao Chou and Zhiheng Li designed the studies and
formation is a result of reduced intermediates trapping inside catalyst, finished the experiments. Weichao Chou, Xin Chou, Peng Wu, and Hua
mainly based on the mesoporosity and moderate acid strength of cata­ Liu performed the material characterizations and analyzed the experi­
lyst [78]. Fortunately, Pt/CeCrO2− x catalyst has a moderate acid mental results. Weichao Chou, Dong Liu wrote the manuscript. Dong
strength, which improves the degree of depolymerization, and prevents Liu, Chongchong Wu, and Weizhen Li supervised the project and
strong acidity from retaining large amounts of phenolic compounds reviewed the manuscript.
adsorbed on the catalyst surface. These smaller intermediate fragments
are able to diffuse into the pore of the catalyst, and subsequently un­
dergo a hydrodeoxygenation reaction. Declaration of Competing Interest
On the other hand, the catalyst and ethanol undergo an efficient
Guerbet reaction, facilitating the hydrogen transfer process and gener­ The authors declare that they have no known competing financial
ating hydrogen gas [52]. The specific details are shown in Supplemen­ interests or personal relationships that could have appeared to influence
tary Note S2. These active hydrogens are applied as reducing equivalents the work reported in this paper.
necessary for the in-situ hydrogenolysis and HDO reaction. The acetal­
dehyde derived from ethanol can be further converted to higher alco­ Acknowledgements
hols, such as 1-butanol by aldol condensation. Ethanol and acetaldehyde
in turn undergo an acetal reaction to produce a certain amount of ethane The authors gratefully acknowledge financial support from the Na­
and, 1,1-diethoxy, which can significantly increase the octane number tional Natural Science Foundation of China (22108309), Key Research
(ON). The material is widely used as an efficient anti-knock agent for and Development Project (Major Project of Scientific and Technological
motor gasoline [80]. The strong interaction occurs between the oxo­ Innovation) of Shandong Province (2020CXGC010308), and the Taishan
philic CeO2 support and oxygen-containing functional groups, such as Scholar Program of Shandong (No. ts20190919).
carbonyl groups. In addition, the addition of Cr significantly increases
the oxygen vacancy content of the catalyst, further enhancing the Appendix A. Supporting information
hydrodeoxygenation process. Mesoporous Pt/CeCrO2− x catalyst with
sufficient acid site density and mild acid strength has a well-balanced Supplementary data associated with this article can be found in the
acidity which leads to an efficient dehydration activity and a low online version at doi:10.1016/j.apcatb.2022.121625.
phenolic trapping potential.
In general, oxophilicity, alcoholophilicity, sufficient acidity, oxygen References
vacancies and active Guerbet reaction are the significant characteristics
of Pt/CeCrO2− x catalysis system, making this catalyst highly effective for [1] M. Antar, D. Lyu, M. Nazari, A. Shah, X. Zhou, D.L. Smith, Biomass for a sustainable
bioeconomy: an overview of world biomass production and utilization, Renew.
the complete conversion of lignocellulose into high energy density, bio-
Sustain. Energy Rev. 139 (2021), 110691.
oil and natural gas. [2] S.S. Wong, R. Shu, J. Zhang, H. Liu, N. Yan, Downstream processing of lignin
derived feedstock into end products, Chem. Soc. Rev. 49 (2020) 5510–5560.
[3] Y. Ding, B. Shan, X. Cao, Y. Liu, M. Huang, B. Tang, Development of bio oil and bio
6. Conclusions
asphalt by hydrothermal liquefaction using lignocellulose, J. Clean. Prod. 288
(2021), 125586.
The objective of this paper is to achieve the complete utilization of [4] J. Gupta, K. Papadikis, E.Y. Konysheva, Y. Lin, I.V. Kozhevnikov, J. Li, CaO catalyst
raw lignocellulose in one step by cleverly designing and utilizing the for multi-route conversion of oakwood biomass to value-added chemicals and fuel
precursors in fast pyrolysis, Appl. Catal. B Environ. 285 (2021), 119858.
synergistic catalysis between polymetallic material and acid-base to [5] X. Dou, W. Li, C. Zhu, X. Jiang, Catalytic waste Kraft lignin hydrodeoxygenation to
obtain chemicals and bio-oil with high energy density. The Cr-doped liquid fuels over a hollow Ni-Fe catalyst, Appl. Catal. B Environ. 287 (2021),
catalyst based on CeO2 and Pt serves multiple purposes, including 119975.
[6] J. Park, H.S. Cahyadi, U. Mushtaq, D. Verma, D. Han, K.-W. Nam, S.K. Kwak,
catalyzing substrate hydrogenolysis and hydrodeoxygenation as well as J. Kim, Highly efficient reductive catalytic fractionation of lignocellulosic biomass
the ethanol Guerbet reactions in-situ hydrogen production. This one-pot over extremely low-loaded Pd catalysts, ACS Catal. 10 (2020) 12487–12506.
“hydro-liquefaction process” is quantitative, giving little or no biochar [7] M. Li, P. Wang, Z. Ji, Z. Zhou, Y. Xia, Y. Li, S. Zhan, Efficient photocatalytic oxygen
activation by oxygen-vacancy-rich CeO2-based heterojunctions: synergistic effect
residual. of photoexcited electrons transfer and oxygen chemisorption, Appl. Catal. B
As shown by the N2 isothermal adsorption-desorption curve, HR- Environ. 289 (2021), 120020.
TEM, XRD and XPS analysis, Pt/CeCrO2− x was confirmed as oxygen- [8] L. Leng, J. Li, X. Yuan, J. Li, P. Han, Y. Hong, F. Wei, W. Zhou, Beneficial
synergistic effect on bio-oil production from co-liquefaction of sewage sludge and
deficient mesopores nano-particles, which deepen the depolymeriza­ lignocellulosic biomass, Bioresour. Technol. 251 (2018) 49–56.
tion and HDO process. The H2-TPR, NH3-TPD and Pyridine-FTIR ex­ [9] H.R. Guimarães, J.M. Bressanin, I.L. Motta, M.F. Chagas, B.C. Klein, A. Bonomi,
periments further emphasized that the introduction of Cr can increase R. Maciel Filho, M.D.B. Watanabe, Bottlenecks and potentials for the gasification of
lignocellulosic biomasses and Fischer-Tropsch synthesis: a case study on the
the SMSI and surface acidity. One of the main reasons for the high
production of advanced liquid biofuels in Brazil, Energy Convers. Manag. 245
catalytic activity of Pt/CeCrO2− x lies in its well-balanced acidity which (2021), 114629.
results in both effective dehydration (sufficient acidity) and low active [10] J. Xu, L. Dai, C. Zhang, Y. Gui, L. Yuan, Y. Lei, B. Fan, Ionic liquid-aided
intermediates trapping potential (not too high acid strength). The oxo­ hydrothermal treatment of lignocellulose for the synergistic outputs of carbon dots
and enhanced enzymatic hydrolysis, Bioresour. Technol. 305 (2020), 123043.
philic CeO2 doped with Cr changes the properties of the functional [11] C. Yuan, S. Wang, B. Cao, Y. Hu, A.E.-F. Abomohra, Q. Wang, L. Qian, L. Liu, X. Liu,
groups on the catalyst surface. Compared with the conventional CeO2, Z. He, Optimization of hydrothermal co-liquefaction of seaweeds with

13
W. Chou et al. Applied Catalysis B: Environmental 316 (2022) 121625

lignocellulosic biomass: merging 2nd and 3rd generation feedstocks for enhanced [38] P.D. Muley, C. Henkel, K.K. Abdollahi, C. Marculescu, D. Boldor, A critical
bio-oil production, Energy 173 (2019) 413–422. comparison of pyrolysis of cellulose, lignin, and pine sawdust using an induction
[12] J. Remón, M. Casales, J. Gracia, M.S. Callén, J.L. Pinilla, I. Suelves, Sustainable heating reactor, Energy Convers. Manag. 117 (2016) 273–280.
production of liquid biofuels and value-added platform chemicals by [39] X. Xu, L. Liu, Y. Tong, X. Fang, J. Xu, D.-e Jiang, X. Wang, Facile Cr3+-doping
hydrodeoxygenation of lignocellulosic bio-oil over a carbon–neutral Mo2C/CNF strategy dramatically promoting Ru/CeO2 for low-temperature CO2 methanation:
catalyst, Chem. Eng. J. 405 (2021), 126705. unraveling the roles of surface oxygen vacancies and hydroxyl groups, ACS Catal.
[13] Y. Dong, B. Tian, F. Guo, S. Du, Y. Zhan, H. Zhou, L. Qian, Application of low-cost 11 (2021) 5762–5775.
Fe-based catalysts in the microwave-assisted pyrolysis of macroalgae and [40] C. Li, Y. Nakagawa, M. Yabushita, A. Nakayama, K. Tomishige, Guaiacol
lignocellulosic biomass for the upgradation of bio-oil, Fuel 300 (2021), 120944. hydrodeoxygenation over iron–ceria catalysts with platinum single-atom alloy
[14] P. Sudarsanam, H. Li, T.V. Sagar, TiO2-based water-tolerant acid catalysis for clusters as a promoter, ACS Catal. 11 (2021) 12794–12814.
biomass-based fuels and chemicals, ACS Catal. 10 (2020) 9555–9584. [41] C.P. Jiménez-Gómez, J.A. Cecilia, I. Márquez-Rodríguez, R. Moreno-Tost,
[15] H.V. Ly, B. Lee, J.W. Sim, Q.K. Tran, S.-S. Kim, J. Kim, B. Brigljević, H.T. Hwang, J. Santamaría-González, J. Mérida-Robles, P. Maireles-Torres, Gas-phase
H. Lim, Catalytic pyrolysis of spent coffee waste for upgrading sustainable bio-oil hydrogenation of furfural over Cu/CeO2 catalysts, Catal. Today 279 (2017)
in a bubbling fluidized-bed reactor: experimental and techno-economic analysis, 327–338.
Chem. Eng. J. 427 (2022), 130956. [42] L. Zeng, L. Cui, C. Wang, W. Guo, C. Gong, In-situ modified the surface of Pt-doped
[16] X. Ouyang, X. Huang, J. Zhu, M.D. Boot, E.J. Hensen, Catalytic conversion of lignin perovskite catalyst for soot oxidation, J. Hazard. Mater. 383 (2020), 121210.
in woody biomass into phenolic monomers in methanol/water mixtures without [43] P. Venkataswamy, D. Damma, D. Jampaiah, D. Mukherjee, M. Vithal, B.M. Reddy,
external hydrogen, ACS Sustain. Chem. Eng. 7 (2019) 13764–13773. Cr-doped CeO2 nanorods for CO oxidation: insights into promotional effect of Cr on
[17] M.R. Rover, A. Aui, M.M. Wright, R.G. Smith, R.C. Brown, Production and structure and catalytic performance, Catal. Lett. 150 (2020) 948–962.
purification of crystallized levoglucosan from pyrolysis of lignocellulosic biomass, [44] D. Chen, Q. Ma, L. Wei, N. Li, Q. Shen, W. Tian, J. Zhou, J. Long, Catalytic
Green Chem. 21 (2019) 5980–5989. hydroliquefaction of rice straw for bio-oil production using Ni/CeO2 catalysts,
[18] E.M. Villota, H. Lei, M. Qian, Z. Yang, S.M.A. Villota, Y. Zhang, G. Yadavalli, J. Anal. Appl. Pyrolysis 130 (2018) 169–180.
Optimizing microwave-assisted pyrolysis of phosphoric acid-activated biomass: [45] K.A. Resende, A.H. Braga, F.B. Noronha, C.E. Hori, Hydrodeoxygenation of phenol
impact of concentration on heating rate and carbonization time, ACS Sustain. over Ni/Ce1− xNbxO2 catalysts, Appl. Catal. B Environ. 245 (2019) 100–113.
Chem. Eng. 6 (2018) 1318–1326. [46] Y. Feng, B. Huang, C. Yang, Q. Shao, X. Huang, Platinum porous nanosheets with
[19] B. Tsegaye, C. Balomajumder, P. Roy, Optimization of microwave and NaOH high surface distortion and Pt utilization for enhanced oxygen reduction catalysis,
pretreatments of wheat straw for enhancing biofuel yield, Energy Convers. Manag. Adv. Funct. Mater. 29 (2019) 1904429.
186 (2019) 82–92. [47] C. Li, Y. Nakagawa, M. Tamura, A. Nakayama, K. Tomishige, Hydrodeoxygenation
[20] L. Offner-Marko, A. Bordet, G. Moos, S. Tricard, S. Rengshausen, B. Chaudret, K. of guaiacol to phenol over ceria-supported iron catalysts, ACS Catal. 10 (2020)
L. Luska, W. Leitner, Bimetallic nanoparticles in supported ionic liquid phases as 14624–14639.
multifunctional catalysts for the selective hydrodeoxygenation of aromatic [48] P. Sirous-Rezaei, D. Creaser, L. Olsson, Reductive liquefaction of lignin to
substrates, Angew. Chem. 130 (2018) 12903–12908. monocyclic hydrocarbons: ReS2/Al2O3 as efficient char inhibitor and
[21] P. Halder, S. Kundu, S. Patel, A. Setiawan, R. Atkin, R. Parthasarthy, J. Paz- hydrodeoxygenation catalyst, Appl. Catal. B Environ. 297 (2021), 120449.
Ferreiro, A. Surapaneni, K. Shah, Progress on the pre-treatment of lignocellulosic [49] J. Pang, M. Yin, P. Wu, X. Li, M. Zheng, T. Zhang, Advances in catalytic
biomass employing ionic liquids, Renew. Sustain. Energy Rev. 105 (2019) dehydrogenation of ethanol to acetaldehyde, Green Chem. (2021).
268–292. [50] X. Huang, C. Atay, T.I. Korányi, M.D. Boot, E.J. Hensen, Role of Cu–Mg–Al mixed
[22] Z. Cao, M. Dierks, M.T. Clough, I.B.D. de Castro, R. Rinaldi, A convergent approach oxide catalysts in lignin depolymerization in supercritical ethanol, ACS Catal. 5
for a deep converting lignin-first biorefinery rendering high-energy-density drop-in (2015) 7359–7370.
fuels, Joule 2 (2018) 1118–1133. [51] Z. Sun, As Couto Vasconcelos, G. Bottari, M.C. Stuart, G. Bonura, C. Cannilla,
[23] X. Wu, X. Fan, S. Xie, J. Lin, J. Cheng, Q. Zhang, L. Chen, Y. Wang, Solar energy- F. Frusteri, K. Barta, Efficient catalytic conversion of ethanol to 1-butanol via the
driven lignin-first approach to full utilization of lignocellulosic biomass under mild Guerbet reaction over copper-and nickel-doped porous, ACS Sustain. Chem. Eng. 5
conditions, Nat. Catal. 1 (2018) 772–780. (2017) 1738–1746.
[24] M.M. Abu-Omar, K. Barta, G.T. Beckham, J.S. Luterbacher, J. Ralph, R. Rinaldi, [52] Z.-K. Li, H.-T. Wang, H.-L. Yan, J.-C. Yan, Z.-P. Lei, S.-B. Ren, Z.-C. Wang, S.-
Y. Román-Leshkov, J.S. Samec, B.F. Sels, F. Wang, Guidelines for performing G. Kang, H.-F. Shui, Catalytic ethanolysis of Xilinguole lignite over layered and
lignin-first biorefining, Energy Environ. Sci. 14 (2021) 262–292. mesoporous metal oxide composites to platform chemicals, Fuel 287 (2021),
[25] Z. Sun, G. Bottari, A. Afanasenko, M.C. Stuart, P.J. Deuss, B. Fridrich, K. Barta, 119560.
Complete lignocellulose conversion with integrated catalyst recycling yielding [53] X. Shen, C. Zhang, B. Han, F. Wang, Catalytic self-transfer hydrogenolysis of lignin
valuable aromatics and fuels, Nat. Catal. 1 (2018) 82–92. with endogenous hydrogen: road to the carbon-neutral future, Chem. Soc. Rev. 51
[26] Q. Xia, Z. Chen, Y. Shao, X. Gong, H. Wang, X. Liu, S.F. Parker, X. Han, S. Yang, (2022) 1608–1628.
Y. Wang, Direct hydrodeoxygenation of raw woody biomass into liquid alkanes, [54] B.G. Reed-Berendt, D.E. Latham, M.B. Dambatta, L.C. Morrill, Borrowing hydrogen
Nat. Commun. 7 (2016) 1–10. for organic synthesis, ACS Cent. Sci. 7 (2021) 570–585.
[27] Y. Jing, Y. Guo, Q. Xia, X. Liu, Y. Wang, Catalytic production of value-added [55] S. Yamaguchi, M. Yabushita, M. Kim, J. Hirayama, K. Motokura, A. Fukuoka,
chemicals and liquid fuels from lignocellulosic biomass, Chem 5 (2019) K. Nakajima, Catalytic conversion of biomass-derived carbohydrates to methyl
2520–2546. lactate by acid–base bifunctional γ-Al2O3, ACS Sustain. Chem. Eng. 6 (2018)
[28] T.D. Matson, K. Barta, A.V. Iretskii, P.C. Ford, One-pot catalytic conversion of 8113–8117.
cellulose and of woody biomass solids to liquid fuels, J. Am. Chem. Soc. 133 (2011) [56] X. Huang, T.I. Korányi, M.D. Boot, E.J. Hensen, Catalytic depolymerization of
14090–14097. lignin in supercritical ethanol, ChemSusChem 7 (2014) 2276–2288.
[29] C. Li, M. Zheng, A. Wang, T. Zhang, One-pot catalytic hydrocracking of raw woody [57] X. Huang, T.I. Korányi, M.D. Boot, E.J. Hensen, Ethanol as capping agent and
biomass into chemicals over supported carbide catalysts: simultaneous conversion formaldehyde scavenger for efficient depolymerization of lignin to aromatics,
of cellulose, hemicellulose and lignin, Energy Environ. Sci. 5 (2012) 6383–6390. Green Chem. 17 (2015) 4941–4950.
[30] X. Si, R. Lu, Z. Zhao, X. Yang, F. Wang, H. Jiang, X. Luo, A. Wang, Z. Feng, J. Xu, [58] J. Pang, M. Zheng, L. He, L. Li, X. Pan, A. Wang, X. Wang, T. Zhang, Upgrading
Catalytic production of low-carbon footprint sustainable natural gas, Nat. ethanol to n-butanol over highly dispersed Ni–MgAlO catalysts, J. Catal. 344
Commun. 13 (2022) 1–9. (2016) 184–193.
[31] I. Dincer, Green methods for hydrogen production, Int. J. Hydrog. Energy 37 [59] Z. Wang, J. Pang, L. Song, X. Li, Q. Yuan, X. Li, S. Liu, M. Zheng, Conversion of
(2012) 1954–1971. ethanol to n-butanol over NiCeO2 based catalysts: effects of metal dispersion and
[32] Y. Wang, F. Wang, Q. Song, Q. Xin, S. Xu, J. Xu, Heterogeneous ceria catalyst with NiCe interactions, Ind. Eng. Chem. Res. 59 (2020) 22057–22067.
water-tolerant Lewis acidic sites for one-pot synthesis of 1, 3-diols via Prins [60] S. Hu, W.-X. Li, Sabatier principle of metal-support interaction for design of
condensation and hydrolysis reactions, J. Am. Chem. Soc. 135 (2013) 1506–1515. ultrastable metal nanocatalysts, Science 374 (2021) 1360–1365.
[33] P. Sirous-Rezaei, Y.-K. Park, Catalytic hydropyrolysis of lignin: suppression of coke [61] N. Hao, K. Alper, K. Tekin, S. Karagoz, A.J. Ragauskas, One-pot transformation of
formation in mild hydrodeoxygenation of lignin-derived phenolics, Chem. Eng. J. lignocellulosic biomass into crude bio-oil with metal chlorides via hydrothermal
386 (2020), 121348. and supercritical ethanol processing, Bioresour. Technol. 288 (2019), 121500.
[34] X. Chen, Q. Che, S. Li, Z. Liu, H. Yang, Y. Chen, X. Wang, J. Shao, H. Chen, Recent [62] B. Biswas, A. Kumar, R. Kaur, B.B. Krishna, T. Bhaskar, Catalytic hydrothermal
developments in lignocellulosic biomass catalytic fast pyrolysis: strategies for the liquefaction of alkali lignin over activated bio-char supported bimetallic catalyst,
optimization of bio-oil quality and yield, Fuel Process. Technol. 196 (2019), Bioresour. Technol. 337 (2021), 125439.
106180. [63] S. Cheng, L. Wei, J. Julson, M. Rabnawaz, Upgrading pyrolysis bio-oil through
[35] N.C. Nelson, B.W. Boote, P. Naik, A.J. Rossini, E.A. Smith, I.I. Slowing, Transfer hydrodeoxygenation (HDO) using non-sulfided Fe-Co/SiO2 catalyst, Energy
hydrogenation over sodium-modified ceria: enrichment of redox sites active for Convers. Manag. 150 (2017) 331–342.
alcohol dehydrogenation, J. Catal. 346 (2017) 180–187. [64] S.T. Hossain, E. Azeeva, K. Zhang, E.T. Zell, D.T. Bernard, S. Balaz, R. Wang,
[36] L. Lei, Y. Wang, Z. Zhang, J. An, F. Wang, Transformations of biomass, its A comparative study of CO oxidation over Cu-O-Ce solid solutions and CuO/CeO2
derivatives, and downstream chemicals over ceria catalysts, ACS Catal. 10 (2020) nanorods catalysts, Appl. Surf. Sci. 455 (2018) 132–143.
8788–8814. [65] A. Li, D. Yao, Y. Yang, W. Yang, Z. Li, J. Lv, S. Huang, Y. Wang, X. Ma, Active
[37] T. Stedile, L. Ender, H. Meier, E. Simionatto, V. Wiggers, Comparison between Cu0–Cuσ+ sites for the hydrogenation of carbon–oxygen bonds over Cu/CeO2
physical properties and chemical composition of bio-oils derived from catalysts, ACS Catal. 12 (2022) 1315–1325.
lignocellulose and triglyceride sources, Renew. Sustain. Energy Rev. 50 (2015) [66] V. Muravev, G. Spezzati, Y.-Q. Su, A. Parastaev, F.-K. Chiang, A. Longo,
92–108. C. Escudero, N. Kosinov, E.J. Hensen, Interface dynamics of Pd–CeO2 single-atom
catalysts during CO oxidation, Nat. Catal. 4 (2021) 469–478.

14
W. Chou et al. Applied Catalysis B: Environmental 316 (2022) 121625

[67] J. Lin, C. Ma, Q. Wang, Y. Xu, G. Ma, J. Wang, H. Wang, C. Dong, C. Zhang, [74] C.A. Trickett, T.M. Osborn Popp, J. Su, C. Yan, J. Weisberg, A. Huq, P. Urban,
M. Ding, Enhanced low-temperature performance of CO2 methanation over J. Jiang, M.J. Kalmutzki, Q. Liu, Identification of the strong Brønsted acid site in a
mesoporous Ni/Al2O3-ZrO2 catalysts, Appl. Catal. B Environ. 243 (2019) 262–272. metal–organic framework solid acid catalyst, Nat. Chem. 11 (2019) 170–176.
[68] W. Chou, P. Wu, M. Luo, W. Li, S. Li, Effects of Al, Si, Ti, Zr promoters on catalytic [75] T. Li, J. Wang, F. Wang, L. Zhang, Y. Jiang, H. Arandiyan, H. Li, The effect of
performance of iron-based Fischer–Tropsch synthesis catalysts, Catal. Lett. 150 surface wettability and coalescence dynamics in catalytic performance and catalyst
(2020) 1993–2002. preparation: a review, ChemCatChem 11 (2019) 1576–1586.
[69] Z. Kong, Y. Li, Y. Wang, Y. Zhang, K. Shen, X. Chu, H. Wang, J. Wang, L. Zhan, [76] Y. Zhang, S. Zhao, J. Feng, S. Song, W. Shi, D. Wang, H. Zhang, Unraveling the
Monodispersed MnOx-CeO2 solid solution as superior electrocatalyst for Li2S physical chemistry and materials science of CeO2-based nanostructures, Chem 7
precipitation and conversion, Chem. Eng. J. 392 (2020), 123697. (2021) 2022–2059.
[70] L. Bui, H. Luo, W.R. Gunther, Y. Román-Leshkov, Domino reaction catalyzed by [77] A. Hezam, K. Namratha, Q.A. Drmosh, D. Ponnamma, J. Wang, S. Prasad,
zeolites with Brønsted and Lewis acid sites for the production of γ-valerolactone M. Ahamed, C. Cheng, K. Byrappa, CeO2 nanostructures enriched with oxygen
from furfural, Angew. Chem. 125 (2013) 8180–8183. vacancies for photocatalytic CO2 reduction, ACS Appl. Nano Mater. 3 (2019)
[71] K. Tanabe, Solid Acids and Bases: Their Catalytic Properties, Elsevier, 2012. 138–148.
[72] V.L. Sushkevich, P.A. Kots, Y.G. Kolyagin, A.V. Yakimov, A.V. Marikutsa, I. [78] P. Chen, Q. Zhang, R. Shu, Y. Xu, L. Ma, T. Wang, Catalytic depolymerization of the
I. Ivanova, Origin of water-induced Brønsted acid sites in Sn-BEA zeolites, The, hydrolyzed lignin over mesoporous catalysts, Bioresour. Technol. 226 (2017)
J. Phys. Chem. C 123 (2019) 5540–5548. 125–131.
[73] R.C. Nelson, B. Baek, P. Ruiz, B. Goundie, A. Brooks, M.C. Wheeler, B.G. Frederick, [79] H. Shafaghat, Y.F. Tsang, J.-K. Jeon, J.M. Kim, Y. Kim, S. Kim, Y.-K. Park, In-situ
L.C. Grabow, R.N. Austin, Experimental and theoretical insights into the hydrogen- hydrogenation of bio-oil/bio-oil phenolic compounds with secondary alcohols over
efficient direct hydrodeoxygenation mechanism of phenol over Ru/TiO2, ACS a synthesized mesoporous Ni/CeO2 catalyst, Chem. Eng. J. 382 (2020), 122912.
Catal. 5 (2015) 6509–6523. [80] I. Agirre, M. Güemez, A. Ugarte, J. Requies, V. Barrio, J. Cambra, P. Arias, Glycerol
acetals as diesel additives: kinetic study of the reaction between glycerol and
acetaldehyde, Fuel Process. Technol. 116 (2013) 182–188.

15