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Addition of gold to the Pt–CsPW catalyst has an enhancing effect on the HDO of DMTHF, with a twofold increase of turnover rate at Pt sites.

Acidic cesium salt of tungstophosphoric heteropoly acid, Cs2.5H0.5PW12O40 (CsPW), is an excellent solid acid catalyst for the reaction of phenylacetaldehyde with biorenewable monoterpenic alkenes: limonene, α-terpineol, α-pinene and β-pinene. Simultaneously with a conventional oxonium-ene cyclization to give an oxabicyclo[3.3.1]nonene compound, phenylacetaldehyde undergoes Friedel-Crafts alkylation by the monoterpenes resulting in a new product with an unusual fused tetracyclic structure, obtained in ca. 80 % yield. A combined yield for both products was up to 95 %. Styrene oxide can be also used as a starting material for these reactions to give the same products in up to 85 % combined yield. A novel one-pot tandem process thus developed involves the isomerization of styrene oxide into phenylacetaldehyde and cycloaddition of the latter to the monoterpene, with both steps being catalyzed by CsPW. The reactions were performed in green solvents diethylcarbonate or anisole, which have high sustainability ranks in modern solvent selection guides, comparable to those of ethanol and water.

The conversion of diethyl ether (DEE) to ethene and ethanol was studied at a gas-solid interface over bulk and supported Bronsted solid acid catalysts based on tungsten Keggin heteropoly acids (HPAs) at 130-250 °C and ambient pressure. The yield of ethene increased with increasing reaction temperature and reached 98% at 220-250 °C (WHSV = 2.2 h-1). The most active HPA catalysts were silica-supported H3PW12O40 and H4SiW12O40 and the bulk heteropoly salt Cs2.5H0.5PW12O40. The HPA catalysts outperformed zeolites HZSM-5 and USY reported elsewhere. A correlation between catalyst activity and catalyst acid strength was established, which indicates that Bronsted acid sites play an important role in DEE elimination over HPA catalysts. The results point to the reaction occurring through the consecutive reaction pathway: DEE → C2H4 + EtOH followed by EtOH → C2H4 + H2O, where ethene is both a primary product of DEE elimination and a secondary product via dehydration of the primary product EtOH. Evidence is provided that DEE elimination over bulk HPA and high-loaded HPA/SiO2 catalysts proceeds via the surface-type mechanism.

2,5-Dimethylfuran is deoxygenated to n-hexane with 100% yield on a bifunctional Pt/C-Cs2.5H0.5PW12O40 catalyst under very mild conditions (90 °C, 1 bar H2) in a one-step gas-phase process. A proposed mechanism includes a sequence of hydrogenolysis, hydrogenation and dehydration steps occurring on Pt and proton sites of the bifunctional catalyst.

2,5-Dimethyltetrahydrofuran (DMTHF) is deoxygenated to

Aerobic oxidative desulfurization (ODS) of model liquid fuel (dodecane spiked with dibenzothiophene (DBT)) was carried out in the presence of bulk and supported Keggin-type heteropoly acids H3+nPMo12-nVnO40 (HPA-n, n = 0–3) as heterogeneous catalysts and benzaldehyde as a sacrificial reductant. In the presence of bulk H4PMo11VO40 (HPA-1), 100% of DBT was removed from fuel (converted to DBT sulfone) at 60 °C and ambient air pressure. Multiple catalyst reuse without loss of activity was demonstrated. The ODS reaction was strongly inhibited by radical scavengers. An unbranched radical chain mechanism was proposed.

Keggin-type heteropoly acids supported on activated carbon (HPA/C) are active catalysts for oxidative desulfurization (ODS) of diesel fuel under mild conditions in a biphasic system composed of a benzothiophene-containing model diesel fuel (heptane) and aqueous 30% H2O2. The catalytic activity of HPA/C was found to decrease in the order of HPA: H3PMo12O40 > H3PW12O40 > H4SiW12O40. The most active catalyst, H3PMo12O40/C, exhibited 100% removal of benzothiophenes from model diesel fuel at 60 °C, and could be recovered and reused without loss of activity. This catalyst outperforms other recently reported heterogeneous catalysts for ODS in similar systems. Kinetic and DRIFTS studies provide new insights into the mechanism of ODS reaction on carbon-supported HPAs.

The aliphatic alcohols (methanol, ethanol, 1- and 2-propanol) were used for the upgrading of petroleum asphaltenes. The process was performed under supercritical (sc) conditions at 350 °C. CHNSO analysis and GC methods were used to characterize the elemental and chemical composition of the products preliminarily divided into three fractions: hexane-soluble (HSF), benzene-soluble (BSF), and insoluble residue (IR). It was shown that the sc alcohols leads to the decrease of total content of sulfur and nitrogen in the products (HSF + BSF + IR) by 18–23 and 31–33 wt%, correspondingly, as compared with the initial asphaltenes (IA). The highest yield of the soluble fractions (HSF and BSF) was observed for 1-propanol and ethanol. It appeared that the alcohols used as a reaction media are partially consumed by incorporating in the product molecules as alkoxy substituents. The H and O content of HSF and BSF for all alcohols was significantly higher than that for IA. The composition of hexane-soluble fraction obtained after sc upgrading is quite similar to chemical composition of the diesel fraction, specifically to straight-run gas oil. The efficiency of each supercritical alcohol used for the upgrading of asphaltenes is analyzed and discussed.

H3PW12O40 heteropoly acid supported on SiO2 and its bulk acidic cesium salt Cs2.5H0.5PW12O40 are demonstrated to be highly active and recyclable solid catalysts for Prins cyclization allowing for the clean, high-yielding synthesis of Florol® from isoprenol and isovaleraldehyde. Florol®, a valuable floral odorant employed in a vast variety of commercial products, was obtained in ca. 80 % yield under nearly ambient conditions. Dimethylcarbonate or diethylcarbonate used as green reaction media, low catalyst loadings and moderate conditions are important features that contribute for the sustainability of the method.

Abstract A world without plastics is unimaginable now and probably also in future. With the growing use of plastic, the problem of waste plastic disposal is also growing. Recycling the plastics is a promising option to avoid the serious environmental challenge caused by them. Among the various options for recycling, catalytic conversion of plastics to hydrocarbons is very attractive. Catalytic pyrolysis depolymerizes the plastics to an oil which can be used as a liquid fuel. This is a sustainable way to utilize the waste, simultaneously promising to meet the energy demand. We studied the use of sulphated zirconium hydroxide as a catalyst for the pyrolysis of different types of plastics such as polypropylene, low density polyethylene, high density polyethylene and a mixture of all three. The objective was to understand the effect of the catalyst and the temperature on the composition of the oil as well as to find an optimum condition for maximum oil yield. Various reaction conditions and their influence on the product distribution are studied. The catalyst is effective in enhancing the reaction rate, altering the product selectivity and narrowing the product distribution of the reaction. At optimum conditions, we obtained more than 79% yield of oil which contains mainly C10–C24 hydrocarbons. The fuel properties are suitable to be used as a fossil fuel substitute. Graphic Abstract

Hydroconversion (hydrogenation and hydrogenolysis) of biomass-derived furanic compounds giving furan ring-hydrogenation and ring-cleavage products attracts interest for sustainable production of chemicals and fuels. Here, the hydroconversion of 2,5-dimethylfuran (DMF), chosen as a model furanic compound, was investigated at a gas-solid interface over carbon-supported Pt, Pd, Rh and Ru metal catalysts in a fixed-bed reactor at 70&ndash, 90 &deg, C and ambient pressure. Pt/C was mainly active in ring cleavage of DMF to produce 2-hexanone as the primary product, followed by its hydrogenation to 2-hexanol and hexane. In contrast, Pd/C, Rh/C and Ru/C selectively hydrogenated the furan ring to 2,5-dimethyltetrahydrofuran (DMTHF). The turnover frequency (TOF) of metal sites in the gas-phase DMF hydroconversion was determined from zero-order kinetics in the absence of diffusion limitations. The TOF values decreased in the sequence Pt &gt, Rh &gt, Pd &gt, &gt, Ru, similar to the liquid-phase reaction. The TOF values for the gas-phase reaction were found to be one order of magnitude greater than those for the liquid-phase reaction. This indicates that the gas-phase process is potentially more efficient than the liquid-phase process. TOF values for hydroconversion of ring-saturated furan derivatives, tetrahydrofuran and DMTHF, on Pt/C, were much lower than those for DMF.

The isomerization of caryophyllene oxide, one of the most widespread sesquiterpenes found in various essential oils, is catalyzed by the acidic Cs salt of tungstophosphoric heteropoly acid, Cs2.5H0.5PW12O40, to give rare polycyclic oxygenated sesquiterpenes with a clovane structure. Cloven-9-ol and clovan-2,9-diol can be obtained with up to 80% combined selectivity and 60% individual selectivity each (under different reaction conditions), which is the best result reported for these compounds so far. The process is environmentally benign and can be performed not only in conventional solvents such as 1,2-dichloroethane and acetone but also in eco-friendly “green” organic solvents such as dimethylcarbonate, diethylcarbonate and 2-methyltetrahydrofuran. The reactions occur under ambient conditions at low catalyst loadings without catalyst leaching. The solid catalyst can be simply centrifuged from the reaction mixture, and low boiling solvents can be separated from reaction products by distillation.

Keggin-type polyoxometalates (POM) immobilized on alkylaminophosphazene (RPN)-functionalized silica (POM/RPN-SiO2) are new effective single-site solid catalysts for oxidative desulfurization (ODS) of diesel fuel under mild conditions in a biphasic system composed of a benzothiophene-containing model diesel fuel (heptane) and aqueous 30% H2O2. The catalytic activity of POM/RPN-SiO2 was found to be influenced by the choice of POM and the amine R group in RPN, decreasing in the order PMo > PW > SiW and Bz > iBu > iPr, respectively. The most effective catalyst, PMo/BzPN-SiO2 (PMo = PMo12O403−), exhibited 100% removal of dibenzothiophene from model diesel fuel at 60 °C and ambient pressure and could be reused without loss of activity. This catalyst outperforms other recently reported heterogeneous catalysts for ODS in similar systems. 13C, 29Si and 31P MAS NMR, FTIR, SEM, BET and elemental analysis were used to characterize the structure of surface phosphazene and POM species in the new catalysts.

Ketonisation of acetic acid to acetone was studied in the gas phase using γ-Al2O3, TiO2, ZrO2 and CeO2 as the catalysts in the temperature range of 180–350 °C and ambient pressure. Catalyst activity was found to increase in the order Al2O3

An original method for direct synthesis of tetramethyl orthosilicate from SiO2 raw minerals and supercritical methanol was developed for the first time in a flow mode. The process promoted by KOH was performed at 270 °C and 100 atm using 3 A zeolite molecular sieves to shift the reversible reaction toward TMOS formation by removing released water. The equilibrium constant Keq of the reaction was determined as 0.839E-08. Silica gel (100 wt% SiO2), quartz sand (97 wt% SiO2), expanded perlite (73 wt% SiO2) and vermiculite (38 wt% SiO2) were tested as SiO2 minerals. The highest equilibrium concentration of TMOS equal to 20.4 g/L was achieved for silica gel that can be increased using larger amount of water adsorbent.

Acidic Cs salt of tungstophosphoric heteropoly acid, Cs2.5H0.5PW12O40 (CsPW), is excellent solid acid catalyst for liquid-phase cycloaddition reactions of biomass-based and easily available from essential oils monoterpenic compounds, such as limonene, α-terpineol, α-pinene, β-pinene and nerol, with aldehydes, including benzaldehyde, crotonaldehyde as well as biomass-derived cuminaldehyde and trans-cinnamaldehyde. The reactions give oxabicyclo[3.3.1]nonene compounds potentially useful for the fragrance and pharmaceutical industries in good to excellent yields. The process is environmentally benign and can be performed in biomass-derived solvent 2-methyltetrahydrofuran and eco-friendly “green” organic solvents such as dimethylcarbonate and diethylcarbonate under mild conditions at low catalyst loadings without leaching problems. The solid CsPW catalyst can be easily separated from the reaction media and low-boiling solvents can be removed by distillation. Silica-supported H3PW12O40 also demonstrated good performance in these reactions.

Silica-supported zinc oxide possessing acid and dehydrogenation functions is an efficient, noble-metal-free bifunctional catalyst for the environment-friendly synthesis of p-Cymene from renewable monoterpene feedstock by gas-phase dehydroisomerisation of α-pinene and limonene in a fixed-bed reactor. The reaction involves acid-catalysed terpene isomerisation to p-menthadienes followed by dehydrogenation to form p-Cymene. Dehydroisomerisation of α-pinene produces p-Cymene with 90% yield at 100% conversion at 370 °C and WHSV = 0.01–0.020 h−1. The reaction with limonene gives a 100% p-Cymene yield at 325 °C and WHSV = 0.080 h−1. ZnO/SiO2 catalyst shows stable performance for over 70 h without co-feeding hydrogen.

Hydrodeoxygenation (HDO) of 2,5-dimethyltetrahydrofuran (DMTHF) was studied at a gas-solid interface in a fixed-bed microreactor in the presence of bifunctional metal-acid catalysts comprising Pt/C and acidic heteropoly salt Cs2.5H0.5PW12O40 (CsPW). The Pt–CsPW catalyst deoxygenated DMTHF to n-hexane with >99% selectivity under mild conditions (90–100 °C, ambient pressure) and was much more efficient than monofunctional Pt/C. On the basis of kinetic studies, a mechanism for the HDO of DMTHF over Pt–CsPW was proposed, which includes a sequence of hydrogenolysis, dehydration and hydrogenation steps catalysed by Pt and proton sites of the bifunctional catalyst. The turnover rate of HDO increased with increasing Pt particle size suggesting that the hydrogenolysis of C–O bond in furanic compounds on Pt is a structure-sensitive reaction.

The impact of CaO on oakwood pyrolysis was explored by the Py-GC/MS at 500 °C. Ca(OH)2 presents on the CaO surface, indicating its partial hydration (noted as CaOOH). CaOOH promoted the ketonisation of carboxylic acids to aliphatic ketones, furfural to cyclopentanone/2-cyclopentenone, facilitated the elimination of the methoxy-phenolic compounds. The catalyst loading did not show any significant effect on the formation of acetone, while a noticeable reduction in the phenolics was revealed. Increasing catalyst loading almost eliminated CO2, acids, furans, aldehydes, ether groups, whilst the fractions of alcohols, esters, sugars, and alkoxybenzene decreased noticeably. The use of partially hydrated CaOOH in the CFP can create conditions where by-products generated during the ketonisation and phenolics upgrading reactions (CO2, H2O, CO) interact through the adsorption enhance water-gas-shift reaction and through coking reactions with formation of H2 used for hydrogenation during multistep conversion of furfural to cyclopentanone in a vapour phase.

The reactions of biomass-based substrates, i.e., limonene, α-pinene, β-pinene, terpinolene, α-terpineol, nerol and linalool, with benzaldehyde in the presence of tungstophosphoric heteropoly acid H 3 PW 12 O 40 (HPW) supported on silica give an oxabicyclo[3.3.1]nonene compound with fragrance characteristics in good to excellent yields. The reactions apparently involve the formation of α-terpenyl carbenium ion by the protonation of alkene or dehydration of alcohol followed by the nucleophilic attack of benzaldehyde. The subsequent oxonium-ene cyclization of the resulting oxocarbenium ion gives the oxabicyclic product. The process is an environmentally benign and heterogeneous and can be performed under mild conditions with low catalyst amounts and no significant leaching of active components.

We studied the catalytic hydrogenation of CO2 to methane using nickel-niobia composite catalysts. Catalysts containing 10–70 wt% Ni were synthesized by wet impregnation and tested for CO2 hydrogenation in a flow reactor. 40 wt% was found to be the optimum Ni loading, which resulted in CO2 conversion of 81% at 325 °C. We also calcined the Nb2O5 support at different temperatures to study the influence of calcination temperature on the catalytic performance. 40 wt% Ni loaded on Nb2O5, which was calcined at 700 °C gave higher methanation activity (91% conversion of CO2). Time on stream study for 50 h showed a stable activity and selectivity; thus confirming the scope for practical application. E.S.G. and N.R.S acknowledge the financial support from NOW CAPITA project (732.013.002). ASE acknowledges the financial support from the MINECO projects MAT-2013-45008-P and MAT2016-81732-ERC. EVRF gratefully acknowledge support from MINECO for his Ramón y Cajal grant (RyC-2012-11427) and University of Alicante for the project GRE-13-31. Generalitat Valenciana is also acknowledged for financial support (PROMETEOII/ 2014/004).

© 2019 American Chemical Society. Isomerization of cyclohexane was investigated in the presence of monofunctional acid and bifunctional metal-acid catalysts based on Keggin-type heteropoly acid H3PW12O40 and Pt and Au as the metal components using a differential fixed-bed microreactor at 180-300 °C, ambient pressure and a C6H12/H2 partial pressure ratio of 0.04-0.14. Particular emphasis was placed on the acidic Cs salt, Cs2.5H0.5PW12O40 (CsPW) as the acid catalyst and Pt/CsPW, Au/CsPW, and PtAu/CsPW as the bifunctional catalysts. Pt/CsPW and Au/CsPW were more efficient than the monofunctional acid catalyst CsPW, and Pt/CsPW was more active than Au/CsPW with both giving >99% selectivity to methylcyclopentane. It was found with Pt/CsPW that the cyclohexane dehydrogenation step equilibrated at a molar ratio of Pt and H+ surface sites Pt/H+ ≥ 0.7, which is much higher than for Pt/zeolite. PtAu/CsPW bimetallic catalyst exhibited a 2-fold higher activity in cyclohexane isomerization and a 3.5-fold higher activity in the accompanying dehydrogenation of cyclohexane to benzene than the mixture of Pt/CsPW and Au/CsPW with the same metal loading. The enhancing effect of gold is assigned to PtAu bimetallic particles, which had a higher Pt dispersion than the Pt in Pt/CsPW. Scanning transmission electron microscopy-energy dispersive X-ray spectroscopy (STEM-EDX) revealed bimetallic PtAu particles in PtAu/CsPW with a wide range of Pt/Au atomic ratios. No enhancing effect of gold was found in the case of carbon-supported catalyst PtAu/C physically mixed with CsPW, and the STEM-EDX analysis revealed no modification of Pt sites by Au in this catalyst.

© 2018 Elsevier B.V. The isomerization of α-pinene oxide in the presence of Cs2.5H0.5PW12O40 (CsPW) heteropolysalt as solid acid catalyst is reported. The reactions were performed in various solvents, which allowed to obtain trans-carveol, trans-sobrerol and pinol in 60–80% yield each, which exceed the yields reported so far. The CsPW catalyst could be recovered and reused without loss of its activity and selectivity.

The sulfidation of NiMo catalyst by thermal decomposition of support surface-bound thiols to generate stoichiometric amount of H2S has proved to be a clean and remarkable approach for catalyst activation. The role of loading of thiol groups on the formation and dispersion of MoS2 active phase on the mesoporous silica support was further evaluated. The catalytic activity of the supported catalysts and a reference catalyst was evaluated in the hydrodesulfurization (HDS) of dibenzothiophene. The soft acid-soft base interaction between Mo metal and thiol groups enhanced proportionately the metal’s dispersion on the thiol containing support. The thermal decomposition of thiols to generate H2S result in slow and uniform sulfidation of the NiMo to form the NiMoS catalyst. This approach of in-situ generation of H2S for sulfidation provides a promising green method of activating the HDS catalysts without direct use of H2S. Key: hydrodesulfurization; sulfidation; thiol; silica; dibenzothiophene

Aiming at developing a simple, feasible method for SO2 and NOx removal, in this work, various doping amounts of heteropolyacid and heteropolyacid salts were prepared and used in wet absorption for simultaneous removal of SO2 and NO. The desulfurization and denitrification performance was evaluated by investigating dynamic SO2 and NO absorption in a simulated reactor containing a heteropoly compound (HPC) solution along with various factors influencing the reaction. The results demonstrate that this system had a high removal efficiency of SO2 and modest NO removal. The amount of Wolfram (W) doping and the pH of the solution affecting the removal performance was studied, and a stable SO2 removal efficiency higher than 95% was obtained for HPW1Mo at a pH value of 5.5. In addition, the desulfurization performance of NaPWMo with a 50% removal efficiency was higher than that of the HPWMo solution (20%) after a 60 min reaction time. A high concentration of the NaPWMo solution and the presence of O2 were beneficial to desulfurization at room temperature. In addition, the removal efficiency of SO2 or NO by NaPWMo was only affected by its own gas concentration rather than their mutual influences on each other. This work should be beneficial to the optimization leading to the development of simultaneous desulfurization and denitrification systems in practical applications.

NiMo/SiO2 hydrodesulfurization catalyst prepared through the polyoxometalate route using Keggin type phosphomolybdates has high activity in HDS of thiophene at 350–400 °C and 1 bar pressure. The NiMo/SiO2 pre-catalyst retains intact Keggin structure of phosphomolybdic polyoxometalate, which transforms on stream into a NiMo sulfidic active phase. The pre-catalyst also possesses Bronsted and Lewis acidity, which is lost during the HDS reaction. This catalyst undergoes faster sulfidation and shows higher thiophene conversion and higher butene selectivity than conventional industrial NiMo/Al2O3 catalyst with similar Mo loading. The polyoxometalate catalyst preparation route is therefore considered to be a performance enhancement methodology for HDS catalysis.

Deoxygenation and decomposition of ethers and esters, including anisole, diisopropyl ether (DPE), and ethyl propanoate (EP), was investigated using bifunctional metal–acid catalysis at a gas–solid interface in the presence and absence of hydrogen. The bifunctional catalysts studied comprised Pt, Ru, Ni, and Cu as the metal components and Cs2.5H0.5PW12O40 (CsPW), an acidic Cs salt of Keggin-type heteropoly acid (HPA) H3PW12O40, as the acid component, with the main focus on Pt–CsPW catalyst. It was found that bifunctional metal–acid catalysis in the presence of H2 is more efficient for ether and ester deoxygenation than the corresponding monofunctional metal and acid catalysis and that metal- and acid-catalyzed pathways play different roles in these reactions. With Pt-CsPW, hydrodeoxygenation of anisole, a model for the deoxygenation of lignin, occurred with 100% yield of cyclohexane under very mild conditions (60–100 °C and 1 bar of H2). This catalyst had the highest activity in anisole deoxygenation for a gas-phase catalyst system reported so far. The catalyst activity decreased in the order of metals: Pt ≫ Ru > Ni > Cu. For HPA-catalyzed DPE and EP decomposition, relationships between the turnover reaction rate (turnover frequency) and the HPA acid strength were found, which can be used to predict the activity of acid catalysts in these reactions.

The cesium salt of tungstophosphoric heteropoly acid, Cs2.5H0.5PW12O40, is an active and environmentally friendly heterogeneous catalyst for the liquid-phase acetylation of nopol and several biomass-derived terpenic alcohols (i.e., α-terpineol, nerol, geraniol, linalool, menthol, isoborneol, perillyl alcohol, carveol, isopulegol, carvacrol and nerolidol) with acetic anhydride. The resulting flavor and fragrance acetic esters, which are widely used in perfumery, household and food products, are obtained in good to excellent yields. The reactions occur at room temperature with low catalyst loadings without substantial catalyst leaching and can be performed with stoichiometric amounts of an acetylating agent in solvent free systems.

Bulk and supported hydrodesulfurization catalysts based on Mo and W and containing Co or Ni as promoters and phosphorus as a modifier are prepared through the polyoxometalate route using Keggin type phosphomolybdates and phosphotungstates and tested in the HDS of thiophene at 350–400 °C and 1 bar pressure. The corresponding oxidic pre-catalysts retain intact Keggin structure of the parent polyoxometalates and possess Bronsted and Lewis acidity. In the course of sulfidation, the oxidic pre-catalysts transform into an active sulfidic phase with the loss of Keggin structure and catalyst acidity. Catalyst activity increases in the order of supports: SiO 2 2 2 O 3 . CoMoP/γ-Al 2 O 3 catalyst prepared through the polyoxometalate route shows higher HDS activity and butene selectivity than industrial catalyst of comparable composition. The results indicate that polyoxometalate catalyst preparation route can be considered a performance enhancement methodology for HDS catalysis.

Dehydration of MeOH to dimethyl ether and EtOH to diethyl ether and ethene was studied at the gas-solid interface in the presence of bulk and SiO2-supported Keggin heteropoly acids (HPAs) H3PW12O40 (PW) and H4SiW12O40 (SiW) as catalysts. The catalysts were prepared by HPA impregnation from water and MeOH. Their acid strength, texture and structural integrity was characterised using NH3 adsorption calorimetry, BET, XRD and DRIFT spectroscopy. The strength of acid sites in HPA/SiO2 catalysts increased monotonously with HPA loading. In the dehydration of MeOH and EtOH, the turnover reaction rate for PW catalysts was higher than for SiW catalysts in agreement with their acid strength. HPA catalysts prepared from water and MeOH had a very close acid strength and showed similar activities in alcohol dehydration. The steady-state catalyst activity was found to correlate with the density of catalyst proton surface sites rather than with the HPA loading. This indicates that alcohol dehydration occurred via a mechanism of surface-type HPA catalysis at the gas-solid interface rather than a bulk-type (pseudo-homogeneous) catalysis.

One-pot conversion of mechanically activated cellulose to sorbitol was investigated over bifunctional catalysts based on Ru (0.6, 1 and 3 wt.%) and cesium salts of heteropoly acids (HPA) Cs2.1H0.9PW12O40 and Cs3HSiW12O40 (Cs-PW and Cs-SiW, respectively). The maximal yield of sorbitol equal to 59 % and selectivity 94 % were achieved over the 1%Ru/Cs3HSiW12O40 catalyst. Physicochemical and catalytic data showed that the rate-determining step, i.e. the hydrolysis of cellulose, depended on the surface acidity of catalysts, whereas Ru content in catalyst affected both the hydrolysis and the hydrogenation steps. The kinetic parameters for one-pot conversion of cellulose were determined by mathematical modeling approach and were successfully used for the prediction of the yields of sorbitol and mannitol.

Isomerisation of n-hexane was studied in the presence of acid and bifunctional metal-acid catalysts based on Keggin-type heteropoly acids (HPA), in particular focusing on Cs2.5H0.5PW12O40 (CsPW) and Pt/CsPW as the catalysts, using a fixed-bed microreactor under differential conditions (n-hexane conversion ≤ 10%) at 180–220 °C, ambient pressure and a ratio of n-hexane and H2 partial pressures of 0.06–0.24. The turnover rate of HPA-catalysed isomerisation was found to correlate with the acid strength of HPA (initial enthalpy of ammonia adsorption). Bifunctional Pt-HPA catalysts were more efficient than monofunctional HPA catalysts. In the isomerisation over Pt/CsPW bifunctional catalyst, n-hexane dehydrogenation step was found to equilibrate at a molar ratio of Pt and H+ surface sites Pts/H+ ≥ 0.8, corresponding to a Pt loading ≥6%. Bimetallic PtAu/CsPW catalyst showed higher activity in n-hexane isomerisation than Pt/CsPW, although the Au alone without Pt was inert. In the presence of Au, the turnover rate at Pt sites increased more than twofold. The effect of Au is attributed to PtAu alloying. Scanning transmission electron microscopy–energy dispersive X-ray spectroscopy (STEM-EDX) and X-ray diffraction (XRD) analyses of PtAu/CsPW indicated the presence of bimetallic PtAu nanoparticles with a wide range of Pt/Au atomic ratios.

Red mud, a by-product of the Bayer process in the aluminium industry, is co-processed with beechwood for the in-situ upgrading of fast pyrolysis vapour products. It is revealed that the co-processing of beechwood with thermally pre-treated red mud enhanced the vapour upgrading effect. Individual oxides (α-Al 2 O 3 , Fe 2 O 3 , SiO 2 , and TiO 2 ), which are the main constituents of red mud were also tested for the identification of their individual impact on the upgrading process. A biomass/catalyst weight ratio of 1:4 showed the strongest effect on the product distribution. Red mud was found to reduce the yield of phenolic compounds and promote the formation of cellulose- and hemicellulose-derived furfurals and hemicellulose-derived acetic acid, which can be used for the production of a broad range of chemicals and liquid transportation fuels. α-Al 2 O 3 and Fe 2 O 3 reduced the relative yield of phenols as well, whereas the formation of furfurals was promoted by Fe 2 O 3 and TiO 2 . SiO 2 showed negligible effect on fast pyrolysis vapours. The impact of catalysts on the product distribution is discussed for phenols, furfurals, and acids, for which the strongest effects were observed.

Gas-phase hydrogenation of a wide range of ketones to alkanes, including hydrogenation of aliphatic ketones and acetophenone, was investigated using bifunctional metal–acid catalysis. The catalysts were comprised of a metal (Pt, Ru, Ni, and Cu) supported on acidic caesium salt of tungstophosphoric heteropoly acid Cs2.5H0.5PW12O40 (CsPW). The reaction occurred via a sequence of steps involving hydrogenation of ketone to alcohol on metal sites followed by dehydration of alcohol to alkene on acid sites and finally hydrogenation of alkene to alkane on metal sites. Catalyst activity decreased in the order: Pt > Ru >> Ni > Cu. Pt/CsPW showed the highest catalytic activity, giving almost 100% alkane yield at 100 °C and 1 bar pressure. Evidence is provided that the reaction with Pt/CsPW at 100 °C is limited by ketone-to-alcohol hydrogenation, whereas at lower temperatures (≤60 °C) by alcohol dehydration yielding alcohol as the main product. The catalyst comprised of a physical mixture of Pt/C + CsPW was found to be highly efficient as well, which indicates that the reaction is not limited by migration of intermediates between metal and acid sites in the bifunctional catalyst.

Bulk Zn(II)-Cr(III) mixed oxides with a Zn/Cr atomic ratio of 1:1–20:1 were found to be active catalysts for the gas-phase ketonisation of carboxylic acids (acetic and propionic) to form acetone and 3-pentanone, respectively, at 300–400 °C and ambient pressure. Zn-Cr (10:1) oxide showed the best performance, significantly exceeding that of the parent oxides ZnO and Cr2O3. The catalytic activity was further enhanced by supporting Zn-Cr (10:1) oxide on TiO2 and γ-Al2O3. With 20%Zn-Cr/Al2O3, ketonisation of propionic acid occurred with 97% selectivity to 3-pentanone at 99% conversion at 380 °C. Zn-Cr oxides were characterised by BET, XRD, DRIFTS of pyridine and acetic acid adsorption and microcalorimetry of ammonia adsorption. From DRIFTS, carboxylic acid adsorbed dissociatively on Zn-Cr oxide to form a surface metal carboxylate in bidentate bridging bonding mode. A mechanism for ketonisation of carboxylic acids via β-ketoacid intermediate route has been proposed.

Dehydration of ethanol was studied at a gas–solid interface over a wide range of solid Bronsted acid catalysts based on Keggin-type heteropoly acids (HPAs) in a continuous flow fixed-bed reactor in the temperature range of 90–220 °C focussing on the formation of diethyl ether (DEE). The catalysts included H3PW12O40 (HPW) and H4SiW12O40 (HSiW) supported on SiO2, TiO2, Nb2O5 and ZrO2 with sub-monolayer HPA coverage, as well as bulk acidic Cs salts of HPW (Cs2.5H0.5PW12O40 and Cs2.25H0.75PW12O40) and the corresponding core–shell materials with the same total composition (15%HPW/Cs3PW12O40 and 25%HPW/Cs3PW12O40, respectively) comprising HPW supported on the neutral salt Cs3PW12O40. The ethanol-to-DEE reaction was found to be zero order in ethanol in the range of 1.5–10 kPa ethanol partial pressure. The acid strength of catalysts was characterised by ammonia adsorption microcalorimetry. A fairly good correlation between the catalyst activity (turnover frequency) and the catalyst acid strength (initial enthalpy of ammonia adsorption) was established, which demonstrates that Bronsted acid sites play important role in ethanol-to-DEE dehydration over HPA catalysts. The acid strength and the catalytic activity of core–shell catalysts HPW/Cs3PW12O40 did not exceed those of the corresponding bulk Cs salts of HPW with the same total composition, which contradicts the literature claims of the superiority of the core–shell HPA catalysts.

The alkylation of benzene by propane to yield isopropylbenzene (iPrPh) was studied using bifunctional Pd-acid catalysts, such as Pd-heteropoly acid and Pd-zeolite, in a fixed bed reactor at 300 °C and 1 bar pressure. Keggin-type tungstosilicic acid H4SiW12O40 (HSiW) and zeolite HZSM-5 were used as the acid components in these catalysts. The reaction occurred most efficiently over 2%Pd/25%HSiW/SiO2, giving iPrPh with up to 88% selectivity. The Pd-HSiW catalyst was more selective than the Pd-HZSM-5; the latter gave only 11–18% iPrPh selectivity. The reaction proceeded via a bifunctional mechanism including the dehydrogenation of propane to form propene on Pd sites, followed by the alkylation of benzene with the propene on acid sites. The effect of Pd loading in Pd-HSiW and Pd-HZSM-5 catalysts indicated that the first step reached quasi-equilibrium at 1.5–2% Pd loading and the second step became rate limiting. The addition of gold to Pd-HSiW enhanced the activity of this catalyst, although the Au-HSiW without Pd was inert.

Hydrodeoxygenation (HDO) of 3-pentanone to yield n -pentane was carried out using bifunctional metal-acid catalysis at a gas-solid interface at 40–80 °C and 1 bar H 2 pressure in a fixed-bed microreactor. The bifunctional catalysts studied comprised Pt as the metal component and Cs 2.5 H 0.5 PW 12 O 40 (CsPW), an acidic Cs salt of Keggin-type heteropoly acid H 3 PW 12 O 40 , as the acid component. The bifunctional HDO pathway included hydrogenation of ketone to secondary alcohol on metal sites followed by dehydration of the alcohol to alkene on acid sites and finally alkene hydrogenation to alkane on metal sites. Addition of gold to the Pt/CsPW was found to increase both catalyst hydrogenation activity (turnover rate at Pt sites) and catalyst stability to deactivation, although the Au alone without Pt was almost totally inert. The enhancement of catalyst performance is suggested to be caused by PtAu alloying. Scanning transmission electron microscopy–energy dispersive X-ray spectroscopy (STEM-EDX) and X-ray diffraction (XRD) analysis of the PtAu/CsPW catalysts indicated the presence of bimetallic PtAu nanoparticles with a wide range of Pt/Au atomic ratios (0.5–7.7).

Terpenes are an abundant class of natural products, which is important for flavor and fragrance industry. Many acid catalyzed reactions used for upgrading terpenes still involve mineral acids as homogeneous catalysts and/or toxic solvents. Heteropoly acids represent a well-established eco-friendly alternative to conventional acid catalysts. As these reactions are usually performed in the liquid phase, solvents play a critical role for the process sustainability. In the present work, we developed a catalytic route to valuable fragrance ingredients, dihydrocarvone and carvenone, from limonene oxide by its isomerization using silica-supported tungstophosphoric acid as a heterogeneous catalyst and dialkylcarbonates as green solvents. The reaction pathway can be switched between dihydrocarvone and carvenone (obtained in 90% yield each) simply by changing the reaction temperature. In addition, we developed an efficient method for kinetic separation of trans-limonene oxide from commercial cis/trans-limonene oxide mixture and stereoselective synthesis of trans-dihydrocarvone.