catalysts

Article
Influence of Synthesis Methodology on the Properties and
Catalytic Performance of Tin, Niobium, and Tin-Niobium
Oxides in Fructose Conversion
Thatiane Veríssimo dos Santos Martins , Dhara Beatriz de Amorim Pryston,
Simoni Margareti Plentz Meneghetti * and Mario Roberto Meneghetti *

Group of Catalysis and Chemical Reactivity, Institute of Chemistry and Biotechnology, Federal University of
Alagoas, Av. Lourival Melo Mota, Tabuleiro do Martins, Maceió 57072-970, Brazil
* Correspondence: simoni.plentz@gmail.com (S.M.P.M.); mrm@qui.ufal.br (M.R.M.)

Abstract: Pure and mixed oxides were synthesized using three methods, namely, coprecipitation,
hydrothermal treatment using CTAB and Pechini treatment using glycerol, and investigated for
the transformation of fructose, aiming to determine the influence of textural, structural, and acid-
base properties on conversion and selectivity. All systems led to fructose conversion in an aqueous
medium, and the factors that influenced the transformation were the textural and structural properties,
as well as the number of acid sites present in the catalysts. The best conversions were observed
using mixed oxides, highlighting SnNb (CTAB) and SnNb (GLY), showing the importance of the
modulation of properties using the synthesis method. All systems were selective mainly for 5-HMF
(5-hydroxymethylfurfural) and, to a lesser extent, for the products of the retro-aldolic route, and this
selectivity was preserved, regardless of the catalytic system used.

Keywords: biomass; biorefinery; fructose; mixed oxide; tin; niobium

Citation: Martins, T.V.d.S.;
Pryston, D.B.d.A.; Meneghetti, S.M.P.;
Meneghetti, M.R. Influence of
Synthesis Methodology on the
1. Introduction
Properties and Catalytic Performance
of Tin, Niobium, and Tin-Niobium
The dependence of society on fossil sources to produce chemicals and energy has
Oxides in Fructose Conversion. generated several environmental and economic concerns, and research has been intensified
Catalysts 2023, 13, 285. to establish environmentally friendly alternatives [1,2]. Renewable biomass, in particu-
https://doi.org/10.3390/ lar carbohydrates, is an excellent candidate for use as a raw material that facilitates the
catal13020285 transition from the fossil industry to biorefineries, since it is abundant, presents excellent
cost-effectiveness and constitutes a promising starting material for obtaining a wide range
Academic Editors: Linda Zh
of products of great industrial interest, many of which are considered commodities [3,4].
Nikoshvili, Lioubov Kiwi-Minsker
Among carbohydrates, fructose is considered an important chemical platform to
and Valentin Yu Doluda
produce chemical inputs such as glucose, 5-hydroxymethylfurfural (5-HMF), glyceralde-
Received: 23 December 2022 hyde, pyruvaldehyde, lactic acid, dihydroxyacetone, formic acid, acetic acid and levulinic
Revised: 23 January 2023 acid [5–8]. Thus, the search for active catalytic systems in the conversion of fructose
Accepted: 25 January 2023 has been growing, and it is worth mentioning that the nature of the catalysts directs
Published: 27 January 2023 the routes in the transformation of sugars, thereby improving the conversion results of
these pathways [9,10].
The reactions conducted in the presence of homogeneous catalytic systems are more
selective and efficient than those conducted in heterogeneous systems [11]. However, the
Copyright: © 2023 by the authors.
disadvantages related to equipment corrosion, difficulty in separating the final product and
Licensee MDPI, Basel, Switzerland.
limitations during recycling and reuse of the catalyst [11,12] drive the quest for efficient
This article is an open access article
distributed under the terms and
heterogeneous catalysts that are easy to separate and reuse.
conditions of the Creative Commons
Among them, metal oxides have attracted great attention as attractive solid catalysts
Attribution (CC BY) license (https:// for biomass conversion, since they have unique properties such as thermal and chemical
creativecommons.org/licenses/by/ stability, typically having a dual character due to the presence of Lewis and Brønsted
4.0/). acid sites [11–13]. Despite some promising results with the use of monometallic oxides,

Catalysts 2023, 13, 285. https://doi.org/10.3390/catal13020285 https://www.mdpi.com/journal/catalysts

Catalysts 2023, 13, 285 2 of 18

the strategy of synthesizing mixed oxides aims to modulate the textural and chemical
properties of the system by strengthening the thermal and chemical stability. One example
is based on reports of the use of tin oxide and niobium in biorefinery processes [14–19].
The weak Lewis-acidity of the tin species was considered a determining factor in
the isomerization reaction [20]. The use of sulfated tin oxide prepared by hydrothermal
synthesis applied in the esterification of levulinic acid was also reported, and the results
showed that the chemical structure and catalytic performance of these sulfated materials
strongly depend on the treatment of nanoparticles before the sulfate procedure [21]. Studies
of mesoporous tin oxides applied in the acetalization of glycerol under solvent-free condi-
tions demonstrated that the activity is intrinsically related to the structure and acidity of
these systems [22].
Niobium oxide has a wide range of applications in various industrial sectors [19], and
studies have shown its catalytic potential, with high selectivity to 5-HMF (5-hydroxyme-
thylfurfural) due to its high Bronsted-acidity [19]. Other work reported that its acidic
properties are essential for the conversion of glucose into levulinic acid [23].
Considering all the properties of the pure oxides mentioned above, it is assumed that
the mixed oxides of these materials can represent interesting systems in the field of biomass
transformation, as they constitute new materials with physicochemical characteristics
and particular catalytic properties compared to pure oxides. It is important to note that
these properties can be modulated through different synthesis methods with controlled
morphologies, particle sizes, crystalline structures and amounts/natures of acidic sites. In
the case of a synthetic approach, it is necessary to apply a simple method that can result in
materials with adequate catalytic efficiency.
In a recent study by our research group, pure and mixed oxides based on tin and
niobium were synthesized using the Pechini method. In this case, the possibility of
using glycerol instead of ethylene glycol in the esterification step was demonstrated,
thus generating materials with excellent properties, which were obtained via a greener
synthesis-process [24].
In this work, aiming to expand the information available on the influence of the syn-
thesis methodology on the properties of this type of material, coprecipitation, surfactant-
modeled-hydrothermal (CTAB) and Pechini (using glycerol) methods were used. Comple-
mentarily, a study was carried out to determine the influence of their textural, structural,
and acid-base properties on the transformation of fructose. According to the research car-
ried out, this is the first time that oxides based on tin and niobium have been synthesized
by different methods and applied in this reaction.

2. Results and Discussion

Catalytic systems based on tin and niobium oxides were obtained by (co)precipitation,
modeled by the CTAB template and by the Pechini method, using glycerol as the polyol [24].
Such systems were characterized and investigated in the conversion of fructose, aiming to
determine how their properties drive this reaction.

2.1. Characterization of the Catalysts

Initially, for the mixed oxides, the amount of niobium present in the materials was
determined, and values of 11.6, 15.8 and 16.9% were attained for SnNb (PPT), SnNb (CTAB)
and SnNb (GLY), respectively [24].
The X-ray diffraction patterns of the various materials are shown in Figure 1. For the
pure tin oxides, despite the synthesis method used, the signals present in the diffractograms
(Figure 1a) confirm the polycrystalline and single-phase nature of the systems. In this case,
tin oxides can be classified as tetragonal rutile (JCPDS no. 41-1445), as confirmed by the
crystallographic planes (110), (101), (200), (211), (220), (002) (310), (112), (301), (202) and
(321). Comparatively, Sn(PPT) showed a narrowing of the diffraction peaks, suggesting a
gradual increase in crystallinity due to crystallite agglomeration. The tin oxides synthesized
 Catalysts 2023, 13, x FOR PEER REVIEW 3 of 19

this case, tin oxides can be classified as tetragonal rutile (JCPDS no. 41-1445), as confirmed
Catalysts 2023, 13, 285 by the crystallographic planes (110), (101), (200), (211), (220), (002) (310), (112), (301), (202) 3 of 18
and (321). Comparatively, Sn(PPT) showed a narrowing of the diffraction peaks, suggest-
ing a gradual increase in crystallinity due to crystallite agglomeration. The tin oxides syn-
thesized by the other methods showed a considerable decrease in intensity in the reflec-
bytion
theplane
other(110),
methods
whichshowed
suggests athat
considerable
there is greatdecrease
disorder in intensity
generated in the
in the reflection
material [22]. plane
(110), which suggests that there is great disorder generated in the material [22].

(a) (b)

(c)
Figure 1. XRD patterns of the catalysts: (a) Sn(PPT), Sn(CTAB) and Sn(GLY); (b) Nb(PPT),
Figure 1. XRD patterns of the catalysts: (a) Sn(PPT), Sn(CTAB) and Sn(GLY); (b) Nb(PPT), Nb(CTAB)
Nb(CTAB) and Nb(GLY); and (c) SnNb(PPT), SnNb(CTAB) and SnNb(GLY).
and Nb(GLY); and (c) SnNb(PPT), SnNb(CTAB) and SnNb(GLY).
XRD patterns for niobium oxide are shown in Figure 1b. Nb(PPT) showed an amor-
XRD
phous patterns
profile, but for niobium
Nb(CTAB) andoxide are shown
Nb(GLY) showedin the
Figure 1b. Nb(PPT)planes
crystallographic showed an amor-
(001),
phous
(180), (181), (002), (321), (182), (215), (216) and (481), which indicate the predominance of (180),
profile, but Nb(CTAB) and Nb(GLY) showed the crystallographic planes (001),
(181), (002), (321),phase
the orthorhombic (182),(T(215),
Nb2O5(216)
-JCPDS and (481),[25].
30-0873) which indicate
However, it isthe
notpredominance
possible to rule of the
orthorhombic phase
out the presence, to a(Tlesser
Nb2 O 5 -JCPDS
extent, 30-0873)
of the [25]. However,
pseudohexagonal phase itwith
is not possible to rule out
crystallographic
planes
the in (001),
presence, to a(100),
lesser(101), (002),
extent, (110)
of the and (102) (TT Nbphase
pseudohexagonal 2O5-JCPDS
with280317). The most planes
crystallographic
accentuated differences are noticed in the range between 25 and 40°, and it is
in (001), (100), (101), (002), (110) and (102) (TT Nb2 O5 -JCPDS 280317). The most accentuated important
differences are noticed in the range between 25 and 40◦ , and it is important to note that the
positions of the signals referring to the hexagonal phase and the orthorhombic phases are
so close that it is difficult to differentiate between the two. This result is attributed to the
presence of vacancies or impurities in the materials [26,27].
For all mixed oxides (Figure 1c), it is possible to observe the predominant presence
of the tetragonal phase, with broader and less-intense signals compared to the precursors,
suggesting that the difference in ionic radii due to the replacement of Sn4+ by Nb5+ caused
the distortion of the cell lattice of SnO2 . Analyzing the diffractograms, it is possible to
verify the fact that there was an enlargement of the reflection peaks, which may be related
to the crystallite size and the short-range disorder.
 to note that the positions of the signals referring to the hexagonal phase and the ortho-
rhombic phases are so close that it is difficult to differentiate between the two. This result
is attributed to the presence of vacancies or impurities in the materials [26,27].
For all mixed oxides (Figure 1c), it is possible to observe the predominant presence
of the tetragonal phase, with broader and less-intense signals compared to the precursors,
Catalysts 2023, 13, 285 suggesting that the difference in ionic radii due to the replacement of Sn4+ by Nb5+ caused 4 of 18
the distortion of the cell lattice of SnO2. Analyzing the diffractograms, it is possible to
verify the fact that there was an enlargement of the reflection peaks, which may be related
to the crystallite size and the short-range disorder.
The spectra in the mid-infrared region are shown in Figure 2. For SnO2 , the presence
The spectra in the mid-infrared region are shown −1 wasin Figure 2. For SnO2, the presence
of a broad band in the range of 497 and 662 cm observed, which is attributed to
of a broad band in the range of 497 and 662 cm−1 was observed, which is attributed to the
the O-Sn-O and Sn-O stretching modes and SnO 2
O-Sn-O and Sn-O stretching modes and SnO2 flexion [28,29]. For flexion [28,29].
niobium For niobium
oxides, typicaloxides,
typical vibrations were observed in the range of 410 to 931 cm −1 , giving rise to a broad
vibrations were observed in the range of 410 to 931 cm , giving rise to a broad band at-
−1

bandtributed
attributed tovibrations
to the the vibrations
of the of the Nb-O-Nb
Nb-O-Nb bonds ofbonds of thedistorted
the slightly slightlyoctahedral
distortedNbO octahedral
6

NbOand6 andthe the symmetrical

symmetrical stretching
stretching of the of
Nb-Othe Nb-O
species species
present in present
highly in highly
distorted distorted
environ-
ments [30].[30].
environments The signal at 1625atcm
The signal 1625 cm−1attributed
−1 can be to water molecules
can be attributed to wateradsorbed
molecules on adsorbed
the
surface of this material. There is also the presence of a band at 3412 cm −1, probably− 1
due to
on the surface of this material. There is also the presence of a band at 3412 cm , probably
the vibration of the Nb-OH bond
due to the vibration of the Nb-OH bond [30]. [30].

Sn (PPT)

Nb (PPT)

Transmittance (%)
Transmittance (%)

Sn (CTAB)

Nb (CTAB)

Sn (GLY)
Nb (GLY)

4000 3500 3000 2500 2000 1500 1000 500

4000 3500 3000 2500 2000 1500 1000 500
-1 -1
Wavenumber (cm ) Wavenumber (cm )

(a) (b)

SnNb (PPT)
Transmittance (%)

SnNb (CTAB)

SnNb (GLY)

4000 3500 3000 2500 2000 1500 1000 500

-1
Wavenumber (cm )
(c)

Figure 2. Infrared spectra of the catalysts: (a) Sn(PPT), Sn(CTAB) and Sn(GLY); (b) Nb(PPT),
Nb(CTAB) and Nb(GLY); and (c) SnNb(PPT), SnNb(CTAB) and SnNb(GLY).

The mixed oxides presented vibrations similar to the pure ones. There is a broad
band in the region between 410 and 931 cm−1 that is attributed to the symmetrical and
asymmetrical stretching of metal-oxygen bonds, respectively. The signal at 3412 cm−1 and
the bands at ~1100 cm−1 and 1350–1400 cm−1 can be attributed to bound metal-OH [31].
Some characteristics of the oxides were investigated using Raman spectroscopy (see
Figure 3). It is important to remember that the SnO2 synthesized by the various synthesis
protocols has a rutile structure (more stable phase) and belongs to the space group D4h 14

(P42/mnm) [32]. Among these vibrations, the A1g , B1g , B2g and Eg modes are active in
Raman, while A2u , Eu and B1u are infrared active and optically inactive [33]. It has already
been reported in the literature that the A1g , B1g and B2g bands indicate the vibration modes
of the Sn-O bonds, while the Eg band reveals the oxygen vacancies [32]. The SnO2 Raman
spectrum (Figure 3a) mainly exhibited two bands at approximately 630 and 770 cm−1 ,
 bands at ~1100 cm−1 and 1350–1400 cm−1 can be attributed to bound metal-OH [31].
Some characteristics of the oxides were investigated using Raman spectroscopy (see
Figure 3). It is important to remember that the SnO2 synthesized by the various synthesis
protocols has a rutile structure (more stable phase) and belongs to the space group
(P42/mnm) [32]. Among these vibrations, the A1g, B1g, B2g and Eg modes are active in Ra-
Catalysts 2023, 13, 285 man, while A2u, Eu and B1u are infrared active and optically inactive [33]. It has already 5 of 18
been reported in the literature that the A1g, B1g and B2g bands indicate the vibration modes
of the Sn-O bonds, while the Eg band reveals the oxygen vacancies [32]. The SnO2 Raman
spectrum (Figure 3a) mainly exhibited two bands at approximately 630 and 770 cm−1,
which areare
which attributed
attributedtotovibration
vibration modes
modes AA 1g1g
and
and B2gB, 2g , respectively.
respectively. Thisisfact
This fact is a strong
a strong
indication
indication that SnO2 has a tetragonal structure. In addition to the two signals, there is an-there is
that SnO 2 has a tetragonal structure. In addition to the two signals,
another −1 , which is attributed to the IR-active A
otherweak signalatatapproximately
weak signal approximately 694694
cm−1cm, which is attributed to the IR-active A2u LO 2u
LO mode
mode(the (themode
mode of of longitudinal
longitudinal optical-phonons).
optical-phonons). AnotherAnother
mode was mode wasatdetected
detected 572 at
cm−1−, 1attributed
572 cm to the
, attributed to smaller particle-size
the smaller of SnO2of
particle-size [34].
SnO2 [34].
A1g B2g A1g B2g TO

Nb-O streching and symmetry Mainly Nb-O stretching

related vibrations

Sn (PPT)
Nb (PPT)

Intensity (a.u)
Intensity (a.u)

Sn (CTAB) Nb (CTAB)

Sn (GLY)
Nb (GLY)

Catalysts 2023, 13, x400

FOR PEER500REVIEW 600 700 800 200 400 600 800 1000 1200 6 of 19
-1 -1
Raman shift (cm ) Raman shift (cm )
(a) (b)

A1g B2g Replacement of Sn for Nb

4+ 5+

SnNb (PPT)
Intensity (a.u)

SnNb (CTAB)

SnNb (EG)

200 300 400 500 600 700 800 900 1000

-1
Raman shift (cm )
(c)
Figure 3.3.Raman
Figure Ramanspectra
spectra of catalysts:
of the the catalysts: (a) Sn(PPT),
(a) Sn(PPT), Sn(CTAB)
Sn(CTAB) and Sn(GLY);
and Sn(GLY); (b) Nb(CTAB)
(b) Nb(PPT), Nb(PPT),
Nb(CTAB) and Nb(GLY); and (c) SnNb(PPT), SnNb(CTAB) and SnNb(GLY).
and Nb(GLY); and (c) SnNb(PPT), SnNb(CTAB) and SnNb(GLY).

Raman spectra
Raman spectra of of the
the niobium
niobium oxides
oxides are
are shown
shown in in Figure
Figure 3b,
3b, and
and the
the low-resolution
low-resolution
signal located at 990 cm −−11 is attributed to the vibration modes of A1g(ν1) of the octahedral
signal located at 990 cm is attributed to the vibration modes of A1g (ν1) of the octahedral
NbO6 [35,36].
NbO The signals that appear between 200 and 300 cm−1 are characteristic
−1 are of the
6 [35,36]. The signals that appear between 200 and 300 cm characteristic of
bending modes of the Nb–O–Nb bonds [37], and the signals
the bending modes of the Nb–O–Nb bonds [37], and the signals present in the range present in the range of 400–of
800 cm−1 cm
400–800 are−attributed
1 are attributed to symmetric and asymmetric
to symmetric stretchingstretching
and asymmetric of the Nb-O-Nb
of the bond
Nb-O-Nb[37].
A signal
bond [37].observed
A signalat approximately
observed ∼700 cm−1∼
at approximately is700
attributed
cm−1 isto the orthorhombic
attributed Nb2O5 TO
to the orthorhombic
mode [35]. The Nb O samples synthesized by the
Nb2 O5 TO mode [35]. The Nb2 O5 samples synthesized by the various methods
2 5 various methods belong to thebelong
space
group (P2 2 2 ). In this crystalline structure, there are two Nb 5+ sites, and the5+
to the space group (P21 21 21 ). In this crystalline structure, there are two Nb sites, and
1 1 1 first Nb 5+ is

bonded
the to four
first Nb 5+ O atoms,
2-
is bonded to form
to four 2- corner-sharing
O atoms, NbO4 tetrahedra.
to form corner-sharing NbO The second Nb is
4 tetrahedra. The
5+

bondedNb
second to 5+sixisObonded
2- atoms, to form
to six O2- NbOatoms,6 octahedrons
to form NbO [36].
6 octahedrons [36].
Figure 3c shows the spectra of the mixed oxides. The band at approximately 632 cm−1
is attributed to the A1g mode associated with symmetrical stretching of the Sn-O bond [37].
Considering that mixed oxides are formed by Sn, O and Nb atoms and that the crystalline
structure of tin oxide belongs to the P42/mnm point group and tetragonal Bravais lattice,
it can be inferred that the crystalline structure is distorted by the insertion of niobium
Catalysts 2023, 13, 285 6 of 18

Figure 3c shows the spectra of the mixed oxides. The band at approximately 632 cm−1
is attributed to the A1g mode associated with symmetrical stretching of the Sn-O bond [37].
Considering that mixed oxides are formed by Sn, O and Nb atoms and that the crystalline
structure of tin oxide belongs to the P42/mnm point group and tetragonal Bravais lattice,
it can be inferred that the crystalline structure is distorted by the insertion of niobium
atoms into the lattice, causing the appearance of oxygen vacancies during synthesis. This
network-sharing promotes the appearance of defects, and this same phenomenon has
already been reported in other studies, for metal oxides [38].
For all spectra of pure or mixed oxide (Figure 3) it is not possible to discard the presence
of the band related to the Eg mode, which is a strong indicator of oxygen vacancies. The
appearance of this band is expected at approximately 474 cm−1 , and just a low resolution
signal is observed in some cases.
DRS UV–vis spectra were also produced (Figure 4), and provide important information
about the nature of niobium and tin atoms in these systems. The UV–Vis DRS spectra
for the SnO2 samples (Figure 4a) showed an intense absorption band at approximately
300 nm, due to the high binding-energy, which is characteristic of cassiterite, and the strong
interaction of the ligand-to-metal-charge-transfer (LMCT)-type [39]. For Nb72 O
Catalysts 2023, 13, x FOR PEER REVIEW samples
of5 19
(Figure 4b), bands at approximately 350 nm were observed, corresponding to orthorhombic
and/or hexagonal geometries [40].

Figure 4. DRS-UV–vis
Figure 4. DRS-UV‒visspectra of the
spectra of thecatalysts:
catalysts:(a)(a) Sn(PPT),
Sn(PPT), Sn(CTAB)
Sn(CTAB) and Sn(GLY);
and Sn(GLY); (b) Nb(PPT),
(b) Nb(PPT),
Nb(CTAB)
Nb(CTAB) andand Nb(GLY);and
Nb(GLY); and(c)
(c) SnNb(PPT),
SnNb(PPT), SnNb(CTAB)
SnNb(CTAB) andand
SnNb(GLY).
SnNb(GLY).

TheThe spectraofofmixed
spectra mixedoxides
oxides synthesized
synthesized by
by different
differentmethods
methods (Figure 4c) 4c)
(Figure are are dif-
different from those of pure materials, and such evidence is also corroborated by
ferent from those of pure materials, and such evidence is also corroborated by XRD and XRD and
Raman spectroscopy. Previous studies suggest that the tendency to change the absorption
maximum to shorter wavelengths (200–250 nm) may be indicative of the superposition of
tetrahedral Sn species and the strong interaction with octahedral niobium species
(formation of Nb-O-Sn bonds), indicating charge-transfer transitions between atoms [41].
The textural properties and the nitrogen adsorption- and desorption-isotherms are
Catalysts 2023, 13, 285 7 of 18

Raman spectroscopy. Previous studies suggest that the tendency to change the absorption
maximum to shorter wavelengths (200–250 nm) may be indicative of the superposition of
tetrahedral Sn species and the strong interaction with octahedral niobium species (forma-
tion of Nb-O-Sn bonds), indicating charge-transfer transitions between atoms [41].
The textural properties and the nitrogen adsorption- and desorption-isotherms are
shown in Figure 5. According to IUPAC, they are type IV with H1 hysteresis loops,
suggesting that cylindrical channels are well defined. Sn(PPT) and Nb(PPT) are detected
in areas of 30 and 115.5 m2 g−1 , respectively. However, SnNb(PPT) showed a decrease
Catalysts 2023, 13, x FOR PEER REVIEW in
8 of 19
surface area (78.51 m2 g−1 ) when compared to Nb(PPT), which can be attributed to the
agglomeration of metallic cations during the synthesis process.

Figure
Figure 5.
5. Nitrogen
Nitrogen adsorption-
adsorption- and
and desorption-isotherms
desorption-isothermsand
andtextural
texturalproperties
propertiesof
of the
the catalysts:
catalysts:
(a) Sn(PPT), Nb(PPT) and SnNb(PPT); (b) Sn(CTAB), Nb(CTAB) and Nb(GLY) and SnNb(CTAB);
(a) Sn(PPT), Nb(PPT) and SnNb(PPT); (b) Sn(CTAB), Nb(CTAB) and Nb(GLY) and SnNb(CTAB); and
and (c) Sn(GLY), Nb(GLY) and SnNb(GLY).
(c) Sn(GLY), Nb(GLY) and SnNb(GLY).

For SnNb(CTAB), there

For SnNb(CTAB), therewas
wasananincrease
increase
in in surface
surface area,
area, which
which suggests
suggests thatpres-
that the the
presence
ence of the template influences this parameter, as there is a reduction in the aggregationthe
of the template influences this parameter, as there is a reduction in of
aggregation of metallic cations, since the hydrogen atoms of the hydroxyl groups (-OH
groups) related to the metallic species can interact with the main cationic groups
(C16H33)(CH3)3N+ (hydrophilic groups) of CTAB micelles, disfavoring the crystallization of
individual cations. This same increasing effect is observed in the case of SnNb(GLY), and
Catalysts 2023, 13, 285 8 of 18

metallic cations, since the hydrogen atoms of the hydroxyl groups (-OH groups) related
to the metallic species can interact with the main cationic groups (C16 H33 )(CH3 )3 N+ (hy-
drophilic groups) of CTAB micelles, disfavoring the crystallization of individual cations.
This same increasing effect is observed in the case of SnNb(GLY), and there are indications
that the higher surface-area values of mixed oxides can be attributed to the strong inter-
action between species, which inhibits individual crystallization, reducing the number of
clusters and the particle growth [42,43].
The thermal analyses of the materials were evaluated, and the presence of organic
matter was not verified through the TG curves (Figure S1, Supplementary Materials). All
oxides suffer a mass loss (between 0.8 and 12%) in just one step in the temperature range
of 100 to 150 ◦ C, corresponding to the release of physiosorbed water, suggesting that the
materials exhibit thermal stability in the evaluated range.
The catalytic activity of materials such as oxides can be driven by the presence of
acidic sites. Therefore, it is important to know the nature, quantity and strength of the
acid sites present in their structures. Thus, the acid properties of the solids were studied
by monitoring the pyridine adsorption using infrared spectroscopy, to assess the presence
of Lewis and Brønsted acid-sites (Figure S2, Supplementary Information). The bands at
1445, 1540 and 1489 cm−1 were attributed to Lewis acid sites, Brønsted acids, and the
overlapping of these sites, respectively [11]. For all SnO2 samples, weak vibrations were
observed, corresponding to the presence of Lewis and/or Brønsted acid-sites.
For all Nb2 O5 samples, signs similar to those found in the literature were observed,
since this system consists mainly of NbO6 distorted octahedra and NbO4 tetrahedra, and
the surface hydroxyl groups (-OH) function as Brønsted acid sites, while the tetrahedra
function as Lewis acid sites [44,45]. From this perspective, structural variation in the oxides
leads to changes in the nature of acidic sites and in their strength [46]. In addition, the use
of Nb2 O5 in aqueous reactions suggests a “water-tolerant solid-acid catalysts” system, and
this type of system proves to be resistant to water, in contrast to the classic Lewis acids such
as AlCl3 , which suffer severe poisoning by water, undergoing deactivation due to the strong
coordination of water in the metallic center (Lewis acids) or hydrolytic decomposition of
the system [47]. In this work, Nb2 O5 showed intense absorption-bands for Brønsted acid
sites and weak and/or moderate bands for Lewis acid sites.
Some studies indicate that the properties of mixed oxides strongly depend on the
preparation method employed, and it was observed in the present study that with the
presence of niobium in the lattice, there was also an increase in the Lewis–Brønsted ratio
(IA /IB ), mainly for SnNb(CTAB) and SnNb(GLY), resulting in catalytic systems with high
synergy and an improved balance in acid strength (Figure 6). It should be noted that
SnNb(PPT) did not have such a sharp increase in (AL /AB ) as was observed in the others,
clearly showing the influence of the synthesis method on its properties.
To evaluate the resistance and stability of the acid sites, pyridine was used, and infrared
spectra were acquired at 100, 200 and 300 ◦ C. When pyridine is chemically absorbed
at Lewis or Brønsted acid-sites, according to the temperature required to break such
interactions, it can be considered weak (below 200 ◦ C), moderate (between 200 and 300 ◦ C)
or strong (above 300 ◦ C). For SnO2 , weak vibrations related to Lewis and/or Brønsted acid-
sites were observed. For Nb2 O5 , strong vibrations were observed for the Brønsted acid sites,
and weak and/or moderate interactions were also detected for the Lewis acid sites. On
the other hand, for the mixed oxides, a better-resolved profile of the spectra was observed,
with more prominent signals related to the Lewis acids, and Brønsted-related bands also
detected, in addition to the overlap of both species (Figure S2, Supplementary Information).
This can be better observed by examining the AL /AB results, where the significant increase
is notorious for all temperatures (Figure 6). The modulation of these characteristics in
mixed oxides is essential to make this system more versatile for application in various
biorefinery platforms [38].
 Catalysts2023,
Catalysts 2023,13,
13,285
x FOR PEER REVIEW 10 of 1918
9 of

Figure 6.
Figure 6. Amount
Amount ofof Lewis
Lewis and
and Bronsted
Bronstedacid-sites
acid-sitesand
andratio
ratioofofthe
thenumber
numberofofLewis
Lewisand
andBronsted
Bronsted
acid-sites (AL/AB) of the catalysts.
acid-sites (AL /AB ) of the catalysts.

In this
In this context,
context, itit is
is evident
evident that
thatthe
thesynthesis
synthesisof ofSnNb
SnNbwas wasfundamental
fundamentalfor fora abalance
balance
between the
between the Lewis
Lewis and
and Brønsted
Brønsted acid-sites,
acid-sites,which
whichallows
allowsthesethesesystems
systemstotobecome
becomemore more
versatile for
versatile forapplication
applicationinindifferent
different biorefinery
biorefinery platforms.
platforms. In previous
In previous studies,
studies, it wasit found
was
found
that thethat the number,
number, nature and nature and relative
relative strengthstrength of acid
of acid sites in sites
someinmaterials
some materials can be
can be adjusted
adjusted using different synthetic strategies, including the use of templates
using different synthetic strategies, including the use of templates and different calcination and different
calcination temperatures
temperatures [22]. [22].
SEM micrographs of the
SEM micrographs of the materials
materials areare shown
shown inin Figure
Figure 7,7, and
andthetheimages
imagesfor for
SnNb(CTAB) and SnNb(GLY) showed great similarity, indicating
SnNb(CTAB) and SnNb(GLY) showed great similarity, indicating the formation of ma- the formation of
materials
terials withwith morphological
morphological disorder
disorder due due
to thetogreater
the greater interaction
interaction amongamong the species
the species during
during synthesis,
synthesis, resultingresulting in the formation
in the formation of smallerofparticles.
smaller Similar
particles. Similarwas
behavior behavior
observed wasin
the synthesis of porous, spherical materials from different oxides (Ce, Fe and Mn), and
observed in the synthesis of porous, spherical materials from different oxides (Ce, Fe since
Mn),
the since the functionality
functionality of the reagent of the reagent
species species
played played anrole
an important important role in the
in the structure, and struc-
using
ture, andinstead
glycerol using glycerol
of ethyleneinstead of ethylene
glycol resulted glycol resulted
in smaller in smaller
channels [48]. channels [48].
 SEM micrographs of the materials are shown in Figure 7, and the images for
SnNb(CTAB) and SnNb(GLY) showed great similarity, indicating the formation of mate-
rials with morphological disorder due to the greater interaction among the species during
synthesis, resulting in the formation of smaller particles. Similar behavior was observed
Catalysts 2023, 13, 285
in the synthesis of porous, spherical materials from different oxides (Ce, Fe and Mn),10since
of 18
the functionality of the reagent species played an important role in the structure, and us-
ing glycerol instead of ethylene glycol resulted in smaller channels [48].

Catalysts 2023, 13, x FOR PEER REVIEW 11 of 19

Sn(PPT) Sn(CTAB) Sn(GLY)

Nb(PPT) Nb(CTAB) Nb(GLY)

SnNb(PPT) SnNb(CTAB) SnNb(GLY)

Figure
Figure 7.
7. Scanning-electron-microscopy
Scanning-electron-microscopy (SEM)
(SEM) images
images of
of the
the catalysts.
catalysts. The
The scale
scale bar
bar of
of all
all images
images is
is
100 μm (see Figures S3, S4 and S5, Supplementary Information).
100 µm (see Figures S3–S5, Supplementary Information).

2.2. Catalytic Assays in Fructose Transformation

The series of oxides based on tin and niobium obtained by various synthesis methods
were investigated as catalysts in the conversion of fructose in an aqueous medium, at
150 ◦ C (see Figure 8 and Figure S6, Supplementary Information). Using the mixed oxides,
significantly higher values of fructose conversion were achieved than those observed for
the pure oxides. For example, the conversion was 75.7, 76.9 and 69.8% in 2 h of reaction
when using SnNb (G), SnNb (CTAB) and SnNb (PPT), respectively, and this tendency was
maintained during the investigated reaction time.
 were investigated as catalysts in the conversion of fructose in an aqueous medium, at 150
°C (see Figure 8 and Figure S6, Supplementary Information). Using the mixed oxides, sig-
nificantly higher values of fructose conversion were achieved than those observed for the
pure oxides. For example, the conversion was 75.7, 76.9 and 69.8% in 2 h of reaction when
using
Catalysts SnNb
2023, 13, 285 (G), SnNb (CTAB) and SnNb (PPT), respectively, and this tendency was main- 11 of 18
tained during the investigated reaction time.

Figure 8. Fructose conversion

Figure 8. at 150 °C
Fructose using at
conversion Sn(PPT), Nb(PPT)
150 ◦ C using andNb(PPT)
Sn(PPT), SnNb(PPT); Sn(CTAB),
and SnNb(PPT); Sn(CTAB),
Nb(CTAB) and Nb(GLY) and SnNb(CTAB);
Nb(CTAB) and
and Nb(GLY) and Sn(GLY),and
SnNb(CTAB); Nb(GLY)
Sn(GLY),and SnNb(GLY).
Nb(GLY) and SnNb(GLY).

The co-precipitation method, often referred to as analogous to the sol-gel process, is

The co-precipitation method, often referred to as analogous to the sol-gel process, is
an efficient chemical route for obtaining metal oxides, and has the advantages of obtaining
an efficient chemicalhigh
route for obtaining
yields and purity,metalbeing oxides, and has the
easily reproducible andadvantages
having a low of obtaining
cost [49,50]. The
high yields and purity,
method being easily
that uses reproducible
surfactant is known toand having
provide a greatera low cost between
interaction [49,50].theThereagents,
minimizing possible diffusion-restrictions during the
method that uses surfactant is known to provide a greater interaction between the rea- synthesis. In this case, the presence
of the template directly influences the modulation of the specific surface area and pore size,
gents, minimizing possible diffusion-restrictions during the synthesis. In this case, the
as there is a reduction in the aggregation of metallic cations, due to their interaction with
presence of the template directly
the cationic groups,influences
for example thewith
modulation of the the
CTAB, disfavoring specific surface
individual area
crystallization of
and pore size, as there is a reduction
the cations [22,42,43]. inThethe aggregation
methodology of metallic
developed cations,
by Pechini, duethe
in which tometal
theircations
interaction with the are chelated
cationic and, with
groups, fortheexample
help of polyalcohol,
with CTAB, are cross-linked
disfavoring to the
create a gel through the
individual
esterification, allows for a wide distribution of metallic
crystallization of the cations [22,42,43]. The methodology developed by Pechini, in which cations throughout the polymer
structure, promoting an increase in the surface area and improving the distribution of
the metal cations aremetals
chelated and, with the help of polyalcohol, are cross-linked to create
in the polymeric network, and being quite suitable for the manufacture of highly
a gel through the esterification, allows for a wide distribution of metallic cations through-
pure oxides [15,51].
out the polymer structure, Amongpromoting anthe
all systems, increase
SnNb(CTAB) in theand
surface
SnNb(GLY) area systems
and improving
provided the thehighest
fructose conversions, and in addition to
distribution of metals in the polymeric network, and being quite suitable containing the highestfor the manufac- sites,
numbers of acidic
they have the highest surface areas, of 173.2 and 166.6 m2 g−1 , respectively. SnNb(PPT)
ture of highly pure oxides [15,51].
has practically half of the surface area of these materials (78.51 m2 g−1 ). The larger surface
Among all systems, the SnNb(CTAB)
area promotes better contact and SnNb(GLY)
between substratesystems provided
and catalyst, and, as the highest
already mentioned,
fructose conversions, andusing
when in addition to containing
template (CTAB) the method
or the Pechini highesta numbers of acidic
greater interaction sites,species
between
they have the highest occurs during
surface synthesis,
areas, providing
of 173.2 and 166.6 greater
m2homogeneity
g−1, respectively.of the material.
SnNb(PPT) As evidence
has of
this, using these two methods it was possible to achieve
practically half of the surface area of these materials (78.51 m g ). The larger surface area
2 −1 a higher niobium content in the
materials (15.8% in SnNb(CTAB), 16.9% in SnNb(GLY), and only 11.6% in SnNb(PPT)). In
promotes better contact between substrate and catalyst, and, as already mentioned, when
Catalysts 2023, 13, 285 12 of 18

addition, it is important to note that the results obtained using Raman spectroscopy and
DRS analysis for the mixed oxides suggest the occurrence of a structural distortion, which
can cause the appearance of oxygen vacancies during synthesis, resulting in defects which
constitute active sites for fructose conversion. [17].
The soluble products formed during the transformation of fructose included glucose,
5-HMF (5-hydroxymethylfufural), levulinic acid, formic acid, glyceraldehyde, dihydrox-
yacetone, pyruvaldehyde, lactic acid and acetic acid. The selectivity profiles are shown
in Figure 9 for mixed oxides (for pure oxides, in Figure S7, Supplementary Information),
and all systems exhibit great selectivity for 5-HMF and, to a lesser extent, for products
of the retro-aldolic pathway (lactic acid and its intermediates glyceraldehyde, dihydrox-
yacetone and pyruvaldehyde). In general, a trend toward a decrease in selectivity to
5-HMF (5-hydroxymethylfurfural) is observed with an increase in AL /AB (Figure 6), con-
firming that the Brønsted acid sites present in the material are mainly responsible for the
Catalysts 2023, 13, x FOR PEER REVIEW 13 of 19
dehydration of fructose. The Lewis acid sites play a fundamental role in the isomerization
of glucose into fructose and in the retro-aldolic pathway.

Figure
Figure 9. 9. Selectivity
Selectivityfor soluble
for products
soluble identified
products in the
identified fructose
in the conversion
fructose at 150
conversion at °C,
150using 1.5 ×
◦ C, using
10 −3 g of SnNb(PPT), SnNb(CTAB) and SnNb(GLY).
1.5 × 10−3 g of SnNb(PPT), SnNb(CTAB) and SnNb(GLY).

During
During these
these reactions,
reactions, some
some insoluble
insoluble or
or partially
partially soluble
soluble products
products may
may be
be formed,
formed,
causing turbidity
turbidity and
andbrown
browncoloration
coloration
in in
thethe samples.
samples. Such
Such materials,
materials, known
known as hu-
as humines,
mines, are formed mainly by the polymerization of fructose or the decomposition of 5-
HMF (5-hydroxymethylfufural), due to high temperatures, long reaction-times or the na-
ture of the catalyst [52,53]. Regardless of the synthesis method, the qualitative analysis of
the reactional samples (Figure 10) allows us to infer that using niobium oxides considera-
bly increases the coloring and turbidity, while using tin oxides produces the smallest
3, x FOR PEER REVIEW 14 of 19
Catalysts 2023, 13, 285 13 of 18

HMF (5-hydroxymethylfufural), due to high temperatures, long reaction-times or the na-

are formed mainly by the polymerization of fructose or the decomposition of 5-HMF
ture of the catalyst(5-hydroxymethylfufural),
[52,53]. Regardless of the duesynthesis method, the long
to high temperatures, qualitative analysis
reaction-times or of
the nature of
the reactional samples (Figure 10) allows us to infer that using niobium oxides considera-
the catalyst [52,53]. Regardless of the synthesis method, the qualitative analysis of the
bly increases the coloring
reactional and turbidity,
samples (Figurewhile using
10) allows tininfer
us to oxides
that produces the oxides
using niobium smallestconsiderably
change in these properties. Bycoloring
increases the using mixed oxides, while
and turbidity, the formation of low-solubility
using tin oxides produces theprod-
smallest change
in these
ucts was significantly properties.
reduced, By using mixed
in comparison oxides,
to the thepure
use of formation of low-solubility
niobium-oxides. products was
There-
fore, the structuralsignificantly
and texturalreduced,
changes in and
comparison to theofuse
the number of pure
acid sites niobium-oxides.
observed in mixed Therefore, the
structural and textural changes and the number of acid sites observed in mixed oxides
oxides resulted in better conversions, maintaining the advantage of reduced humine-for-
resulted in better conversions, maintaining the advantage of reduced humine-formation.
mation.
0.5 h↓ 6 h↓ 0.5 h↓ 6 h↓ 0.5 h↓ 6 h↓

Sn(PPT) Sn(CTAB) Sn(GLY)

Nb(PPT) Nb(CTAB) Nb(GLY)

SnNb(PPT) SnNb(CTAB) SnNb(GLY)

Figure 10. Visual aspects
Figureof10.the samples
Visual during
aspects of the the reaction
samples using
during catalysts
the reaction (1.5 catalysts
using × 10−3 g)(1.5
at 150
× 10°C
−3 g) at 150 ◦ C
(0.5 and 6 h). (0.5 and 6 h).

The possibility of The possibility

recovery of recovery
and reuse and reuse
of the catalyst is of
of the
greatcatalyst is of great
importance importance
in the pro- in the
processes of biorefineries, and in previous studies the
cesses of biorefineries, and in previous studies the chemical stability of some of thesechemical stability of some of these
mixed oxides was evidenced, as the catalyst can be recovered and reused for four cycles,
mixed oxides was evidenced, as the catalyst can be recovered and reused for four cycles,
and no leaching of species for the reaction medium was observed [24,54].
and no leaching of species for the reaction medium was observed [24,54].
Finally, a comparison with studies involving bifunctional catalysts applied in fructose
Finally, a comparison
conversionwith studiesmedium
in aqueous involving bifunctional
reported catalystsallows
in the literature, appliedus in fruc- that the
to indicate
tose conversion insystems
aqueous medium
discussed reported
here have greatin potential,
the literature, allows us
as conversions to indicate
of 75.7, 76.9 andthat
69.8% were ob-
the systems discussed here have great potential, as conversions of 75.7, 76.9 and
served at 2 h of reaction when using SnNb (G), SnNb (CTAB) and SnNb (PPT), respectively.69.8%
were observed at In 2 haddition, it is important
of reaction when using to highlight
SnNb (G), the SnNb
fact that(CTAB)
all systems
andexhibit
SnNb high(PPT),selectivity for
5-HMF and,
respectively. In addition, to a lesser extent,
it is important for products
to highlight the factfrom
thatthe
allretro-aldol pathway.
systems exhibit highTo exemplify,
studies using mixed oxides of cerium and niobium (25,
selectivity for 5-HMF and, to a lesser extent, for products from the retro-aldol pathway. 50 and 75% of Nb 2 O5 ) obtained
using the coprecipitation method, led to fructose conversions lower than 75%, and the
To exemplify, studies using mixed oxides of cerium and niobium (25, 50 and 75% of
maximum selectivity for 5-HMF was around 45%. The reuse of the 25% CeO2 /75% Nb2 O5
Nb2O5) obtained using the coprecipitation method, led to fructose conversions lower than
catalyst showed a reduction in the catalytic activity after the first reaction [55]. In the same
75%, and the maximumway, theselectivity
use of mixedfor 5-HMFcontaining
tin-oxides was around 45%.proportions
different The reuseofofmolybdenum
the 25% (SnMoX,
CeO2/75% Nb2O5 catalyst showed a reduction in the catalytic activity after
X = 5, 25, 50 and 75%), taken by the precipitation method, were evaluated the first reaction
in the conversion
[55]. In the same way, the use of mixed tin-oxides containing different proportions of mo-
lybdenum (SnMoX, X = 5, 25, 50 and 75%), taken by the precipitation method, were eval-
uated in the conversion of fructose compared to pure oxides. Regarding the mixed oxides,
using SnMo25 at 150 °C a conversion of 73.2% was observed. However, a change in selec-
Catalysts 2023, 13, 285 14 of 18

of fructose compared to pure oxides. Regarding the mixed oxides, using SnMo25 at 150 ◦ C
a conversion of 73.2% was observed. However, a change in selectivity was observed as the
Mo content in the materials increased. Thus, the SnMo5 system showed high selectivity
for 5-HMF (~75%), while for SnMo25 the selectivity for this product was very low (ap-
proximately 20%), with a preferential tendency for products from the retro-aldol pathway.
In terms of stability, SnMo25 was used in six cycles, and no significant decrease in yield,
selectivity or substantial leaching were detected [13].

3. Materials and Methods

3.1. Materials
Tin(IV) chloride (99.995% trace-metals basis, Sigma–Aldrich, St. Louis, MI, USA)),
niobium(V) chloride (>99.995%, Sigma–Aldrich), citric acid (>99.0%, Sigma–Aldrich), am-
monium hydroxide (Sigma–Aldrich), nitric acid (>65.0%, Sigma–Aldrich), glycerol (>99.0%,
Sigma–Aldrich), ethylene glycol (>99.0%, Sigma–Aldrich), cetyltrimethylammonium bro-
mide (CTAB) (>99.0%, Sigma–Aldrich) and fructose (>99.0%, Sigma–Aldrich) were obtained
commercially, and used as received. Sulfuric acid (>95%) was purchased from Dynamics.

3.2. Preparation of Catalysts Using the Coprecipitation Method

Pure and mixed catalysts were obtained using aqueous solutions of tin chloride (IV)
and/or niobium chloride (V) (SnCl4 and/or NbCl5 ) at a concentration of 0.1 mol/L, and
coprecipitation was achieved by the slow addition of ammonium hydroxide. Soon after,
the precipitated material was left to rest for 4 h and then vacuum filtered, washed with
deionized water, and dried at 115 ◦ C for 8 h. The material obtained was sieved with a
100-mesh granulometry sieve, and then macerated for further analysis. Finally, the solids
were calcined at 500 ◦ C, for 4 h.

3.3. Preparation of Catalysts Using the CTAB-Surfactant-Template Method

Initially, 9 g of the surfactant cetyltrimethylammonium bromide (CTAB) was dissolved
in 75 mL of deionized water under constant stirring, to ensure the homogeneity of the
system. Then, 12 mL of NH4 OH (25% wt.) dissolved in 48 mL of distilled water was added
under stirring. The metal precursors (tin chloride (IV) and/or niobium chloride (V)) were
dissolved in 150 mL of deionized water and added dropwise to this first solution under
constant stirring, until a white paste was formed. This suspension was maintained under
stirring for 3 h, followed by aging at 25 ◦ C for 48 h. The obtained product was filtered,
washed, dried, macerated and calcined at 500 ◦ C, for 4 h.

3.4. Preparation of Catalysts Using the Modified Pechini Method

Initially, solutions of tin chloride (IV) and/or niobium chloride (V) (SnCl4 and/or
NbCl5 ) and citric acid, with concentrations of 0.479, 0.462 and 1.66 mol/L were prepared
using a mass ratio of 3:1 (citric acid: metal). Then, this material was stirred and heated to
70 ◦ C. Upon reaching the desired temperature, the material was removed from the system
and immersed in an ice bath, to promote the onset of precipitation. Subsequently, the
solution was returned to the stirring system, and ammonium hydroxide was gradually
added for 4 h, until complete precipitation. Then, the citrate was filtered, washed, and
dried at 120 ◦ C. The formed citrates were dissolved in distilled water and nitric acid. Then,
glycerol was added in a molar proportion of 60:40, in relation to the amount of citric acid.
The solution was heated to 70 ◦ C under stirring to promote the polymerization reaction.
After the elimination of nitrous oxides and water, the resin was obtained, and finally, the
solid was crushed and heated at 350 ◦ C for 3 h to eliminate the polymeric matrix, and
calcinated at 500 ◦ C for 4 h.

3.5. Characterization of the Catalysts

All materials were macerated in a mortar and sieved (100 mesh), and the description
of the catalysts and the codes used for their identification are shown in Table 1.
Catalysts 2023, 13, 285 15 of 18

Table 1. Code of the catalysts and the respective descriptions.

Code Description
Sn(PPT)
Pure oxide obtained using the coprecipitation method
Nb(PPT)
SnNb(PPT) Mixed oxide obtained using the coprecipitation method
Sn(CTAB)
Pure oxide obtained using CTAB as the template method
Nb(CTAB)
SnNb(CTAB) Mixed oxide obtained using CTAB as the template method
Sn(GLY)
Pure oxide obtained using the Pechini method, using glycerol
Nb(GLY)
SnNb(GLY) Mixed oxide obtained using the Pechini method, using glycerol

For catalyst characterization, X-ray-diffraction (XRD) measurements were performed

using a Shimadzu diffractometer, model XRD-6000, and a Cu Kα radiation (1.5418 Å)
source with a nickel filter to obtain wide-angle diffraction patterns in the 2θ = 3–40◦
range. Crystallite size (nm) was calculated using the Debye–Scherrer equation. Nitrogen-
adsorption measurements were performed at 77.15 K, using a gas-adsorption analyzer (Mi-
cromeritics, model ASAP-2020). The textural properties were estimated from N2 adsorption
isotherms, using the Brunauer–Emmett–Teller (BET) equation and Barrett–Joyner–Halenda
(BJH) method. Before the analysis, all the samples were pretreated under vacuum at
423.15 K for 24 h. Thermogravimetric (TG/DTG) analyses were performed using a Shi-
madzu analyzer, model DTG-60H, with an N2 flow-rate of 40 mL·min− 1 in the temperature
range of 30–800 ◦ C at a heating rate of 10 ◦ C·min− 1 . Fourier-transform-infrared (FTIR)
spectra were obtained with a Shimadzu IR Prestige 21 infrared spectrophotometer, using
tablets of potassium bromide (KBr). Eighty scans were performed in transmittance mode
in the spectral range of 4000–400 cm− 1 at a resolution of 4.0 cm− 1 . Raman spectroscopy
was performed at ~30 ◦ C, using a 532 nm laser, 10 mW power, 100× objective, and 16 data
acquisitions in 120 s with respect to silica on HORIBA scientific equipment, model XploRA.
The UV–Vis-DRS spectra were obtained on a Shimadzu model UV-2600 at a resolution of
8 cm− 1 . Scanning-electron-microscopy analyses were performed on a Shimadzu instru-
ment, model SSX-550 Superscan, with a tungsten filament. Initially, the samples were
metallized in a Sanyu Electron instrument, quick coater SC-701, for 8 min with a 10 mA
gold current target.

3.6. Fructose Conversion

All experiments were performed in 4 mL closed reactors under magnetic stirring and
heating, at several reaction times. The fructose solution (0.016 g of fructose in 2 mL of
deionized water) and 1.5 × 10−3 g of catalysts were used. Conversion, yield, and selectivity
were calculated from the results of quantification using HPLC. For this, the reaction product
was filtered using 0.45 µm porosity membrane-filters (MilliporeTM), and then injected
into a chromatograph (HPLC) with refractive-index (IR) detection. The analyses were per-
formed on a SHIMADZU (Japan) model CTO-20A liquid chromatograph with an isocratic
pump, RID-10A refractive index detector and manual injection system, with a sampling
handle of 20 µL. The chromatographic column Varian MetaCarb H Plus 300 × 7.8 mm
and precolumn Varian MetaCarb H Plus were obtained from Varian (Palo Alto, CA, USA),
operating with a column temperature of 55 ◦ C, and the eluent was a sulfuric acid solution
(0.005 mol·L−1 ) with a flow of 0.70 mL·min−1 . For the quantification of the reaction prod-
ucts, calibration curves of standard solutions were prepared. The chromatograms obtained
were treated using LabSolutions software (Shimadzu Corporation 2010, Kyoto, Japan). The
fructose conversion and the yield and selectivity of each product formed were calculated as
presented in the Supplementary Information. For reuse studies, the catalyst was removed
from the reaction medium by centrifugation, and calcined at 550 ◦ C for 4 h.
Catalysts 2023, 13, 285 16 of 18

4. Conclusions
Using the catalysts presented in this study, it was possible to efficiently convert fructose
in an aqueous medium, and the factors that influenced the transformation were the textural
and structural properties, as well as the number of acid sites. The materials that presented
the best conversions were the mixed oxides, with a prominence of SnNb(CTAB) and
SnNb(GLY), showing the importance of the modulation of properties using the synthesis
method. All systems were selective mainly for 5-HMF (5-hydroxymethylfurfural) and, to a
lesser extent, for the products of the retro-aldolic route, and this selectivity was preserved,
regardless of the catalytic system used. The reuse test for SnNb(GLY), which showed
stability for four cycles with no significant reduction in terms of conversion, suggested that
the hydrophobic characteristics of the rutile structure of SnO2 in contrast to Nb2 O5 resulted
in water-tolerant acid sites.

Supplementary Materials: The following supporting information can be downloaded at:

https://www.mdpi.com/article/10.3390/catal13020285/s1: Information concerning fructose conver-
sion, yield and selectivity of each product formed, Figure S1: Thermal profiles (TG) of the catalysts:
(a) Sn(PPT), Sn(CTAB) and Sn(GLY); (b) Nb(PPT), Nb(CTAB) and Nb(GLY); and (c) SnNb(PPT),
SnNb(CTAB) and SnNb(GLY); Figure S2: FTIR spectra using pyridine as probe molecule: (a) Sn(PPT),
Sn(CTAB) and Sn(GLY); (b) Nb(PPT), Nb(CTAB) and Nb(GLY); and (c) SnNb(PPT), SnNb(CTAB)
and SnNb(GLY); Figure S3. Scanning electron microscopy (SEM) images of the catalysts Sn(PPT),
Sn(CTAB) and Sn(GLY).; Figure S4. Scanning electron microscopy (SEM) images of the catalysts
Nb(PPT), Nb(CTAB) and Nb(GLY).; Figure S5. Scanning electron microscopy (SEM) images of the
catalysts SnNb(PPT), SnNb(CTAB) and SnNb(GLY).; Figure S6. Fructose conversion at 150 ◦ C us-
ing (a) Sn(PPT), Sn(CTAB) and Sn(GLY), (b) Nb(PPT), Nb(CTAB) and Nb(GLY) and (c) Nb(GLY)
SnNb(PPT) SnNb(CTAB) and SnNb(GLY).; Figure S7. Selectivity for soluble products identified in the
fructose conversion at 150 ◦ C using 1.5 × 10−3 g of catalyst (a) Sn(PPT) and Nb(PPT); (b) Sn(CTAB)
and Nb(CTAB); (c) Sn(GLY) and Nb(GLY).; Table S1: Yield (%) for soluble products identified in the
fructose conversion at 150 ◦ C in absence of catalyst or using 1.5 × 10−3 g of catalyst (a) Sn(PPT) and
Nb(PPT); (b) Sn(CTAB) and Nb(CTAB); (c) Sn(GLY) and Nb(GLY).
Author Contributions: Conceptualization, T.V.d.S.M., D.B.d.A.P., S.M.P.M. and M.R.M.; methodology,
T.V.d.S.M., D.B.d.A.P., S.M.P.M. and M.R.M..; investigation, T.V.d.S.M., D.B.d.A.P., S.M.P.M. and
M.R.M.; resources, S.M.P.M. and M.R.M.; writing—original draft preparation, T.V.d.S.M., D.B.d.A.P.,
S.M.P.M. and M.R.M.; writing—review and editing, T.V.d.S.M., D.B.d.A.P., S.M.P.M. and M.R.M.;
visualization, T.V.d.S.M., D.B.d.A.P., S.M.P.M. and M.R.M.; supervision, S.M.P.M. and M.R.M.; project
administration, S.M.P.M. and M.R.M.; funding acquisition, S.M.P.M. and M.R.M. All authors have
read and agreed to the published version of the manuscript.
Funding: This research was supported by the National Council for Scientific and Technological
Development (CNPq), the Brazilian Federal Agency for the Improvement of Higher Education
(CAPES), the Brazilian Innovation Agency (FINEP), and the Alagoas Research Foundation (FAPEAL).
T.V.d.S.M. and D.B.d.A.P. express their appreciation for fellowships granted by CAPES and CNPq.
S.M.P.M. and M.R.M. thank CNPq for research fellowships.
Data Availability Statement: Not applicable.
Acknowledgments: The authors also thank the LSCAT/CTEC/UFAL, TecNano/ICF/UFAL, and
GON/IF/UFAL teams for their contributions.
Conflicts of Interest: The authors declare no conflict of interest.

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