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Intermetallic compounds (IMCs) are interesting materials in the field of heterogeneous catalysis due to their ordered structure and tunable electronic properties. These IMCs can act as precursor to synthesize metal/metal oxide composite catalysts that are more active than just the starting IMCs. In this work, Sm2Co7 and SmCo5 IMCs were used as precursors to prepare highly active and stable Co_SmO, Co_Sm2O3 and Co3O4_Sm2O3 catalysts via controlled modification. Transmission electron microscopy (TEM) demonstrated that Co and Sm2O3 Nano crystallites were formed after the modification of the IMC. IMCs derived Co_SmO and Co_Sm2O3 were stable and active in NH3 synthesis with very low activation energy of 55 and 77 kJ mol−1 respectively. The structural, morphological and surface characterization revealed that a strong metal support interaction existed between Co and Sm2O3 (electronic effect) along with the presence of surface steps and edges of Co nano crystallites (structural effect) that activate the N2 at low temperature (360 °C). Similarly, Co3O4_Sm2O3 derived from the IMC were found to exhibit high CO2 and butane conversion in butane dry reforming at low temperature (550 °C) with excellent stability. The study revealed that the presence of Co3O4 and Sm2O3 active sites in close proximity (geometrical effect) promoted the simultaneous adsorption or activation of butane and CO2. The Co_Sm2O3 and Co3O4_Sm2O3 derived from IMCs exhibited superior catalytic performance in both NH3 synthesis and butane dry reforming compared to similar compositional catalyst synthesized by hydrothermal route. These studies pave the way to potential uses of IMCs as precursors to derive composite metal/metal oxide catalysts that are highly stable and active despite their low surface areas.

Catalytic activity of TiO2, 2%Re–TiO2 and 10%Re–TiO2 in the conversion of carbohydrates into levulinic acid under autoclave conditions was evaluated. These materials were prepared by aerogel method, for the first time to the best of our knowledge, and characterized by XPS, SEM-EDX, DRIFTS, DR UV-vis, Raman, N2 adsorption/desorption isotherms, TGA and XRD. Further, the surface acidity was probed by NH3-TPD and pyridine-FT-IR where it was observed that increasing the amount of rhenium doped into TiO2 led to an increase in the total number of acid sites (Lewis + Brønsted) but with an overall lower strength. The presence of both Brønsted and Lewis acid sites led to the hypothesis that these materials may be well suited for conversion of carbohydrates into levulinic acid. Indeed a levulinic acid yield of 57% was reached over 10%Re–TiO2 for a low mass ratio catalyst to glucose (1 : 5). Moreover, the 10%Re–TiO2 catalyst was reused in the conversion of glucose for four catalytic cycles without a significant loss of the catalytic activity.

TiO2 pillared clay was prepared by intercalation of titan polyoxocation into interlamelar space of an Algerian montmorillonite and used for the photocatalytic degradation of the linuron herbicide as a target pollutant in aqueous solution. The TiO2 pillared montmorillonite (Mont-TiO2) was characterized by X-ray photoelectron spectroscopy (XPS), X-Ray diffraction (XRD), X-Ray fluorescence (XRF), scanning electronic microscopy (SEM), thermogravimetry and differential thermal analysis (TG-DTA), Fourier transformed infra-red (FT-IR), specific area and porosity determinations. This physicochemical characterization pointed to successful TiO2 pillaring of the clay. The prepared material has porous structure and exhibit a good thermal stability as indicated by its surface area after calcination by microwave. The effects of operating parameters such as catalyst loading, initial pH of the solution and the pollutant concentration on the photocatalytic efficiency and COD removal were evaluated. Under initial pH of the solution around seven, pollutant concentration of 10 mg/L and 2.5 g/L of catalyst at room temperature, the degradation efficiency and COD removal of linuron was best then the other operating conditions. It was observed that operational parameters play a major role in the photocatalytic degradation process. Copyright © 2021 by Authors, Published by BCREC Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).

A series of tetrabutyl ammonium (TBA) salts of V-included Keggin-type polyoxoanions with W (TBA4PW11V1O40 and TBA5PW10V2O40) and Mo (TBA4PMo11V1O40 and TBA5PMo10V2O40) as addenda atoms were prepared using a hydrothermal method. These synthesized materials were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), UV-Vis diffuse reflectance (DRS UV-Vis), thermogravimetric analysis (TGA), CHN elemental analysis (EA), inductively coupled plasma spectrometry (ICP-MS), and N2 physisorption techniques to assess their physicochemical/textural properties and correlate them with their catalytic performances. According to FT-IR and DRS UV-Vis, (PVXW(Mo)12−XO40)(3+X)− anions are the main species present in the TBA salts. Additionally, CHN-EA and ICP-MS revealed that the desired stoichiometry was obtained. Their catalytic activities in the liquid-phase aerobic oxidation of benzyl alcohol to benzaldehyde were studied at 5 bar of O2 at 170 °C. Independently of the addenda atom nature, the catalytic activity increased with the number of V in the Keggin anion structure. For both series of catalysts, TBA salts of polyoxometalates with the highest V-substitution degree (TBA5PMo10V2O40 and TBA5PW10V2O40) showed higher activity. The maximum benzyl alcohol conversions obtained were 93% and 97% using (TBA)5PMo10V2O40 and (TBA)5PW10V2O40 as catalysts, respectively. In all the cases, the selectivity toward benzaldehyde was higher than 99%.

Imparting hydrophobicity to solid acid catalysts is critical to regulating their performances by allowing the creation of a less polar environment and improved partitioning of the reactants. Here we present different approaches for the preparation of silica-based catalysts comprising sulfonic acid (-SO3H) sites and hydrophobic decyl (-C10) chains by either simultaneous or sequential postfunctionalization of an azide-functionalized mesoporous silica platform. This set of hybrid bifunctional catalysts is compared in the model esterification of octanol with acetic acid, and the influence of the preparation methods together with the resulting site spatial distribution is discussed. In parallel, we show that pairing the two functional groups affords a maximum synergistic effect compared to more traditional mixed catalysts with random distributions of acid and hydrophobic functions.

The role of Bronsted and Lewis acid sites at the surface of heteropolyacid-based catalysts was studied in resorcinol alkylation with methyl-tert-butylether. Three sets of catalysts, SiO2/HPW, TiO2/HPW and ZrO2/HPW (where HPW stands for phosphotungstic acid hydrate), synthesized by the hydrolytic sol–gel method were investigated. The surface total acidity was characterized by ammonia chemisorption and thermo-programmed desorption. In addition, infrared analysis of adsorbed pyridine was performed to distinguish between Bronsted and Lewis sites. The resorcinol conversion was correlated to the fraction of Bronsted sites present at the catalyst surface based on the total acidity. The results pointed out the importance of considering both Bronsted and Lewis sites as active players in the mechanism of resorcinol alkylation: Lewis sites have the role of adsorbing the substrate close to the tert-butyl cation, which is formed on Bronsted sites. Resorcinol conversion can be increased to a maximum if the right Bronsted/Lewis ratio is attained at the catalyst surface.

A new composite heterogeneous catalytic system is proposed for the transformation of cheap unsaturated fatty acids into value-added molecules through their oxidative cleavage. The valorization of oleic acid to azelaic and pelargonic ones (which are demanded in pharmacology) is specifically studied. The reaction is efficiently performed with a novel composite catalyst inspired from metal recovery technology, namely Ru species supported on a carbon black that was previously oxidized and then functionalized with polydopamine. Being a polymer with hydroxyl and amine groups polydopamine provides moieties acting as tweezers able to complex Ru species. A representation of this novel composite catalyst is built from its characterization by FTIR, TGA, N2 physisorption TEM and XPS. Using NaIO4 as oxidizing agent in a biphasic system at room temperature the conversion of oleic acid, and selectivity towards pelargonic and azelaic acids, reached around 95% after 3 h. The reaction mechanism is explored by UV–Vis spectrophotometry, ICP elementary analysis and NMR spectroscopy, together with recyclability and hot centrifugation tests. The occurrence of a boomerang mechanism is demonstrated. The solid catalyst is indeed recyclable at least 5 times without activity loss, but at the same time Ru species are shown performing the reaction in homogeneous phase namely in a dissolved state. Actually, polydopamine is confirmed to recover Ru species once the reaction ends, guarantying the recyclability of the catalyst. The composite catalyst therefore combines the advantages of homogeneous and heterogeneous catalysis in the investigated reaction.

Shaping is a crucial step to produce technical catalysts that remains as some sort of dark art for catalytic researchers in academia. This contribution discusses aspects concerning the fabrication of technical catalysts based on MnO2 powders aimed for the combustion of hazardous aromatic compounds; namely, benzene and styrene. Both laboratory and pilot plant scale catalytic tests were conducted over tablets and extrudates of the technical catalyst. Key physicochemical properties of these materials; namely, surface area, porosity, crystallinity, and mechanical resistance, were assessed and correlated to the catalytic behaviour. On the one hand, the paper describes the hurdles to be overcome when formulating and testing a technical catalyst whose characteristics must be a good compromise between its physicochemical properties and catalytic behaviour at the pilot plant scale. Furthermore, the importance of adopting adequate security and waste management protocols for testing technical catalysts is highlighted. On the other hand, the following conclusions were drawn from the analysis of results: (i) Between tableting and extrusion, only the latter was found to produce shaped bodies with suitable mechanical resistance for pilot plant scale tests. (ii) Calcination of the fabricated extrudates at temperatures from 500 °C leads to a crystallographic transformation of the MnO2 that had a positive impact on the intrinsic activity of the technical catalyst while favouring its mechanical resistance owing to densification at the expense of a decrease in surface area and enlargement of pore size distribution. (iii) Thanks to pilot plant testing of the catalysts, it was possible to identify a detailed reaction scheme for styrene combustion in which besides the occurrence of oxidation, reactions of hydrogenation, dehydrogenation, ring opening, and isomerization take place by a combination of both surface and free radical mechanisms.

Nanostructured metal oxides are good candidates for applications in heterogeneous catalysis. Recently our consortium has developed the preparation of such materials by exploiting the redox properties of the non-thermal gliding arc plasma (glidarc) in humid air. This contribution aims at sharing with the community active in the field of heterogeneous catalysis that the glidarc technique is an easy and accessible, but powerful technique with a very bright future that can be used for producing heterogeneous oxide catalysts. Therefore, we present here our most recent achievements in the preparation of titanium, iron and manganese oxide catalysts using glidarc. TiO2 nanorods containing both rutile and anatase phases with improved photocatalytic activity under visible light were obtained by oxidizing Ti3+ ions in aqueous solution with the plasma species. Fe2+ ions exposed to the plasma discharge were transformed into sea-urchin-like porous goethite (α-FeOOH) nanostructures via the consecutive oxidation-hydrolysis processes. The synthesized goethite was mesoporous with a high surface area. Clay supported catalysts were also prepared by depositing the goethite particles on kaolinite. Those catalysts (and their calcination products) were active in heterogeneous Fenton degradation of organic dyes. α-MnO2 nanorods were obtained by a rapid reduction of MnO4− ions after exposing an aqueous solution of potassium permanganate to the plasma discharge.

Pyridine is since a long time used as an infrared (IR) molecular probe to characterize the acidity of solids, in particular of heteropolyacids (HPAs). The latter are metal-oxygen-clusters nowadays widely used in acid catalysis. Indeed, thanks to their exceptionally strong Bronsted acidity, they allow operating chemical reactions under significantly milder conditions than required by conventional catalysts. In the case of H3PW12O40, the most acidic Keggin-type HPA, it is well-known that the exposure to pyridine leads to an unusual IR spectrum. Indeed, the band at about 1540 cm−1 associated to the ν19b pyridinium ring stretch mode is split in two. Up to now, this phenomenon was studied with the only aim of understanding its origin, which was proposed to be a tunneling effect related to a frustrated rotation of the pyridinium cation within the solid bulk of H3PW12O40. Here, we demonstrate for the first time that it can actually be used as an analytical tool, namely to probe the degree of dispersion of supported H3PW12O40 units, a key parameter dictating their catalytic performance. We support H3PW12O40 on TiO2 P25 (hydrophilic) and TiO2 T805 (hydrophobic), so yielding samples with different degrees of dispersion, as qualitatively assessed through X-ray photoelectron spectroscopy. Through in situ Fourier-transform IR spectroscopy upon pyridine adsorption, we show that the ν19b pyridinium vibration band only and systematically splits in the presence of agglomerated Keggin units. More precisely, the higher the fraction of agglomerated Keggin units, the more marked the band splitting. So, the latter appears as a fingerprint of agglomerated H3PW12O40. Furthermore, following an easy treatment, the IR spectra allow quantitatively evaluating the fractions of dispersed vs. agglomerated Keggin units within the samples, which is very difficult to achieve through any other technique.

Self-standing macrocellular titanosilicate monolith foams are obtained using a one-pot sol-gel route and show excellent performance in the epoxidation of cyclohexene. Thanks to the High Internal Phase Emulsion (HIPE) templating method, the materials feature a high void fraction, a hierarchically porous texture and good mechanical strength. Highly dispersed Ti species can be incorporated in tetrahedral coordination the silica matrix. These characteristics allow the obtained ‘SiTi(HIPE)’ materials to reach high catalytic turnover in the epoxidation of cyclohexene. The monoliths can advantageously be used to run the reaction in continuous flow mode.

The transformation of γ-valerolactone (GVL) into levulinic acid (LA) requires the use of bifunctional catalysts allowing the hydrogenation and lactonization steps to occur. The aim of this study is to clarify the role played by both redox (Ru) and acid (Nb) sites of the ruthenium-niobium-silicon mixed oxides catalysts, synthesized by sol-gel route, when this reaction is performed in mild conditions. The catalytic performances of the materials are related to an in-depth morphologic and structural characterization, demonstrating that the interaction between the two metals and their relative amount and dispersion are crucial in determining their activity. The results confirm the hydrogenation-dehydration consecutive reaction network and evidence the possibility to selectively produce either GVL or the intermediate γ-hydroxypentanoic acid by an accurate choice of the catalyst composition.

The catalytic performance of various zeolites such as H-ZSM-5, H-Y, H-beta, H-Mordenite in resorcinol alkylation with tertiary butanol demonstrated that pore characteristics have major influence on product selectivity, whereas acid strength and number of acid sites influenced resorcinol conversion. The passivation of external surface of H-beta zeolite by silylation and amine poisoning produced shape selectively O-alkylated resorcinol methyl tert butyl ether (RMTBE) and 4-tert butyl resorcinol (4-TBR). We propose that 4-TBR formation goes over external acid sites through RMTBE isomerization, whereas formation of 4-TBR takes place inside the pores through direct C-alkylation mechanism.

Titanosilicates (Ti-SiO2) are well-known catalysts for the epoxidation of olefins. Isolated Ti inserted in the silica framework in tetrahedral coordination are the active species. Recently, adjusting the hydrophobic/hydrophilic balance of such catalysts’ surfaces has appeared as a promising tool to further boost their performance. However, adjusting the hydrophobic/hydrophilic balance via a one-pot classical sol-gel generally leads to a decrease in the Ti dispersion and/or collapse of the pore network. To overcome this limitation, hydrophobic mesoporous Ti-SiO2 were here synthesized by aerosol-assisted one-pot sol–gel, which allowed the simultaneous control of their Ti loading, degree of methyl-functionalization, and textural properties. Methyl-functionalization was achieved by a partial substitution of tetraethoxy silane (TEOS) by methyltriethoxy silane (MTES) in different ratios. Solid-state29Si-NMR, FTIR, TGA, and vapor-phase water adsorption showed that methyl moieties were effectively incorporated, conferring a hydrophobic property to the Ti-SiO2 catalysts. ICP-AES, DRUV, XPS, and N2 physisorption demonstrated that Ti dispersion and textural properties were both successfully preserved upon the incorporation of the methyl moieties. In the epoxidation of cyclooctene with tert-butyl hydroperoxide as oxidant, the hydrophobic Ti-SiO2 showed higher catalytic performance than pristine Ti-SiO2 prepared without MTES. In addition to disentangling the positive effect of adjusting the hydrophobic/hydrophilic balance of epoxidation catalysts on their performance, this contribution highlights the advantages of the aerosol procedure to synthesize mesoporous functionalized catalysts with very high dispersion of active sites.

The effect of adding secondary additives for tableting vanadium‑aluminum mixed-oxides, VAlO, on key physicochemical properties and on the catalytic performance in propane oxidation was investigated. Graphite was used as the primary shaping agent. The secondary additives were MgO, silica, BN, sepiolite, and ZnO. The hardness, fracture strength, and particle shape of the secondary additives were associated to the changes of the mechanical strength and porosity of the tablets. There was a compromise between mechanical strength and loss of mesoporosity and surface area. Meanwhile, the additives did not establish a chemical interaction with the VAlO material. Therefore, the secondary additives may act as co-catalysts during propane oxidation. BN and sepiolite were best for promoting both the reactivity of the catalytic formulations and the production of propene. This promotion may be due to the combination of a redox mechanism over the VAlO phase and to a surface radical mechanism occurring over the active moieties of BN and sepiolite.

We investigated how secondary additives for tableting vanadium-aluminummixed-oxides affect the mechanical resistance, surface chemistry, and catalytic performance inpropane oxidation of tablets based on this material. The secondary additives were magnesium oxide, silica, boron nitride, sepiolite, and zinc oxide while graphite was used as the primaryshaping agent. Our results showed that the changes in mechanical strength and porosity weredirectly related to the softness and ductility of the secondary additive. Overall, we learned thatwhen manufacturing catalyst tablets, there is a compromise between mechanical strength andloss in mesoporosity and surface area. On the other hand, the components of the formulatedtablets did not show signs of establishing a chemical interaction with the vanadium-aluminummixed oxide. Therefore, the effects of the additives that we found on the catalytic performancewere ascribed to the fact that the selected secondary additives may act as co-catalysts duringpropane oxidation. In this sense, boron nitride and sepiolite were best for promoting both thereactivity of the catalytic formulations while showing a better productivity of propene. The datawas interpreted suggesting that the promotion effect may be due to the combination of a redoxmechanism over the vanadium-aluminum mixed oxide phase and to a surface radical mechanismoccurring over the active moieties of these secondary additives.

Mesoporous Ti–SiO2 nanoparticles were prepared under alkaline conditions in the presence of a surfactant and were subsequently converted into a hierarchical micro-/macroporous TS-1 zeolite with large crystal size using steam assisted crystallization. In this procedure, the precursor nanoparticles were used both as macroporous hard template and as Si and Ti sources. The secondary macroporosity is a reminiscence of the nanoparticles which undergo dissolution and recrystallization upon steaming. The obtained catalyst has structural properties comparable to benchmark TS-1. We show that the successful conversion of the amorphous material into a fully crystalline catalyst stands for its excellent catalytic performance in aqueous media. Besides, the combination of large crystal size with a hierarchical pore structure ensures easy catalyst handling and processing without compromising on the catalytic activity.

In the field of heterogeneous catalysis, the successful integration of enzymes and inorganic catalysts could pave the way to multifunctional materials which are able to perform advanced cascade reactions. However, such combination is not straightforward, for example in the case of zeolite catalysts for which enzyme immobilization is restricted to the external surface. Herein, this challenge is overcome by developing a new kind of hybrid catalyst based on hollow zeolite microspheres obtained by the aerosol-assisted assembly of zeolite nanocrystals. The latter spheres possess open entry-ways for enzymes, which are then loaded and cross-linked to form cross-linked enzyme aggregates (CLEAs), securing their entrapment. This controlled design allows the combination of all the decisive features of the zeolite with a high enzyme loading. A chemo-enzymatic reaction is demonstrated, where the structured zeolite material is used both as a nest for the enzyme and as an efficient inorganic catalyst. Glucose oxidase (GOx) ensures the in situ production of H2O2 subsequently utilized by the TS-1 zeolite to catalyze the epoxidation of allylic alcohol toward glycidol. The strategy can also be used to entrap other enzymes or combination of enzymes, as demonstrated here with combi-CLEAs of horseradish peroxidase (HRP) and glucose oxidase. We anticipate that this strategy will open up new perspectives, leveraging on the spray-drying (aerosol) technique to shape microparticles from various nano-building blocks and on the entrapment of biological macromolecules to obtain new multifunctional hybrid microstructures., A spray drying technique is used to prepare hollow zeolite microparticles into which an enzyme can be entrapped. Via this “Lego-like” strategy, we create hybrid heterogeneous catalysts that can run multistep chemo-enzymatic cascade reactions.

AlSBA-15 catalysts possessing Bronsted acid and Lewis acid–base bifunctionalities catalyze the direct arylation of benzyl alcohols to diarylmethanes with an 85% product yield through C–O bond activation. 2 and 4wt%AlSBA-15 catalysts have been synthesised by adopting a simple and efficient post-synthetic metal implantation route. The synthesised catalysts were characterized using XRD, N2 adsorption and desorption, 27Al MAS NMR, XPS, HR-TEM, NH3 and CO2-temperature-programmed desorption (TPD) and pyridine-transmission-FTIR spectroscopy techniques to confirm the existence of Bronsted acid and Lewis acid–base bifunctionalities. Through various control experiments, it is verified that Bronsted acid sites activate the benzyl alcohol and Lewis base sites interact with phenylboronic acid concurrently to accomplish the coupling reaction. In the recyclability study, 4wt%AlSBA-15 preserves its activity and stability up to 5 cycles. The 4wt%AlSBA-15 catalyst unlike homogeneous catalysts does not require additives, long reaction time and expensive metals.

In 1-butanol dehydration (gas phase) on a Keggin heteropolyacid (HPA) catalyst, the large size of 1-butanol and its significant hydrophobicity make the bulk-type (also called pseudo liquid-type) catalytic mechanism impossible. This drastically limits the catalytic effect on the surface of the HPA, with an activity lower than what it could be. To overcome this limitation, partially substituted ammonium Keggin acid salts with the formula (NH4)xH3−xPW12O40 were here synthesized. Still maintaining enough acidity for the dehydration reaction, the replacement of some protons of H3PW12O40 with NH4+ increases the hydrophobicity of the crystal matrix and allows 1-butanol to enter the bulk of the salt. This consequently makes the protons inside the solid able to catalyse the reaction. The penetration of 1-butanol in the bulk is demonstrated by a combination of in situ methods (Raman, FTIR and XRD) applied during the pre-treatment of the catalyst and the catalytic reaction. When properly activated the pseudo liquid-type mechanism taking place in (NH4)xH3−xPW12O40 leads to a markedly higher 1-butanol conversion in comparison to the surface-type mechanism which is the only one achieved with the non-modified pristine HPA.

An eco-friendly photocatalytic coating, active under a cost-effective near-visible LED system, was synthesized without any calcination step for the removal of organic pollutants. Three types of doping (Fe, N and Fe + N), with different dopant/Ti molar ratios, were investigated and compared with undoped TiO2 and the commercial P25 photocatalyst. Nano-crystalline anatase-brookite particles were successfully produced with the aqueous sol-gel process, also at a larger scale. All samples displayed a higher visible absorption and specific surface area than P25. Photoactivity of the catalyst powders was evaluated through the degradation of p-nitrophenol in water under visible light (&gt, 400 nm). As intended, all samples were more performant than P25. The N-doping, the Fe-doping and their combination promoted the activity under visible light. Films, coated on three different substrates, were then compared. Finally, the photoactivity of a film, produced from the optimal N-Fe co-doped colloid, was evaluated on the degradation of (i) p-nitrophenol under UV-A light (365 nm) and (ii) rhodamine B under LED visible light (395 nm), and compared to undoped TiO2 film. The higher enhancement is obtained under the longer wavelength (395 nm). The possibility of producing photocatalytic films without any calcination step and active under low-energy LED light constitutes a step forward for an industrial development.

The catalytic combustion of diesel soot is addressed with flexible and structured “paper catalysts”. Two different series of catalysts were prepared either by drip impregnation or by a spray method to deposit a mixture of Co, Ba, and K or a mixture of Co and Ce onto SiO2-Al2O3 ceramic paper matrixes. In every case, CeO2 nanoparticles were added to bind the ceramic fibers. SEM images showed that the impregnation method generated catalytic particles concentrated as large chunks (> 10 μm), mainly at ceramic fiber crossings, whereas the spray method produced smaller catalytic particles (< 1 μm) well distributed throughout the ceramic paper. Besides, Co-Ba-K particles appeared better dispersed on the surface of ceramic fibers than Co-Ce due to the presence of K. Additionally, FTIR spectra showed the formation of O2 2− and O2 − species associated with CeO2 (binder) on the samples containing potassium which gave the Co-Ba-K-ceramic paper good catalytic properties, thus making the Co-Ba-K drop impregnated the best catalyst both considering activity and stability. Successive temperature programmed oxidation (TPO) runs up to 700 °C caused the formation of cobalt silicates in the catalytic ceramic paper prepared by the spray method, as indicated by TPR. The formation of these species was probably favored by the smaller size of cobalt particulates and their higher dispersion in the catalysts prepared by the spray method. This provoked the partial loss of the redox properties of Co3O4. TPR experiments also indicated the formation of BaCoO3 in Ba-containing ceramic paper, which could help in maintaining the catalyst activity after several TPO runs through the capacity of this mixed perovskite-type oxide to trap and release NOx. Fil: Leonardi, Sabrina Antonela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina Fil: Tuler, Fernando Esteban. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina Fil: Gaigneaux, Eric M.. Université Catholique de Louvain; Bélgica Fil: Debecker, Damien P.. Université Catholique de Louvain; Bélgica Fil: Miro, Eduardo Ernesto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina Fil: Milt, Viviana Guadalupe. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera". Universidad Nacional del Litoral. Instituto de Investigaciones en Catálisis y Petroquímica "Ing. José Miguel Parera"; Argentina

The gas-phase glycerol (Gly) transformation in the presence of oxygen has been studied on cobalt oxide systems (10 and 20 wt% Co) supported on a synthetic mesoporous aluminium phosphate (AlPO4) calcined at 350 °C, as well as on a binary Co-Al phosphate with a Co content of 10 wt%. Synthetic binary phosphate of Al-M (M = Fe, V) have also been tested. The acidity (number and nature of acid sites) of the solids was determined by pyridine adsorption, whereas the reducibility was determined by H2 TPR. The propene oxidation was employed as a test reaction. The influence of the amount of oxidant agent and the reaction temperature on both the glycerol conversion and the yield to reaction products was studied. The formation of acrylic acid; acetic acid and carbon dioxide was favoured for values of O2/Gly ≥ 2 molar ratio and of temperatures beyond 250 °C. The Co oxide species in the supported systems that were the easiest to reduce (lower H2 desorption temperature) exhibited the highest activity to produce acrylic acid. The formation of acetic acid and carbon dioxide was also promoted, suggesting the participation of the acid sites in addition to redox sites. Among the metals investigated here, Co would form part of the required catalyst for the formation of acrylic acid from glycerol. Based on the identified products in this study, some possible reactions involved in the glycerol transformation into oxidized compounds, have been suggested.

Series of Ni catalysts supported on alumina and mixed xCeO2-Al2O3 oxides with different CeO2 content (1–12 wt%) were prepared by impregnation method. The effect of CeO2 loading on the structure and catalytic properties of supported Ni catalysts in dry methane reforming was studied. The texture, structure and surface properties of the catalysts in their calcined, reduced and used state were studied by using different techniques such as: adsorption-desorption isotherms, XRD, UV–vis DRS, XPS, Raman, H2-TPR, EPR, TPO and TEM. Variation in the electronic environments of the cerium and nickel as a function of the CeO2 content and pretreatment was observed for CeO2-containing Ni catalysts. The couples Ni2+/Nio and Ce3+/Ce4+ were detected in the oxidic, reduced and spent ceria-loaded Ni catalysts. CeO2-containing Ni catalysts exhibited higher activity and stability with time on stream relative to that of alumina-supported Ni. The obvious difference in the behaviors of Ni/xCeO2-Al2O3 and Ni/Al2O3 was related to the difference in their dispersions. Small nanoparticles of 4.7–6.3 nm were observed for CeO2-modified catalysts assuring their high activity and resistance to carbon deposition. The highest activity and stability of Ni catalyst with 6 wt.% CeO2 was due to the higher electron density and accessibility of the active sites caused by the close contact between nickel and cerium species. While, Ni/Al2O3 catalyst exhibited low activity and carbon resistant due to the agglomeration of nickel particles up to 20 nm.

Bio-oils require the elimination of most of the oxygen they contain to stabilize them before their use as fuels. The hydrodeoxygenation (HDO) process consists on eliminating oxygen from the bio-oil at high hydrogen pressures over a solid catalyst. However, catalysts often suffer from prompt deactivation due to extensive coke deposition. Therefore, searching more stable catalysts for HDO is still a challenge for biorefiners. In this work, the HDO of guaiacol as a model compound from bio-oil was carried out in a batch reactor at 523 K, p H2 = 5.5 MPa over potassium modified γ-Al 2 O 3 supported CoMo and NiMo catalysts. Potassium was shown to be an effective activity and selectivity modifier. It led to an increase in the yields to products that may hinder catalysts coking by shifting selectivity from demethylation and methyl substitution reactions to direct C Aromatic OH bond scission and hydrogenation reactions. Changes on selectivity were accompanied by a decrease in guaiacol conversion. The effect produced by potassium was shown to be related to: a reduction in acidity, a decrease in the relative number of Mo species in octahedral coordination, and to an increase in the relative concentration of catalytically inactive NiAl 2 O 4 and CoAl 2 O 4 species. Results of this work contribute to design more stable HDO catalysts from a rather simple modification of conventional hydrotreatment catalysts.

Keggin tungstophosphoric acid (H3PW12O40, HPW) was immobilized onto Santa Barbara Amorphous (SBA-15) type silica to obtain selective catalysts for the resorcinol tert-butylation with methyl-tert-butyl ether. The challenge was to enhance the reaction selectivity to the mono-alkylated product i.e. 4-tert-butylresorcinol at the expenses of other more thermodynamically favored products as the 4,6-di-tert-butylresorcinol. Using HPW@SBA15 catalysts, remarkable selectivity to 4-tert-butylresorcinol was obtained, up to 42% (at 20% of resorcinol conversion). Our finding is that the change in the product distribution was dependent on the catalyst surface chemistry: 4TBR selectivity can be increased adjusting the fraction of Bronsted acid sites versus Lewis ones at the catalyst surface.

Manganese (IV) oxide (MnO2) nanoparticles were synthesized, via a plasma-chemical route by using a gliding arc discharge at atmospheric pressure. α-MnO2 nanorods were obtained from the chemical reduction of KMnO4. The synthesis yield was 96.8% after 4.5 min of exposure of the solution to the plasma. Further increase of the exposure time induced a decrease of MnO2 yield because of its reductive transformation into Mn2+ ions. Particles were characterized by X-ray powder diffraction, scanning electron microscopy, Fourier Transform Infrared spectroscopy, and nitrogen physisorption. The plasma-catalytic properties of the synthesized material were tested in the bleaching of amaranth red (AR). AR bleaching efficiencies of 17 and 44% were respectively obtained when the plasma and plasma-catalyst processes were applied for 30 min with initial pH 10. The influence of the initial pH, and catalyst concentration were investigated: the AR bleaching efficiency increased linearly with the catalyst concentration and increased markedly when the pH of the solution decreased.

Characterizing catalysts under working conditions is crucial to understand and to optimize their behavior and performance. However, when Raman spectroscopy is used, attention has to be paid to laser-induced artefacts. While laser irradiation is often claimed to lead to a temperature gradient between the integral catalyst bed and the sampling point, neither the circumstances when such effect appears, nor if it systematically occurs or not, are really explored in details. The present paper shows that the sensitivity of a catalyst to laser-induced heating largely depends on the gas composition under which the analysis is done, in particular that it depends whether the catalyst has adsorbed reactant molecules or not. These aspects are here addressed via the Raman in situ exploration of H 3 PW 12 O 40 . This heteropolyacid is a widely used acid catalyst due to its very high Bronsted acidity, approaching the superacid region. In particular, we have investigated the impact of laser irradiation in the Raman monitoring of solid H 3 PW 12 O 40 at work under a flow of methanol in nitrogen at 50 °C. When 1 single spectrum of H 3 PW 12 O 40 was measured after 3 h of exposure to methanol, the characteristic C H vibration bands of adsorbed methanol appeared. However, when spectra were measured continuously throughout the experiment, the same C H vibration bands were observed only during the first hour, then they disappeared and the characteristic bands of polyaromatic molecules appeared. Under continuous laser irradiation, adsorbed methanol was thus converted into polyaromatic coke as resulting from a laser-induced heating. However, the spectra collected under pure nitrogen show that the laser does not heat the catalyst in the absence of methanol. UV–Vis revealed the reason of the laser-induced heating in the presence of methanol, and the subsequent formation of coke. Actually the catalyst gets reduced by the adsorbed methanol, what darkens the catalyst bed. Such a darkening renders the catalyst sensitive to laser-induced heating, which in turn leads to the formation of coke. Under continuous laser irradiation, methanol thus auto-initiated its own catalytic conversion, finally leading to the deposition of coke. Such artefact must be avoided if one wants to study the true behavior of the catalyst at work. This paper shows that, for reducible samples analyzed in the presence of reductive molecules, this is only possible by shining the laser intermittently and not continuously. More generally, it actually shows that the adequate way to irradiate a catalyst (continuous vs intermittent) in an in situ / operando Raman analysis depends on the gas flow composition.

Heteropolyacids (HPAs) are metal–oxygen clusters that are nowadays widely used in acid catalysis. Indeed, as they possess a very strong Bronsted acidity, approaching the superacid region, they generally allow performing reactions at lower temperatures than conventional catalysts. In the present paper, we use in situ/operando Raman spectroscopy to optimize the catalytic performance of H3PW12O40—the strongest Keggin-type HPA—in the low temperature (150 °C) gas phase dehydration of methanol to dimethyl ether (DME), which is one of the most promising renewable fuels for the future. Precisely, we demonstrate that the ability of methanol to displace the HPA’s crystallization water located in-between the Keggin units—and thus to reach the acidic protons—decreases with increasing temperature. Actually, we show that one and the same flow of methanol scarcely displaces the crystallization water at reaction temperature 150 °C, whereas, at a temperature as low as 25 °C, it succeeds to completely dehydrate the HPA. By...

The gas phase dehydration of methanol to dimethylether (DME) nowadays attracts more and more interest as DME is one of the most promising renewable fuels for the future. As catalysts, many studies now use heteropolyacids (HPAs) which have an exceptionally high Brønsted acidity. In the present work, H 3PW 12O 40 (the most widely used Keggin-type HPA) was intentionally coked (covered with carbonaceous deposits) by involving methanol in its dehydration pre-treatment at 350 °C. Then, it was compared to a non-coked reference sample in terms of specific surface area, acidity and catalytic performance in the methanol-to-DME reaction at 150 °C, namely, a temperature at which no significant coking occurs. The results show that, in spite of its significantly lower specific surface area due to pore blockage by coke, pre-coked H 3PW 12O 40 is less active in the methanol reaction only during the first three hours. Afterwards, it succeeds in reaching the same conversion as the reference sample, and its performance is stable. Indeed, flowing methanol induces cracking of the secondary particles of H 3PW 12O 40 (revealed through SEM), and this is proposed here to progressively reverse the initially unfavorable pore blockage by coke. So, the present paper shows that coke is not the only factor controlling how the performance of an HPA in the methanol reaction evolves with time-on-stream. Particle cracking due to the reaction flow also plays a role and, in certain conditions, its positive impact wins against the negative impact of coke. Thus, more generally, when performing the methanol reaction itself at 300-350 °C (i.e. conditions under which coking occurs), with the aim of keeping a high catalytic performance as long as possible, one should try to play on both factors instead of only on the production of coke.

A complex kinetics of the photocatalytic decomposition of gaseous ethylene on nanoparticulate Fe(III) doped anatase TiO2 was analyzed in a continuous-flow fixed-bed reactor. The analysis evidenced the production of non-volatile intermediate reaction products, which cover the photocatalyst surface and delay the time of attaining the stationary reactor performance. As a result, the reaction yield slowly increases during the long-lasted (∼3 h) intermediate stage. Based on Raman, FTIR and thermal post-treatment analyses, we assigned the major non-volatile reaction product to polymeric oxidized hydrocarbons: furan and furfural oligomers. A theoretical model is proposed explaining the observed kinetics.

© 2019 American Chemical Society. Herein, we present the aerosol-assisted sol-gel preparation of hierarchically porous TiO 2 -SiO 2 catalysts having a spherelike shell morphology and a high Ti dispersion. In order to control the porosity at the micro-, meso-, and macrolevels, we use the evaporation-induced self-assembly (EISA) of a surfactant, possibly combined with polymer beads as hard templates. These catalysts are tested for the epoxidation of cyclohexene with cumene hydroperoxide as the oxidant, and their performance is compared to the reference TS-1 zeolite. The high catalytic performance observed with the catalysts prepared by aerosol stems from their high specific surface area, but also from the short diffusion path length generated by the meso-/macropore architecture which provides entryways for bulky reactants and products. Besides, these materials can incorporate a higher Ti loading than TS-1 zeolite, while ensuring a good control over the Ti speciation. Thus, the unique features of the aerosol process - which is also known to be scalable - allow us to prepare catalytic materials with high epoxidation activity, also for bulky olefins. ispartof: Chemistry of Materials vol:31 issue:5 pages:1610-1619 status: published

Titania-silica (TiO2-SiO2) mixed oxides are known catalysts for the epoxidation of olefins. It has been demonstrated that their active sites consist in isolated framework Ti atoms. However, the latter species are only obtained when Ti loading is low, limiting the number of active sites and the catalytic performances. Thus, the need to search other approaches to boost them. We succeeded improving the catalytic activity of TiO2-SiO2 mixed oxides in the epoxidation of cyclooctene with hydrogen peroxide by introducing hydrophobic organic moieties at their surface. Hydrophobic TiO2-SiO2 mixed oxides were prepared through a one-pot sol-gel method. Titanium butoxide (TiBut) and tetraethoxy silane (TEOS) were used as the Ti and Si precursors respectively. Hydrophobization was achieved by substituting a fraction of TEOS in the synthesis by methyltriethoxy silane (MTES). The characterization of the Ti species was performed by FTIR, DRUV, and XPS, confirming the presence of significant amount of the active framework Ti. The methylation degree was evaluated by Solid State 29Si-NMR and TGA-MS. Hydrophobic TiO2-SiO2 performed better in the epoxidation reaction than a fully inorganic more hydrophilic TiO2-SiO2 prepared without MTES. A too high methylation degree of the catalysts is however detrimental. Our contribution allows elucidating the debate in literature about the consequence of hydrophobization of epoxidation catalysts on their performance.

Mayenite (Ca₁₂Al₁₄O₃₃) is an attractive, non-expensive material, conventionally prepared over 1300 °C via solid-state reaction, producing a solid with low specific surface area (1 m²/g). Although a recent alternative allowed mayenite formation from 400 °C using hydrothermal method, it still requires a ball-milling step to increase the specific surface area (≥20 m²/g), which is costly and energy-consuming, involving specialized equipment. Herein, we report a new, cost-effective and simple way to produce porous mayenite with enhanced textural properties at lower temperatures (˜275 °C). Initially, non-porous mayenite was directly produced from 250 °C via a self-combustion reaction of nitrates with a double-fuel mixture. Furthermore, the addition of oxalic acid was implemented, obtaining porous mayenite after calcination of a preformed precursor and boosting its specific surface area and pore volume up to 74 m²/g and 0.3 cm³/g, respectively. Such textural enhancement notably increased mayenite catalytic properties in the soot oxidation reaction.

Friedel–Crafts alkylation of resorcinol with methyl tertiary butyl ether was carried out over sulfated zirconia (SZ) catalysts in the liquid phase. The SZ catalysts were synthesized by an impregnation method with different sulfur amounts and characterized by XRD, FT-IR, nitrogen sorption, XPS, SEM, pyridine-FTIR, and NH3-TPD. The effect of the sulfur loading on the total acidity and catalytic activity was investigated. The influence of the nature of the solvents on the alkylation reaction was inspected in terms of their acceptor and donor numbers. The sulfur loading, amount of solvent, temperature, catalyst amount, mole ratio and reusability of the catalyst were examined. The SZ catalyst synthesized by impregnating 1 N sulfuric acid was found to be highly selective for the monoalkylation to 4-tertiary butyl resorcinol (72%) with a resorcinol conversion of ∼70%. The catalyst was recycled thrice with a negligible decrease in the yield for 4-tertiary butylresorcinol. The SZ exhibited the best performance at low temperature (60 °C) among the different types of solid acid catalysts studied so far.

Supported NiO nanocluster catalysts were synthesized by using Ni colloid as a precursor and applied to the aerobic oxidation of 1-phenylethanol. Obtained catalysts were characterized through X-ray absorption fine structure (XAFS), X-ray photoelectron spectroscopy (XPS) and in situ X-ray diffraction (XRD). Activated carbon (AC) supported NiO nanocluster catalyst showed the catalytic activity to the aerobic oxidation of 1-phenylethanol without any additives. Only the AC support allowed the NiO catalyst to be active although the other supports did not. XAFS and in situ XRD revealed that NiO nanocluster was fixed on the supports successfully. XAFS and XPS gave the information about a difference in the local structure, chemical state and electronic state of Ni among the different supports. The obtained catalyst showed the activity more effectively compared to conventional nickel-based catalysts.

This paper examines the effect of the preparation method of sulfated and unsulfated V2O5/TiO2 catalysts on chlorobenzene total oxidation. In particular, the method of incorporation of vanadium, either by impregnation or by direct introduction of V during the preparation of TiO2 or TiO2–SO42− aerogel supports, is discussed. The obtained catalysts have been characterized by means of ICP-AES, N2 adsorption–desorption at 77 K, XRD, Raman spectroscopy, DRIFTS, XPS, H2-TPR and NH3-TPD. Without sulfate, the impregnated catalyst exhibits a higher V dispersion and performs better than the sol–gel catalyst. The beneficial effect of sulfate groups is clearly demonstrated as both the impregnated and one-pot sol–gel samples with sulfate markedly outperform the corresponding samples without sulfate. The sulfated one-pot sol–gel catalyst exhibits the best performance at high temperature, probably thanks to its sulfate-rich surface.

Solid acid catalysts are central in our chemical industry and are major players in the valorization of bioresources. However, there is still a need to develop solid acid catalysts with enhanced acid strength and improved, or tunable, physicochemical profile to enhance the efficiency and sustainability of chemical processes. Here, we present a modular approach to tune the acid strength and surface polarity of silica-supported sulfonic acid catalysts based on a versatile copper-catalyzed azide-alkyne cycloaddition (CuAAC)-based anchoring scheme. We precisely take advantage of the CuAAC-formed triazole link to enhance the activity of the grafted sulfonic acids and to pair the acid sites with secondary hydrophobic functions. The beneficial effects of both the triazolium link and the paired hydrophobic site, as well as the optimal positioning of the sulfonic moiety on the triazole ring, are discussed in model esterification reactions. ispartof: Chemistry vol:25 issue:27 pages:6753-6762 ispartof: location:Germany status: Published online

The evolution of the morphology, crystalline structure, and textural properties of α-MnO2 nanorods, which were obtained after reduction of a KMnO4 solution via gliding arc plasma process, have been followed along their ageing under temporal post-discharge conditions. When aged at 25 °C a partial transformation of α-MnO2 (cryptomelane) to γ-MnO2 (nsutite) occurred with an increase of specific surface area from 98 to 141 m2/g. In parallel, the starting nanorods were converted to nanoneedles after 24 and 48 h, and into nanosheets after 72 h. These transformations are ascribed to the evolution of maturation process of crystallites, thanks to post-discharge species (H2O2, HOONO,…). At the opposite, ageing at 100 °C induced a remarkable transformation of α-MnO2 to γ-MnO2 with a decrease of specific surface area from 98 to 35 m2/g after 3 h, which was in line with the observed agglomeration of nanorods. Finally, whereas a longer ageing at 100 °C provoked an activity diminution of the material, an augmentation of activity of plasma-synthesized α-MnO2 was recorded when implementing ageing at 25 °C.

© 2016 American Chemical Society. Amino acids have huge potential as platform chemicals in the biobased industry. Pd-catalyzed decarboxylation is a very promising route for the valorization of these natural compounds derived from protein waste or fermentation. We report that the highly abundant and nonessential amino acid L-proline is very reactive in the Pd-catalyzed decarboxylation. Full conversions are obtained with Pd/C and different Pd/MeOx catalysts; this allowed the identification of the different side reactions and the mapping of the reaction network. Due to the high reactivity of pyrrolidine, the selectivity for pyrrolidine was initially low. By carefully modifying Pd/ZrO2 with Pb in a controlled mannervia two incipient wetness impregnation stepsthe selectivity increased remarkably. Finally, a thorough investigation of the reaction parameters resulted in an increased activity of this modified catalyst and an even further enhanced selectivity under a low H2 pressure of 4 bar at 235 °C in water. This results in a very selective and sustainable production route for the highly interesting pyrrolidine. ispartof: ACS Catalysis vol:6 issue:11 pages:7303-7310 status: published

Nanostructured hybrid materials made of guest ions and a polyampholytic self-assembled copolymer are here synthesized. Their lamellar organization results from hydrophobic interactions between the copolymer alkyl side chains. Longer side chains improve the organization of hybrids what makes them more attractive to be used as a template for the preparation of sophisticated catalysts. However, they also enhance the hydrophobicity of the copolymer what complicates the synthesis of such hybrids. Dodecyl side chains appear as a compromise that enables to prepare well organized hybrids without sacrificing the copolymer capacity to link ions.

Various iron oxides are used for Fenton reactions to degrade organic pollutants. The degradation efficiency may be improved by transforming an iron oxide phase to another. Here, we report on the transformation of goethite into hematite by thermal treatment at 400 °C. The products were analyzed by X-ray diffractometry, Raman spectroscopy, scanning electron microscopy and N2-physisorption. The catalytic activities were measured for orange II bleaching at initial concentration of 25 mg L−1, pH 3, catalyst concentration of 0.2 g L−1; 5 mM H2O2, 30 °C. Results show that the synthesized goethite was successfully transformed into hematite, and the specific surface area of the material increased from 134 to 163 m2 g−1. The bleaching efficiency of the orange II dye reached 100 % for the hematite product, versus 78 % for goethite. Therefore, a moderate thermal treatment of a plasma-synthesized goethite improves the catalytic oxidation of organic pollutants.

Suzuki coupling is a crucial reaction for the preparation of many high value compounds, especially for the synthesis of pharmaceuticals. Pd-based heterogeneous catalysts are highly regarded for achieving this reaction. However, the knowledge of the Suzuki mechanism with this type of catalysts is relatively limited. In the present paper, the influence of the acidity of heterogeneous catalysts on the Suzuki coupling has been methodically investigated on palladium supported on silica–alumina. A Suzuki coupling model reaction was used to assess if any correlation exists between the performances of the prepared catalysts and their acidity. The results have demonstrated that, the Pd being in an oxidized state, the acid sites at the heterogeneous catalyst surface participate actively to the mechanism of the Suzuki coupling. An optimum of total acidity of the catalysts leading to a peak of performances (conversion and selectivity) was identified. Several assumptions concerning the implication of the catalytic support in the different steps of the Suzuki coupling mechanism are proposed and discussed. Furthermore, the recyclability of the catalyst has been demonstrated, revealing that our catalysts really behave heterogeneously.

Mixed model molybdate catalysts that contain CoMoO4, Bi2Mo3O12, and Fe2Mo3O12 were investigated in the ammoxidation reaction of propene to acrylonitrile to study the redox behavior of the iron molybdate component. The flexible changes of the oxidation state of the Fe component during ammoxidation were followed by examining the intensity changes of the characteristic bands of Fe2Mo3O12 and FeMoO4 in the Raman spectra and could be correlated with the catalyst performance examined by simultaneous MS analysis. Depending on the catalyst composition and the oxygen content in the feed, Fe2Mo3O12 is reduced to a different extent, and consequently, FeMoO4 is formed, which is accompanied by a restructuring of the catalyst and the formation of nanostructured MoOx species. In accordance with previous investigations, operando Raman studies revealed that CoMoO4 and Bi2Mo3O12 influence the redox behavior of Fe2Mo3O12 in different ways.