Kinetics study on supported indium-based catalysts in carbon dioxide hydrogenation
【Abstract】In this work, the effect of support materials on the kinetic behaviors of indium-based catalysts in carbon dioxide hydrogenation was studied. A series of supported indium-based catalysts were prepared and tested. Only group ⅣB metal (Ti, Zr and Hf) oxide supported indium-based catalysts have substantial catalytic activity. Particularly, In1/HfO2 and In1/ZrO2 catalysts show high methanol selectivity, while In1/TiO2 mainly catalyzes the reverse water-gas shift reaction. The steady-state kinetics, in-situ diffuse reflectance infrared Fourier transform spectroscopy and temperature-programmed experiments indicate that the key surface reaction intermediates over In1/HfO2 and In1/ZrO2 are formate and methoxy species, and methanol is produced via stepwise hydrogenation of the surface formate. In1/HfO2 possesses the strongest hydrogen splitting and hydrogenation ability, thus favoring methanol synthesis. Over In1/TiO2, no significant surface carbonaceous species is detected under reaction conditions. The improved CO production might be related to the interfacial oxygen defects facilitating the redox cycle and decomposition of formate intermediate.
【Keywords】 carbon dioxide; catalysts; kinetics; methanol synthesis; in-situ DRIFTS; temperature-programmed experiments;
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