Catalysis Communications 179 (2023) 106686

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Catalysis Communications
journal homepage: www.elsevier.com/locate/catcom

Sol-gel mediated synthesis and characterization of hierarchically porous

Fe2O3/SiO2 monolithic catalyst for high temperature sulfuric
acid decomposition
Neelesh Kumar a, Atindra Mohan Banerjee a, d, *, M.R. Pai a, d, Sher Singh Meena b, A.K. Patra b,
P.U. Sastry b, d, Jagannath c, A.K. Tripathi a, d
a
Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400085, India
b
Solid State Physics Division, Bhabha Atomic Research Centre, Mumbai 400085, India
c
Technical Physics Division, Bhabha Atomic Research Centre, Mumbai 400085, India
d
Homi Bhabha National Institute, Anushaktinagar, Mumbai 400094, India

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

Keywords: To address the issues faced by microparticulate catalysts in fixed bed reactors for high temperature sulfuric acid
Fe2O3/SiO2 decomposition viz. channeling and mass transfer, we report the preparation, characterization of Fe2O3/SiO2
Hierarchically porous hierarchical porous monoliths and testing of its catalytic properties. Monoliths with varying Fe2O3 amounts
Monolith
(5–30 wt%) are synthesized by a modified sol-gel approach and characterized by powder XRD, Mössbauer
Sulfuric acid decomposition
Hydrogen generation
spectroscopy, SAXS, SEM-EDS and XPS. The Fe2O3(15 wt%)/SiO2 monolith exhibited a SO2 yield of ~62% at
800 ◦ C. The spent catalyst investigation established the dynamic nature of catalyst surface to accomplish the
reaction mechanistic demands.

1. Introduction
Through our earlier studies we have established that Fe2O3/SiO2 is a
highly promising catalyst for thermochemical sulfuric acid decomposi­
tion which is the highest temperature step in the Iodine-Sulfur (I–S) and
hybrid‑sulfur (Hy-S) thermochemical cycles for hydrogen generation
[1–3]. The I–S process schematically described in Fig. 1a, consist of
three chemical reactions progressing in a cycle and holds great potential
as a futuristic large-scale hydrogen generation method using either nu­
clear or solar energy addressing both energy and environmental con­
cerns (SI 1.1). The Hy-S cycle is another promising thermochemical
cycle for hydrogen generation, schematically represented in Fig. 1b.
Sulfuric acid decomposition,which the common heat extraction step in
both the cycles, proceeds stepwise as given in eq. SI 1.3 (supplementary
information), with kinetic limitation in SO3 decomposition step and thus
the requirement of a catalyst arises [1].
Till date broadly two categories of catalysts have been investigated
for sulfuric acid decomposition – noble metal based, and metal oxide
based. Noble metal (Pt) supported on metal oxide/carbide like TiO2,
SiO2, Al2O3, SiC, ZrO2, CeO2, BaSO4, Ta2O5 etc. have shown higher
activities but Pt-oxide formation, Pt-leaching, Pt-agglomeration and
sulfate formation of support are some of the major issues reported
[4–10]. Thus, cheaper and stable alternatives like metal oxides in
various forms viz. bulk, supported, doped, composites etc. have been
explored. Oxides of transition metals in bulk form as well as with the
support exhibit comparable activities and higher stability in the corro­
sive environment of H2SO4, SO3, SO2, O2, and H2O gases at high tem­
peratures [11–28]. We established by our earlier studies that the Fe2O3/
SiO2 catalyst holds specific advantages over other candidate oxides,
which include resistance to support sulfation [3], good redox charac­
teristics [1] and stabilization of Fe2O3 nanoparticles via Fe2O3-SiO2 in­
teractions [1,2].
However, an important criterion for the application of a heteroge­
neous catalyst in flow through catalytic industrial reactors is that the
desired physical form should be granular i.e., spheres/monoliths/pellets
etc. of suitable size (few mm) [24–26]. Such macro-
particulatesensureleast pressure drop across the fixed bed catalytic
reactor with adequate intra-granular space for the reactant gases to flow.
But, simultaneous channeling or catalyst bypass of the reactants be­
comes an issue. Fig. 1c explains the mass transfer limitations, in the case
of a non-porous, macroparticulate catalyst, where the reactants cannot
access bulk of the macroparticulate. This phenomenon, results in

* Corresponding author at: Hydrogen Energy and Catalysis Section, Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400085, India.
E-mail address: atinmb@barc.gov.in (A.M. Banerjee).

https://doi.org/10.1016/j.catcom.2023.106686
Received 1 February 2023; Received in revised form 22 April 2023; Accepted 4 May 2023
Available online 5 May 2023
1566-7367/© 2023 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
N. Kumar et al.
incomplete utilization of the entire volume of the catalyst granules and
only the geometric surface area become significantly utilized. Porous
monolithic type catalyst where the active materials can be incorporated
within its porous network offer an appropriate solution [29]. Mass
transfer of the reactants and products across the radius of the monoliths
can occur by diffusion through the pores of the permeable walls as
shown in Fig. 1c. The hierarchical porosity in monoliths ensures avail­
ability of substantial fraction of its surface for catalytic action. In brief,
monoliths offer a feasible solution in terms of mechanical strength,
porosity, diffusion, catalytic performance, stability [29–34].
Thus, it emerges that SiO2 in hierarchically porous monolithic form
has crucial application as catalyst support with the potential of
deployment in large scale fixed bed catalytic reactors. A basic structural
requirement of these monolithic silica, is the presence of multimodal
porosity particularly meso and macro porosity. Porous silica with
multimodal porosity has been reported by utilizing two pore formation
methods [35,36], using inorganic supramolecular templates [37,38], gel
Fig. 1. (a) Schematic Representation of Iodine-Sulfur (I–S) and (b) Hybrid-Sulfur (Hy-S) cycles (c) Schematic representation of mass transfer limitations in a non-
porous macroparticulate catalyst with a hierarchically porous monolith. The schematic is considered for Fe2O3/SiO2 catalyst and the model reaction depicted is gas
phase SO3 decomposition,
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Catalysis Communications 179 (2023) 106686
casting [39,40], using bacterial threads [41,42]. However, extensive
studies were carried out by Nakanishi and group [43–45] for estab­
lishing the sol-gel synthesis methodology for monolithic silica with
controlled phase separation and gelation kinetics during synthesis
employing polyethylene glycols. Such type of monolithic silica was
utilized in chromatographic applications [43–46] and has enormous
potential for application in catalytic reactions [47].
In monolithic silica supported catalyst, the catalytically active
component can be dispersed or immobilized on the matrix by various
methods viz. wet impregnation [48,49], deposition-precipitation [50],
equilibrium-adsorption [1,51], solvothermal [2], polyol [2,52,53] and
other methods. These conventional methods of catalyst component
dispersion yield materials with either non-uniform zones of composition
or structural irregularities or morphological differences [50]. However,
in supported catalyst the objective of attaining a uniform dispersion of
the active component is crucial which can be accomplished only
employing a proper preparation strategy [50]. Arriving at a
N. Kumar et al. Catalysis Communications 179 (2023) 106686

compositional, structural, morphological uniformity all through the 3D
monolith is of prime concern. With an aim to address the above issues, in
this study we attempted the immobilization of Fe2O3 catalysts on SiO2
monoliths with a mixed precursor approach. Herein, the precursor of
silica and iron oxide both were intimately mixed in the starting solutions
to generate the sol and then the monoliths were synthesized via gel
formation, solidification and its consequent thermal decomposition.
In this article, we report the preparation, characterization of a series
of Fe2O3/SiO2 monoliths and testing of the most promising catalyst for
thermochemical sulfuric acid decomposition. The preparations of the
monoliths are carried out using a modified sol-gel route with poly­
ethylene glycol as the gelling and pore forming agent. The iron and
silicon precursor – iron acetyl acetonate and tetra ethyl ortho silicate are
premixed into the sol with an aim to achieve uniform dispersion of the
Fe and Si components in the gel. The thermal decomposition of the so­
lidified gel is monitored by TG-MS to understand the decomposition
mechanism of the gel and consequent pore formation in the monoliths.
The composition, structural, textural and morphological properties of
the prepared monoliths are studied by powder X-ray diffraction (XRD),
Mössbauer spectroscopy, small angle X-ray scattering (SAXS), scanning
electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS)
and X-ray photoelectron spectroscopy (XPS). Finally, the potential of the
monoliths as a catalyst for sulfuric acid decomposition is investigated for
high temperature sulfuric acid decomposition at 800 ◦ C for 25 h in an
indigenously developed flow through quartz catalytic reactor to study
the catalytic performance and stability of the most potential Fe2O3/SiO2
monolith. The spent catalyst is further investigated by various tech­
niques to ascertain the dynamic nature of the catalyst establishing the
compositional and morphological modifications and propose the most
probable mechanism. This study will provide useful insights into the
design strategy of catalytically active monoliths for high temperature
applications.
amount of TEOS is added to it. This solution is initially turbid and so it is
stirred by a magnetic stirrer using a magnetic needle at 500 rpm for 2 h
to obtain a clear sol. Stoichiometric amounts of Fe-acac is subsequently
added targeting a 5, 15 and 30 weight percentage loadings of Fe2O3. The
specific amounts of each component used for synthesis of Fe2O3/SiO2
monoliths are given in Table 1. SiO2 monoliths are also prepared
without Fe-precursor addition in one case. These sols are allowed to gel
and then aged for 72 h at 40 ◦ C to obtain the solid monoliths. The
monoliths are then dried for 48 h in an oven at 80 ◦ C to obtain the as-
synthesized samples. Subsequently, the SiO2 and Fe2O3/SiO2 mono­
liths are calcined at 550 ◦ C for 5 h and finally at 1000 ◦ C for 2 h in air.
The heating rate during the calcinations is kept at 1 ◦ C/min.
2.2. Characterization of the monoliths
To understand the nature of volatile species evolved during thermal
decomposition of the organic-inorganic hybrid structure of the as-
synthesized samples TG-MS is performed using a thermobalance and
the evolved gases are analyzed by a QMS coupled to the TG (SETSYS
Evolution-1750, Setaram). The structural characterization is done by
recording the powder XRD patterns in a Philips X’Pert pro X-ray
diffractometer using Cu Kα radiation (λ = 1.5418 Å) at 40 kV and 30 mA.
The Mössbauer spectra of the samples are recorded using a spectrometer
which employs a source of 57Co in Rh matrix of strength 50 mCi. Ve­
locity scale is calibrated using an iron metal foil. Small angle X-ray
scattering (SAXS) measurements are carried out for the samples using a
small angle goniometer (Rigaku) mounted on a rotating anode X-ray
generator. Scattered X-ray intensity I (Q) is measured by a scintillation
counter by varying the scattering angle 2θ, where Q is the scattering
vector given by 4π.sin (θ)/λ and λ is the wavelength of incident (CuKα) X-
rays. The morphological features of the samples are analyzed by a
scanning electron microscope (FESEM - SUPRA 400VP Gemini, Zeiss)

2. Experimental
Table 1
Details of samples prepared and their textural properties.
2.1. Preparation of the monoliths
Details Sample 1 Sample 2 Sample 3 Sample 4

Tetraethoxysilane (TEOS, Fluka) was used as the silica source and Tetraethyl ortho silicate (TEOS) 7g 7g 7g 7g
iron acetyl acetonate (Fe-acac) as the precursor of iron. Poly(ethylene Ferric Acetylacetonate 0g 0.233 0.7 1.4
Polyethylene glycol (PEG- 1g 1g 1g 1g
glycol) (PEG, Mol. wt. 20,000 g/mol, Aldrich) was used as the phase- 20000)
separation-inducing agent for gelation and nitric acid as the hydrolysis Pyrolysis Temperature 1000 ◦ C 1000 ◦ C 1000 ◦ C 1000
and condensation agent for TEOS. The preparation strategy for the Abbreviation - FS1 FS2 FS3
synthesis of Fe2O3/SiO2 monolithis is schematically shown in Fig. 2. Pore diameter from SAXS 14.5 nm 11.6 nm 10 nm 8.2 nm
Fe2O3% (as per EDS) 0 ~ 4.1 ~13.8 ~26
Briefly, PEG is dissolved in aqueous nitric acid solution and required

Fig. 2. Schematic for the synthesis of Fe2O3/SiO2 monoliths.

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N. Kumar et al. Catalysis Communications 179 (2023) 106686

and the elemental composition are analyzed by energy dispersive X-ray Table 2
spectroscopy (EDS) (Oxford Instruments EDS system attached to the Assignment of peaks obtained in mass spectra of the as-synthesized samples.
FESEM). XPS analysis of the samples are performed at 4339 eV photon m/ Possible Species/ Peak Temperature (from TG-MS)
energy at the PES-BL14 beamline (BARC) at Indus-2, RRCAT, Indore. z evolved gas

SiO2 FS1 FS2 FS3

2.3. Testing of Fe2O3(15. Wt%)/SiO2 monoliths for sulfuric acid
15 CH3- Methyl radical 195 209(very 190 185
decomposition reaction (very minor) 280 228
minor) 260 (major) 295
The catalytic activity of the Fe2O3/SiO2 monolith are evaluated in a 226 (major)
quartz flow through catalytic reactor as discussed in our earlier studies (major) 856
288
[16] and schematically represented in Fig. SI 1. In brief, a syringe pump
(minor)
is utilized to inject concentrated sulfuric acid (98 wt%) into the pre- 17 -OH Hydroxyl radical 175 185 174 182
heater and carried by nitrogen carrier gas (flowing at 40 cc/min). In 228 263 286 (major)
the pre-heater (filled with quartz beads) the acid undergoes vaporization (major) (both (both 320
289 major) major) (major)
and dehydration to sulfur trioxide. In the next zone of the quartz reactor
858
the sulfur trioxide decomposition takes place in presence of the catalyst. 18 H2O 174 185 176 181
The product analysis is done by trapping sulfur dioxide product gas in a moisture 228 263 286 321
standardized sodium hydroxide solution. And the un-reacted acid (major) (both (both (both
condensate from the condenser is collected. The unreacted acid and the 289 prom) prom) prom)
858
sodium hydroxide solutions are analyzed by chemical titrimetric
28 CO Carbon monoxide 196 220 200 187
methods. The catalytic activity is measured by percentage SO2 yield: or ethene (consumed) (very 262 286 323
minor) (major) (major) (major)
No.of moles of SO2 produced
Percentage SO2 Yield = × 100 228 858
No.of moles of H2 SO4 in feed (major)
288
The catalyst is pretreated at a temperature of 500 ◦ Cfor 2 h under N2 (minor)
flow. The catalytic activity of one of the promising Fe2O3/SiO2 monolith 30 HCHO 196 215 190 185
is measured for 25 h at 800 ◦ C at a WHSV of 27 g acid g− 1 h− 1. 228 262 284 (major)
(major) (major) (both 295
288 506 prom) (major)
2.4. Characterization of the spent catalyst
470 569
600
To understand the chemical nature of the spent catalyst it is collected 858
and analyzed by TG-MS, SEM-EDS and XPS is the same equipment and 43 H2 COCH 227 260 190 182
(decomposition of (major) 280 321
conditions as mentioned above.
C2H4O monomer 288 (major) (major)
units),CH3-CO+ 858
3. Results and discussions 44 CO2, C2H4O monomer 195 231 190 183
units, acetaldehyde 229 262 286 218
The details of the sample prepared viz. the weight of each precursor (major) (major) (major) 334
288 (major)
taken, the abbreviation of each sample, and the actual Fe-content as
(major) 563
determined by EDS are listed in Table 1. It is evident from the Table that 372 600
the Fe2O3 weight percentages correspond to 4.1, 13.8 and 26 in FS1, FS2 858
and FS3 respectively. 46 Ethanol (consumed) 195, 217 192 185
230 (major) (major), 211
The Fe-incorporated SiO2 is prepared by the modified sol-gel method
(major) 261 286 304–333
as described in experimental section. The mould employed is a micro- 289 496 460 (major)
titre plate in which the as-synthesized gel is allowed to solidify. Pho­ (very 564
tographs of the obtained SiO2 and Fe2O3/SiO2 as-synthesized solids are minor) 600
shown in Fig.SI 2a. The photograph of the corresponding monoliths 522 858
(major)
obtained after calcinations of the solidified gels at 1000 ◦ C is shown in
984
Fig.SI 2b. The as-synthesized solidified gels which are basically organic- 58 Acetone –[-O-C(CH3) 196 204 190, 293
inorganic hybrids formed by polycondensation process of the hydro­ 2-]n– 224 260 280 (major)
lyzed TEOS in presence of gelling agent PEG. Various volatile chemical Glyoxal C2H2O2 288 (major) (major)
components in this hybrid undergo thermal decomposition during the
calcination process and yield the porous Fe2O3/SiO2 monoliths. Some of
the highest peak intensity is observed. As can be seen from Table 2, the
the reactant species employed to form the gel decomposes and provide
major components evolving by decomposition of the as-synthesized
the porous pathways within the monolithic structure. To understand this
SiO2based gels are methyl (CH3), hydroxyl (OH), moisture (H2O), car­
chemical phenomenon involved in the formation of these pores by
bon monoxide (CO), formaldehyde (HCHO), acetyl (CH3CO), ethanol
decomposition of various components of the organic-inorganic hybrid
(CH3OH) and acetone (CH3COCH3).
moiety, the as-synthesized monoliths are analyzed by TG-MS. The TG
The analysis of the mass loss patterns from the as-synthesized sam­
patterns for the decompositions are shown in Fig. SI. 3 and the details of
ples from Table-2 show that there are two groups of species with each
weight loss calculations are shown in Table SI1. From the figure and
group exhibiting almost similar gas evolution patterns from the samples.
table, it is evident that all the as-synthesized samples undergo weight
H2O and OH evolutions show identical decomposition patterns while all
loss in several steps in the 125–370 ◦ C range.
other species i.e. CH3, CO, HCHO, CH3CO, CH3CHO, and CH3COCH3
The thermal decomposition products are further analyzed by a mass
exhibit similar profiles with minor differences in certain cases in the
spectrometer (MS) to gain a knowledge regarding the decomposition
mass spectra. Mass spectra for each of these species evolved from all the
mechanism of the as-synthesized samples and variations in the decom­
as-synthesized samples are plotted against temperature and two repre­
position patterns with Fe2O3-incorporation. Table 2 lists the masses of
sentative plots for m/z = 18 and 58 are shown in Fig. 3. The temperature
the species which are detected by the MS and the temperature at which

4
N. Kumar et al.
Fig. 3. The evolved gas mass spectra patterns (m/z = 18 and 58) from the as-
synthesized monoliths as a function of temperature
dependent evolved gas mass spectra for all other relevant species are
shown in Fig. SI4. From Fig. 3a it is evident that liberation of water takes
place from as-synthesized SiO2 in 3-steps, a major peak at 228 ◦ C along
with a prominent smaller peak at 174 ◦ C and a minor peak at 289 ◦ C. The
appearances of these peaks are due to liberation of retained water in the
samples even after evaporation and complete drying of the gels. The
hydrated as-synthesized SiO2 samples evolve water on heating but
definitely the mass loss pattern denotes that there must be two/three
different sites at which it is retained. However, upon Fe2O3-immobili­
zation interesting modifications in the water loss pattern are observed.
For as-synthesized FS1, the water evolution as a function of temperature
shows a two-peak pattern instead of three and the first peak is of much
higher intensity and peak area in contrast to that observed for SiO2. Both
the peaks appear shifted to higher temperature region (~185 ◦ C and
263 ◦ C) than that of SiO2. Thus, considerable differences in water
retention pattern, site and capacity appears upon Fe2O3-incorporation in
the SiO2 matrices. Upon further Fe2O3-loading, the as-synthesized FS2
sample evolves water in two steps with peaks at 176 ◦ C and 286 ◦ C. H2O
evolution pattern for the as-synthesized FS3 sample shows a similar two-
step pattern but shifted to further higher temperature. Thus, progressive
shifts in water evolution patterns to higher temperatures could be
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Catalysis Communications 179 (2023) 106686
observed with increased loadings of iron. An unusual feature, which is
additionally observed in case of FS3 is the appearance of a small peak at
~858 ◦ C. This unusual behaviour can be attributed to any one of the two
phenomenon – (1) retention of molecular water or hydroxyl in layer/
deep pores or (2) retention and decomposition of water of crystallization
[54,55]. Increased Fe2O3 content can also result in pore narrowing or in
extreme cases Fe2O3 phase separation and pore blocking which might
also result in this interesting high temperature water retention. Such
retained water can drastically modify solid state material properties viz.
luminescence [55]. The OH species exhibit almost similar evolved gas
analysis pattern in the mass spectra vs. temperature plot, as shown in
Fig. SI4, which indicates that the evolution of OH arises solely as a
fragment of water.
Fig. 3b exhibits the evolution pattern at m/z = 58 from the as-
synthesized samples as a function of temperature. A three-step evolu­
tion of this component is visible from as-synthesized SiO2 with a major
peak appearing at 224 ◦ C and two minor peaks on either side at 196 ◦ C
and 288 ◦ C. The assignment of this component is difficult, but the major
possibility is glyoxal formed from the decomposition-oxidation of the
PEG component [56]. The evolution pattern completely changes in FS1
where only a single major peak appears at 260 ◦ C and a minor peak at
204 ◦ C. The complete change in pattern can be attributed to evolution of
acetone formed from the hydrolysis of Fe(acac). The location of this
major peak substantially shifts to higher temperature region in the case
for FS2 and FS3 as-synthesized samples, indicating a delayed liberation
of this species from the high Fe-content samples.
Evolution of species seen in MS can fairly be linked to the nature of
organic-inorganic hybrids formed via hydrolysis and polycondensation
of TEOS interdispersed in PEG matrix in presence and absence of Fe
(acac). Ethanol (m/z = 46), acetaldehyde (m/z = 44) and formaldehyde
(m/z = 30) in the evolved gas analysis can be released during decom­
position of TEOS, and then these species further decomposed into CO2
and H2O [57–60]. Ethanol is also a product of TEOS hydrolysis. Presence
of Fe(acac) resulted in the evolution of acetone (m/z = 58) during
decomposition, which further decomposed into CO, CO2, and H2O [61].
CH3 (m/z = 156) species can originate via fragmentation of any species
and decomposition products of either PEG/TEOS/acac [61]. Similarly,
CH3CO (m/z = 43) radicals can arise from various precursors which can
further produce CO (m/z = 28) [61,62]. Polyethylene glycol inter­
spersed in the matrix network undergoes decomposition either through
hemolytic cleavage or heterolytic dissociation. Ethanol can also form
during decomposition of PEG as the compounds of a terminal hydroxyl
group (ethanol m/z = 46). Decomposition of C2H4O monomer units (m/
z = 44), whose origin can be ascribed to PEG, result in the evolution of
H2COCH (m/z = 43) that further decomposes to carbon monoxide (CO,
m/z = 28) and methyl radicals (CH3, m/z = 15) [62–67]. The oxidative
decomposition of PEG mostly yielded glyoxal (m/z = 58). Thus, multiple
species with several possibilities of evolution from the organic-inorganic
matrix arise. Based on the findings from the TG-MS patterns and earlier
literature [43–47,57–67] the formation scheme of the Fe2O3/SiO2
monoliths is shown in Fig. 4.
The powder X-ray diffraction patterns of the samples are shown in
Fig. 5a. As can be seen from the figure, all the samples show a broad
hump at 2θ ~ 22 degrees arising due to reflections from short range
ordering in the monolithic amorphous silica phase (mineral name:
crystobalite, tetragonal crystal system, Space Group: P 41212 (92), ICSD
No. 47219). XRD was unable to determine the specific iron oxide phase
and thus we utilized Mössbauer spectroscopy to determine it. Fe2O3 has
four different polymorphic forms (α, β, γ and ε) as discussed in earlier
studies [1,3,11].
Room temperature Mössbauer spectra of the dispersed Fe2O3
monoliths (FS2 and FS3) are shown in Fig. 5b and analysis results are
given in Table SI 3. The Mössbauer spectra for both the samples can be
fitted with two symmetric doublets. The relative area of these two
doubles is found to be 85.5 and 14.5% for samples FS2 whereas it is 82
and 18% for sample FS3. The values of isomer shift (δ) for both samples
N. Kumar et al. Catalysis Communications 179 (2023) 106686

Fig. 4. Schematic representation of the synthesis of the monoliths via hydrolysis of TEOS followed by polycondensation in PEG matrix to yield organic-inorganic
hybrids and subsequent dehydration to as-synthesized monoliths and finally thermal decomposition to yield hierarchical porous monoliths.

are in the range of 0.27–0.5 mm/s which corresponds to high spin
oxidation state of Fe3+ions. Based on the Mössbauer parameters it is
concluded that both doublets are due to the presence of paramagnetic
γ-Fe2O3 phase. The doublet-B with higher isomer shift and low relative
area showing a higher value quadrupole splitting (ΔEQ ¼ 2.181 and
2.298 mm/s), confirms the asymmetry around Fe3+ ions. The possibility
of α-Fe2O3and ε-Fe2O3 phases which were detected in our earlier study
on Fe2O3/SiO2 powders can be neglected because both the phases show
magnetic sextets which is absent in the present samples [1]. In this
study, the Fe-component is in-situ incorporated within the SiO2 species
during synthesis, interspersed in a polymer matrix and the phase evo­
lution seems to completely differ from the outcome in our studies where
Fe2O3 was separately immobilized on the porous SiO2 support. Gener­
ally, γ-Fe2O3 was transformed to either α-Fe2O3 or ε-Fe2O3 phases during
calcinations at 1000 ◦ C during preparation of Fe2O3/SiO2 powders
[1–3]. But, during the present mixed precursor sol-gel approach even
upon calcinations at 1000 ◦ C the γ-Fe2O3 is retained. Thus, behaviour
and evolution of Fe2O3 phase is highly depended upon the method of
synthesis as it is dependent on the local chemical and physical envi­
ronment within which it is nucleating and growing [68–70]. Here, the
iron oxide phase nucleates and grows within a confined environment
and simultaneously with the silica phase. Further growth, during higher
temperature calcination is also quite different than the case where the
iron oxide is dispersed over the preformed porous silica matrix. The

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N. Kumar et al. Catalysis Communications 179 (2023) 106686

Fig. 5. (a) XRD of all the synthesized samples and (b) Room Temperature Mössbauer spectra of the FS2 and FS3 samples, and schematic representation of the unit
cell of the γ-Fe2O3 polymorph which is observed in our study.

Fig. 6. (a) Small angle X-ray scattering profiles of SiO2/Fe2O3. Solid lines are fits to the data. S0 is SiO2 (b) Variation of the mesopore size with wt% (ϕ) of Fe2O3 in
SiO2 matrix.

7
N. Kumar et al.
Mössbauer spectra further suggest the presence of two different iron
oxide sites, one with major occupancy and the other with lower one. The
fraction of iron oxide in the lower occupancy site however increases
from FS2 to FS3.
The small angle X-Ray scattering (SAXS) profiles of the synthesized
monoliths are given in Fig. 6a. The SAXS intensity I(Q) of SiO2 arise from
pores within the silica (SiO2) matrix. In the high-Q region, I(Q) varies
linearly with Q indicating a power-law scattering. The intensity in this
region arises from smaller pores and the exponent in the power-law
indicates morphology of their surface. The data in the low-Q region,
which represents scattering from bigger pores, also vary linearly indi­
cating power-law variation of the intensity. In view of the presence of
multi-scale microstructure, the intensities of the samples were fitted to
the equation [71,72].
( / ) ( / ){ / }α
I(Q) =A.exp. − Q2 .Rg 2 3 +B.exp. − Q2 .Rs 2 3 . [erf (Q.Rg/√6)]3 Q
( / ) { / }β
+C.exp. − Q2 .Rs 2 3 +D. [erf (Q.Rs /√6) ]3 Q
(1)
Where Rg, Rs are the radii of gyration of bigger and smaller pores
respectively, α, β are the power-law exponents of I(Q) in the low-Q and
high-Q regions. The radius of gyration is equal to √(3/5) x R where R is
the radius of the pores. Since the Gunier region of the SAXS profiles in
Fig. 7. SEM images of (a and b) SiO2 (c) FS2 and (d) FS3 samples.
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Catalysis Communications 179 (2023) 106686
the low-Q region is absent, the first term of the Eq. (1) has been ignored
in the fits and the size of bigger pores (Rg) is fixed at >200 nm.
The structural parameters obtained from the fittings are given in the
Table SI3. The pristine silica matrix consists of large sized pores with
mass (pore) fractal structure of fractal dimension 2.85. It also consists of
smaller pores of average radius 7.2 nm with similar structure and fractal
dimension 2.8. The larger fractal dimensions indicate higher pore den­
sity. As the Fe2O3 is incorporated into the silica matrix, the shapes of the
SAXS profiles remain same as that of SiO2 suggesting that the structural
morphology is intact. But, a significant change in the structural pa­
rameters is noticed. As Fe is incorporated in the SiO2 matrix in FS1 and
then increased to FS2, the fractal dimension of the larger pores decreases
suggesting reduction of pore density which may be due to the presence
of solid particles of Fe2O3 in the pores, at least partially occupied. With
further increase in the Fe2O3 concentration in FS3, the larger pores show
surface fractal morphology indicating rough pore boundaries. This may
be due to the presence of some Fe2O3 particles outside the pores (at the
boundary) as well due to very high content of Fe2O3. These findings
corroborate the Mössbauer spectra results where we observed increase
in occupancy of iron oxide in the low occupant site in FS3. Thus, it can
be concluded that the precipitation of iron oxide outside the pore in­
creases as the Fe-content increases.
The variation of the smaller pore or mesopore size as a function of Fe-
N. Kumar et al.
content in the monoliths is shown in Fig. 6(b). Regarding the mesopores,
with an increase in concentration of Fe2O3 from FS1 to FS3, the radius
(R) of the smaller pores gradually decreases to about 4.1 nm (Fig. 6b,
Table 1) whereas the mass (pore) fractal structure changes to the
structure with diffuse pore boundaries (power-law exponent > 4). This
suggests the Fe2O3 particles may be occupied in smaller pores too, both
inside as well outside, surrounding the boundary periphery. This can
result in pore blocking as well in addition to the pore narrowing phe­
nomenon as can be observed from Fig. 6b. As a consequence of this pore
narrowing or blocking a shift in the volatile species decomposition to­
wards higher temperature region is observed in TG-MS of the as-
synthesized samples as we move from FS1 to FS3.
The SEM images of the synthesized SiO2 monolith and the Fe-
incorporated ones are shown in Fig. 7. Fig. 7a shows the outer cylin­
drical surface of two monoliths synthesized. It is evident from these
figures that the diameter of the cylinders is of ~3 mm. The inner surfaces
of the monoliths are explored in Fig. 7 (b-d) for SiO2 and the Fe-
incorporated ones. Fig. 7b exhibits the SEM image of the synthesized
SiO2 monolith which shows that the samples have numerous macro­
scopic pores of varied size and slightly disordered spherical/oval in
shape. The sizes of the macropores vary in the range of ~10 μm to 100
μm. On Fe2O3-incorporation, the nature of macropore distribution is
retained in FS2 but on further Fe-loading the well-defined macro­
porosity is lost in FS3. This result is corroborating the findings of the
SAXS analysis where the precipitation of Fe2O3 outside pores in signif­
icant amount can be noticed for FS3. Such pore constriction phenome­
non is not advantageous with respect to catalytic applications as the
main purpose of interlinked hierarchical porosity is to tackle mass
transfer issues and is thus lost to a significant extent in FS3. The FS2
sample is investigated in detail for understanding the distribution of
pore in the Fe2O3-SiO2 matrix as here reasonable porosity with
maximum Fe-content is achieved. Fig. 8a shows a low magnification
SEM image of FS2 sample and the selected area marked in red square is
magnified and shown in Fig. 8b. On further magnification a clear image
of few spherical and oval shaped macropores are visible of sizes 10–20
μm in Fig. 8c. Mesopore presence and their characteristic is earlier
detected in the SAXS investigations. Thus, it can be fairly concluded that
Fe2O3/SiO2 monoliths of hierarchical porosity is obtained by the sol-gel
method of preparation.
The energy dispersive X-ray emission spectra (EDS) are also recorded
for the samples and the spectra is shown in Fig. SI 5. The elemental
compositions as derived from the spectra are listed in Table. 1. EDS
elemental mapping of O, Si, and Fe for the SiO2 and FS2 sample is shown
in Fig. SI 6. The findings are almost in tune with the nominal
Fig. 8. SEM images of FS2. Red squares show a low magnification SEM image of FS2 sample and the selected area marked in red square is magnified. (For
interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
9
Catalysis Communications 179 (2023) 106686
compositions expected from initial precursor ratios taken.
The X-ray photoelectron spectra (XPS) of monolithic Fe2O3/SiO2
samples revealed surface characteristics which is crucial from the cat­
alytic application point of view. The chemical state of the elemental
species located at the surface (few monolayers) can be obtained from
such studies which take part in heterogeneous catalyzed reaction [73].
The Fe2p XPS spectra of the three synthesized Fe2O3/SiO2 monoliths are
shown in Fig. 9(a). There is no peak associated to the presence of iron on
surface in FS1 and FS2, which shows the absence of iron on outer
structure of monoliths. This could be attributed to the immobilization of
Fe2O3 within the pores of the hierarchically porous silica monolithic
structure. Such a phenomenon in which the catalytically active Fe2O3
remains incorporated within the pores and consequently absent or
shows substantial lower content on the surface have been observed
earlier by our studies [1,2] and also by other authors [74–76]. As the
content of Fe2O3 increases, and their deposition occurs outside the
porous network in FS3, the Fe2p3/2 peak appears at a binding energy of
~711 eV, indicating the presence of Fe3+ on the surface [1]. The sepa­
ration between this peak and the Fe2p1/2 peak is ~13.6 eV which further
confirms the existence of Fe3+ [11,76]. The XPS spectra for O1s in the
samples are shown Fig. 9(b). For FS1 and FS2 the O1s peak could be
deconvoluted only into two peaks – one at ~532 eV due to oxygen in
SiO2 while another at higher BE at ~534.5 eV due to chemisorbed ox­
ygen and hydroxyl groups attached to SiO2. The O1s peak in FS3 in
contrast could be deconvoluted into three peaks. The most prominent
and central peak is assigned to O2− present in the SiO2 support as it is the
major species on the surface. The highest BE peak with values in the
range of 534 eV is attributed to chemisorbed aerial oxygen or adsorbed
moisture or hydroxyl groups on the silica surface [1,2,77,78].The lowest
BE peak (527–529 eV) which was absent in FS1 to FS2 and present in FS3
could be assigned to O2− linked with Fe2O3. Obviously, as per our earlier
findings the deposition of Fe2O3 as separate phase on the outer surface of
the pores of silica and at boundaries mostly led to the appearance in FS3
[1]. The Si2p XPS spectra of the monoliths are shown in Fig. SI 7 which
verifies the presence of silicon as Si 4+ [1].
All the three catalyst samples are tested for sulfuric acid decompo­
sition at 800 ◦ C at a WHSV of 27 g acid g− 1 h− 1 and the result is plotted
in Fig. 10 a. A 10–20 mesh fraction of the sample is extracted and
examined at 800 ◦ C for sulfuric acid decomposition reaction in the
catalytic reactor described in the experimental section. It is evident that
FS2 exhibits the highest catalytic activity among three samples. The 25-
h time-on-stream experimental SO2 yield at 800 ◦ C with FS2 catalyst is
shown in Fig. 10b. The catalytic SO2 yield of ~62% could be achieved at
800 ◦ C and the activity remained almost constant with time. Thus, it can
N. Kumar et al.
Fig. 9. X-ray photoelectron spectra of (a) Fe2p and (b) O1s of the Fe2O3/SiO2 monoliths samples calcined at 1000 ◦ C. The black curve is the recorded spectrum, the
pink, green and orange solid curves are the deconvoluted peaks while the red dashed curve is the envelope. (For interpretation of the references to colour in this
figure legend, the reader is referred to the web version of this article.)
be observed that the performance of the FS2 sample is almost at par with
the Fe2O3/SiO2 catalyst prepared by several other methods [1,2]. In this
case the catalyst is in a particulate or monolithic form and thus can find
application in larger scale fixed bed catalytic reactor applications like
large scale hydrogen production by I–S or Hy-S process.
FS2 spent catalyst after 25 h run is investigated ex-situ for modifi­
cations in structure, morphology, oxidation state and to elucidate the
mechanistic aspects of reaction. Such a study would guide us towards
the better understanding of catalytic properties that can allow us to
identify the factors that increase or decrease the rates of reaction. In
addition to this, ex-situ characterization would inform us the reasons if
any for catalyst deactivation and thus enable us to predict the catalyst
stability on exposure to reaction conditions. Fig. 11a shows the SEM
image and elemental mapping of Fe, O, and Si on the spent catalyst
surface. It can be seen from the EDS that the iron composition remains
almost constant in the spent sample after 25 h reaction run. The
elemental Fe content which is 9.7% in the fresh catalyst, reduced to
9.2% in the spent catalyst. However, this slight change can partly be
accounted for iron sulfate formation during reaction. The XPS pattern of
the spent catalyst is also recorded and analyzed. XPS spectra (Fig. 11b)
shows the appearance of S2p peak at ~169 eV which is attributed to
surface sulfate. However, upon deconvolution of this broad and asym­
metric sulfate peak three distinct peaks could be identified. The highest
BE peak can be attributed to weakly adsorbed SO2 on monolithic Fe2O3/
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Catalysis Communications 179 (2023) 106686
SiO2 surface/pores which gave the peak a typical asymmetry. The lowest
BE peak in contrast can be assigned to the sulfated Fe with Fe-O-Si
linkages [1]. The central major sulfate peak is due to iron sulfated
during reaction immobilized on silica surface [1,79–81]. The compar­
ative Fe2p XPS patterns of the spent and fresh FS2 sample is shown in
Fig. SI 8a. The appearance of Fe-peak in the spent catalyst in contrast to
fresh, establishes the surface re-organization of Fe2O3 species (which
participates actively in the reaction) with Fe being dragged outside the
pores along with sulfate formation during catalytic action [11]. The
comparative O1s spectra of the fresh and spent FS2 monolith are shown
together in Fig. SI 8b for easy understanding. Interestingly, the spent
O1s peak is broad and symmetric and thus is deconvoluted into three
peaks. The central peak with maximum peak area due to O2− in silica
species retains its position at ~532.5 eV. The one at lowest BE can be
assigned to O1s Fe-sulfates which further confirms re-organization of
surface Fe-species during catalytic operation.The peak area of this
deconvoluted peak is substantial indicating the significant presence of
Fe-components outside the pores. Also, chemisorbed oxygen peak is
sufficiently prominent as molecular oxygen is one of the reaction
products of sulfuric acid decomposition and is adsorbed to a consider­
able extent.
To understand the thermal stability of the iron sulfate species which
is found to exist on the spent catalyst surface itis subjected to TG-MS in
the temperature range of 40–1000 ◦ C. Fig. 11c shows the intensity of
N. Kumar et al.
Fig. 10. (a) Catalytic activity of the three synthesized monolithic samples for
sulfuric acid decomposition and (b) the 25-h time-on-stream experimental SO2
yield at 800 ◦ C with FS2 as catalyst at a WHSV of 27 g acid g− 1 h− 1.
evolved gas, having mass number 64 (SO2) as a function of temperature.
The small peak observed at ~260 ◦ C, which was also seen in our earlier
studies [1] is most probably due to thermal desorption of adsorbed SO2
species (observed in XPS) within the hierarchically porous network of
the monoliths. Another small peak appears at ~500 ◦ C which can be
attributed to the initiation of decomposition of iron-sulfate species.
Beyond this temperature a continuous SO2 evolution extending upto
1000 ◦ C could be observed. This slow and prolonged evolution is due to
sluggish desorption of the gaseous SO2 formed by decomposition of
surface Fe-sulfate. From the spent catalyst evaluation, it is evident that
the dispersed Fe2O3 undergoes surface sulfation and the evolution of SO2
occurs by the decomposition of these sulfate species.
From the above spent catalyst investigations, we can fairly propose a
probable mechanism of sulfuric acid decomposition operating over
Fe2O3/SiO2 monoliths which is schematically shown in Fig. 12. A five-
step mechanism is suggested in which the first step is the generations
of surface-active sites on iron oxide by oxygen desorption. At high
temperatures active sites are generated in the iron oxide species located
within the porous monolithic structure in the form of oxygen vacancies
by thermal desorption of oxygen. The multivalent transition metal Fe, in
Fe2O3 supports this thermal oxygen desorption by operation of the Fe2+/
Fe3+ redox couple [1]. Subsequently, the physical process of reactant
SO3 diffusion into the porous structure of the monoliths to the surface-
active site is the second step. Consequently, during catalytic action
and in presence of feed SO3 metastable surface Fe-sulfate intermediate is
generatedby chemisorption of the reactant sulfur trioxide on these
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Catalysis Communications 179 (2023) 106686
oxygen vacant sites through the oxygen in SO3. We obtained some sur­
face sulfate in the spent catalyst and its thermal decomposition yielded
sulfur dioxide.The decomposition of surface sulfates also regenerates the
Fe2O3 catalyst and evolves the product SO2. Finally the gaseous dioxide
diffuses out through the porous structure of the monoliths. A probable
mechanism of sulfuric acid decomposition over the hierarchical porous
Fe2O3/SiO2 monoliths is thus proposed. Each of these steps is required to
operate fast and the step which operates slowly becomes rate deter­
mining. The design of the monoliths should be such that the pores are
interconnected and the physical diffusion process of the reactant and
products are unhindered and does not turn out to be rate-limiting.
Further, the dispersion of the active species (in this case Fe2O3) should
be uniform throughout for effective utilization and uniform intermedi­
ate species (metal sulfate in this case) formation and decomposition. The
global reaction phenomenon encompasses physical steps as well as
chemical steps in the hierarchical porous catalysts. Chemical species
(reactant SO3 and products SO2, O2) will diffuse into the porous network
and adsorb on the active site and subsequent chemical reaction will
occur viz. metal sulfate formation, decomposition and the catalyst
regeneration.
In this study, we successfully prepare 3-D hierarchically porous
Fe2O3/SiO2 monoliths via a sol-gel methodology using a mixed precur­
sor approach. Monoliths of 3 mm diameter and 6 mm height are ob­
tained which has practical application in large scale fixed bed catalytic
reactors. The macropores are in the range of 10–100 μm diameters and
mesopores in the 8–16 nm range. The composition of the Fe2O3 is varied
and interesting findings are obtained. The first important structural
characteristic noticed is the retention of γ-Fe2O3 phase even after cal­
cinations at 1000 ◦ C which is highly unusual for Fe2O3 dispersed over
SiO2. Generally, Fe2O3 undergoes phase transformations to either
α-Fe2O3 or ε-Fe2O3 phases after calcinationas per our previous studies
[1,2]. Secondly, with increasing Fe-content interesting structural and
morphological features evolve. Separate precipitation of Fe2O3 phase in
the FS3 sample in substantial amount is detected by Mössbauer spec­
troscopy and this phenomenon was further established by SAXS, XPS
and directly evident from the SEM images. With increasing Fe-content
pore narrowing is established and in FS3 deposition of the iron oxide
component both inside and outside pore boundaries are evident. As an
extreme outcome, the porous nature is significantly hindered in FS3 and
pore obstruction by precipitated Fe2O3 is also recognized. Thus, the 3D
hierarchical Fe2O3/SiO2 monoliths have a limitation regarding the
extent of uniform Fe2O3 dispersion within the porous network of the
monoliths [1]. A maximum of ~15 wt% of Fe2O3 is an ideal composition
to obtain uniformly distributed Fe2O3/SiO2 monoliths with maximum
porosity.
Finally, the catalytic activity and the spent catalyst investigations led
to the establishment of useful concepts regarding the catalytic action of
Fe2O3/SiO2 monoliths. It is evident from the catalytic activity that the
Fe2O3/SiO2 monoliths are active and stable materials from a practical
application point of view in large scale fixed bed reactors. The surface
and morphological changes during catalytic engagements ascertain that
the chemical nature of the surface of the catalyst is significantly modi­
fied and reorganized. Substantial morphological changes are observed
viz. surface iron sulfate formation, catalyst densification, porosity re­
ductions, Fe2O3 precipitation outside pores in sulfated form but all these
are insignificant to reduce the catalytic performance. The most probable
mechanism is proposed via the spent catalyst characterization whereby
the Fe2O3 component of the monolith attaches itself with the reactant
SO3 to form metastable sulfate which then undergoes decomposition
liberating the product SO2. These results confirm the dynamic nature of
functioning of a heterogeneous catalyst where the catalyst surface par­
ticipates in the reaction mechanism accelerating the reaction rate and
again regenerated in another step [81–83]. Such a participation and
regeneration of the heterogeneous catalyst leaves permanent structural
and morphological changes on the catalyst surface although the activity
is maintained. Thus, a heterogeneous catalyst during catalytic action
N. Kumar et al. Catalysis Communications 179 (2023) 106686

Fig. 11. Spent catalyst (FS2) characterization (a) (i) SEM image with superimposed elemental mapping of Fe, O and Si, (ii)-(iv) the corresponding individual
elemental mapping of Fe, O, and Si, respectively, (b) Deconvoluted S2p X-ray photoelectron spectra after 25 h run, (c) Evolved gas analysis for mass number 64 as a
function of temperature in mass spectrometer of the gases evolved from thermal decomposition of the spent catalyst, and (d) TG pattern of the spent catalyst sample.

undergoes surface modifications depending upon the reaction demands
and the active form of the catalyst can be quite different from starting
materials. Even in a large-scale fixed bed reactor with effective 3-D
porous monolithic catalyst the mechanism with reactant-catalyst sur­
face interactions at molecular level is retained for enhanced scale
product formation. Again, during catalytic operation rapid movement of
gaseous reactant and products are ensured by the hierarchical porous
structure of the monolith. This study with an approach to bridge the gap
between lab scale powder catalyst and an industrial scale catalyst
requirement will provide deep insights in futuristic large scale catalyst
design and application.
4. Conclusion
Hierarchically porous Fe2O3/SiO2 monoliths are successfully syn­
thesized via a modified sol-gel approach. The thermal decomposition
patterns of the organic-inorganic hybrid as-synthesized product eluci­
date the nature of evolved gas which varied significantly with the
presence and extent of iron in the samples. Based on the Mössbauer
spectroscopy studies, the presence of paramagnetic γ-Fe2O3 phase is
confirmed. Macropores of 10–100 μm size and spherical/oval in shape
are clearly visible from the SEM images while mesopores in the range of
8–16 nm are estimated from SAXS studies. Significant, pore narrowing is
observed upon increased Fe2O3 incorporation and beyond a certain Fe-
content porosity loss is also evident. The Fe2O3 (15 wt%) /SiO2 monolith
is active for high temperature sulfuric acid decomposition and is stable
for 25 h operation. The spent catalyst investigation revealed the dy­
namic nature of the catalyst surface which encompasses both physical
and chemical steps of gas diffusion and Fe-sulfate formation and
decomposition. Hierarchically porous Fe2O3/SiO2 monoliths are po­
tential catalysts for deployment in large scale fixed bed catalytic reactors
for high temperature sulfuric acid decomposition.
Credit author statement
Neelesh Kumar: Experimentation, investigation, integration and

12
N. Kumar et al.
Fig. 12. Schematic representation of the most probable reaction mechanism proposed for sulfuric acid decomposition over Fe2O3/SiO2 monolithic catalysts.
compilation of data, graphical representation, manuscript reviewing
and editing, Atindra Mohan Banerjee: Conceptualization, methodology,
experimentation, supervision, data analysis, writing-original draft
preparation, reviewing and editing, M. R. Pai: Experimentation, inves­
tigation, reviewing and editing, Sher Singh Meena: Mössbauer data
collection and analysis, reviewing and editing, A. K. Patra: SAXS data
collection and analysis, reviewing and editing P. U. Sastry: SAXS data
collection and analysis, reviewing and editing, Jagannath: XPS data
collection and analysis, reviewing and editing, A. K. Tripathi: Supervi­
sion, manuscript reviewing and editing, project administration.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
13
Catalysis Communications 179 (2023) 106686
org/10.1016/j.catcom.2023.106686.
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