Thirumalaiswamy Raja

Promotional effect of Fe on the performance of supported Cu catalyst for ambient pressure hydrogenation of furfural

A noble-metal free FeCu based bimetallic catalyst system prepared by facile co-impregnation method was found to be highly admirable for vapour phase selective hydrogenation of furfural to furfuryl alcohol at ambient pressure. Monometallic Cu/γ-Al2O3, Fe/γ-Al2O3 and bimetallic FeCu/γ-Al2O3 catalysts with different Fe loadings were prepared. Structural and morphological features of the catalysts were thoroughly investigated by several physico-chemical characterization techniques. The influence of various reaction parameters, such as Fe loading, reaction temperature and flow of reactants was examined with respect to furfural conversion and furfuryl alcohol yield. The results clearly showed that an optimum amount of Fe is necessary to enhance the catalytic activity of monometallic Cu/γ-Al2O3 for the selective hydrogenation of furfural. The catalyst FC-10 with 10 wt% Fe exhibited excellent activity which led to high furfural conversion (>93%) and furfuryl alcohol selectivity (>98%) under mild reaction conditions. The higher activity of bimetallic FeCu/γ-Al2O3 compared to monometallic Cu/γ-Al2O3 is ascribed to the formation of FeCu bimetallic particles and the existence of oxygen vacancies in the Fe oxide system. The superior activity after Fe loading on the Cu-based catalyst was attributed to the synergy between Cu and Fe. A plausible mechanism is proposed to explain the promoting effect of Fe, which involves synergism between Fe sites with strong oxophilic nature and Cu sites with a high ability for hydrogen activation. Based on the activity results, prolonged catalytic activity and spent catalyst analysis, the developed FeCu/γ-Al2O3 catalyst is inexpensive, eco-benign and robust, which makes it a promising candidate for the efficient conversion of biomass-derived substrates to fine chemicals and drop-in biofuels.

Role of Nanointerfaces in Cu‐ and Cu+Au‐Based Near‐Ambient‐Temperature CO Oxidation Catalysts

Disordered mesoporous Cu‐doped ceria‐zirconia (Cu0.1Ce0.85Zr0.05O2), and gold deposited (Au/Cu0.1Ce0.85Zr0.05O2) catalysts were synthesized and evaluated for CO oxidation. Onset of CO oxidation activity, and 50 % (100 %) CO2 formation occurs at room temperature (RT), and 77 (120)°C, respectively, with Cu0.1Ce0.85Zr0.05O2. A small amount of gold on Cu0.1Ce0.85Zr0.05O2 induces the sustainable oxidation catalysis around RT. Onset of copper reduction temperature decreases from 110 °C on Cu0.1Ce0.85Zr0.05O2 to 48 °C with Au/Cu0.1Ce0.85Zr0.05O2, highlighting the direct interaction between Cu and Au through a Cu–Au interface. Au particles with a (0 0 1) facet deposit on an oxygen‐deficient site of (1 1 1) facet of CeO2‐ZrO2. Any decrease in surface Cu‐content with increasing Au‐content further supports the Au‐Cu‐Ce/Zr interface interactions. Nanointerfaces of Au clusters on Cu next to oxygen‐deficient sites of CeO2‐ZrO2 facilitate all the elementary steps of the CO+O2 reaction to occur in close proximity at ambient conditions.

Ce–Ni mixed oxide as efficient catalyst for H2 production and nanofibrous carbon material from ethanol in the presence of water

Hydrogen production from ethanol steam reforming (H2O/C2H5OH = 3) was studied over Ce–Ni based catalysts issued from different preparation methods (co-precipitation (CP), impregnation (IMP) and incipient wetness impregnation (IWI)). Catalysts prepared by the CP method exhibit higher activity and much better stability compared to the other two types of catalysts. The Ni1CeOY–CP catalyst is able to completely convert ethanol at 450 °C to H2, CO2 and CH4 (almost no CO is observed), with a H2 yield of 3 moles of hydrogen produced per mole of ethanol converted. A very high H2 yield of 4.6 mol molEtOH−1 is achieved over the Ni1CeOY–CP mixed oxide at 650 °C. Correlations between the preparation method, catalytic activity and stability, and type of carbon deposition are discussed. The CP method forms very active small sized NiO (15 nm) and CeO2 (4 nm) nanoparticles, leading to the formation of a lower amount of carbon deposition in the form of nanofibrous carbon materials, the size of which depends on the Ni related nanoparticles. For CP catalysts, the graphitic filaments obtained correspond to carbon nanofibers (CNFs) and carbon nanotubes (CNTs) with a much smaller and homogenous size compared to the filamentous carbon formed over the catalysts issued from the other preparation methods, in relation to the active particles size. The catalytic stability is attributed to the type of carbon formed.

Oxidative dehydrogenation of ethyl benzene to styrene over hydrotalcite derived cerium containing mixed metal oxides

Cerium containing mixed oxides derived from hydrotalcites was prepared and its catalytic activity was studied for oxidative dehydrogenation of ethyl benzene to styrene. Structural, spectroscopic and morphological features of the catalyst have been thoroughly examined with various physico-chemical characterization methods. Raman spectroscopy studies show evidence for oxygen vacancies in lower loadings of cerium which enhanced the oxygen migration. The transmission electron microscopy image showed good dispersion of ceria clusters on the mixed metal oxide. The catalytic activity results suggested that the conversion of ethyl benzene and styrene yield is stable for at least 12 hours without any significant catalyst deactivation. The styrene selectivity and ethyl benzene conversion were higher in a catalyst containing 0.03 mole percentage of cerium. Structural features of the spent catalysts have also been examined to demonstrate the stability of the catalyst during the reaction.

An efficient robust fluorite CeZrO4−δ oxide catalyst for the eco-benign synthesis of styrene

In this work, we have reported CeO2, ZrO2, physically mixed (PH)-CeO2/ZrO2 and fluorite CeZrO4−δ oxides and their catalytic activities for the oxidative dehydrogenation (ODH) of ethyl benzene (EB) to styrene (ST) using molecular oxygen, air and carbon dioxide as oxidants. The catalysts were prepared by a gel-combustion method followed by calcination at 600 °C for 6 h and subjected to catalytic activity measurements. All the catalysts were characterized and studied by various physicochemical methods. The reaction parameters were varied systematically such as different catalysts, oxidants, temperatures, EB flow and oxidant flow. CeZrO4−δ accounted for a 47% styrene yield for 72 h without any significant deactivation under optimized reaction conditions. A thorough analysis of the spent catalysts demonstrated the robustness of the catalyst for this reaction under different oxidants and reaction conditions. Pristine CeO2 deactivated easily and the activity decreased with time on stream of the reaction.

A green chemistry approach to styrene from ethylbenzene and air on MnxTi1−xO2 catalyst

Styrene (ST) is an industrially important commodity chemical, and design of a suitable catalyst, which provides high ethyl benzene (EB) conversion and styrene selectivity at lower temperature with sustainable activity, is one of the major challenges in the field of heterogeneous catalysis. Manganese incorporated in titania (MnxTi1−xO2) anatase lattice, prepared via the solution combustion method, was evaluated for oxidative dehydrogenation (ODH) of EB with O2 or air. MnxTi1−xO2 catalysts were characterized by different physiochemical methods. Up to 15% Mn could be introduced into the TiO2 lattice. TEM and XRD indicate disordered mesoporosity, further confirmed by adsorption isotherm analysis. MnxTi1−xO2 catalysts were evaluated for ST synthesis from EB using air or oxygen as oxidant between 440 and 570 °C. Reaction conditions have been varied systematically, such as catalyst composition, and EB/air/O2 flow. MnxTi1−xO2 shows sustainable 55% styrene yield for 45 h without deactivation under optimum conditions. A thorough analysis of spent catalysts demonstrates the conversion of initial anatase phase MnxTi1−xO2 to Mn3O4 supported on the rutile (R) phase of TiO2. The above change occurs in the first few hours of reaction and the Mn3O4 on R-TiO2 phase is the active phase of the catalyst and responsible for sustainable activity for longer duration.