A novel coprecipitation-reduction process has been proposed for preparing highly selective Cu/ZnO/Al 2O 3 catalysts for methanol synthesis from CO 2 hydrogenation. Compared to the catalysts prepared by the conventiona...A novel coprecipitation-reduction process has been proposed for preparing highly selective Cu/ZnO/Al 2O 3 catalysts for methanol synthesis from CO 2 hydrogenation. Compared to the catalysts prepared by the conventional method, the new catalysts prepared via the new method exhibit much higher BET surface area and pore size, much smaller crystallite size and higher catalytic activity and selectivity in CO 2 hydrogenation to methanol. It is also found that the molar ratio of Cu + to Cu 0 on the surface of the catalyst obtained by coprecipitation-reduction is much higher than that on the reduced catalyst obtained by the conventional method, which could be crucial for its high activity and selectivity for catalytic hydrogenation of CO 2 to methanol.展开更多
Copper-based catalysts for CO2 hydrogenation to methanol are supported on ZrO2 and CeO2,respectively.Reaction results at 3.0 MPa and temperatures between 200 and 300°C reveal that Cu catalysts supported on ZrO2 a...Copper-based catalysts for CO2 hydrogenation to methanol are supported on ZrO2 and CeO2,respectively.Reaction results at 3.0 MPa and temperatures between 200 and 300°C reveal that Cu catalysts supported on ZrO2 and CeO2 exhibit better activity and selectivity than pure Cu catalyst due to Cu-support(ZrO2 and CeO2)interaction.Combining the structural characterizations with in-situ diffuse reflectance infrared Fourier transform spectroscopy(in-situ DRIFTS),Cu/CeO2 shows the higher methanol selectivity due to the formation of main carbonates intermediates,which are closely related with the oxygen vacancies over Cu/CeO2.In contrast,bicarbonate and carboxyl species are observed on Cu/ZrO2,which originates from the hydroxyl groups presented on catalyst surfaces.Difference in CO2 adsorption intermediates results in the distinct methanol selectivity over the two catalysts.展开更多
An In2O3 supported nickel catalyst has been prepared by wet chemical reduction with sodium borohydride(NaBH4) as a reducing agent for selective hydrogenation of carbon dioxide to methanol. Highly dispersed Ni species ...An In2O3 supported nickel catalyst has been prepared by wet chemical reduction with sodium borohydride(NaBH4) as a reducing agent for selective hydrogenation of carbon dioxide to methanol. Highly dispersed Ni species with intense Ni-In2O3 interaction and enhanced oxygen vacancies have been achieved.The highly dispersed Ni species serve as the active sites for hydrogen activation and hydrogen spillover.Abundant H adatoms are thereby generated for the oxygen vacancy creation on the In2O3 surface. The enhanced surface oxygen vacancies further lead to improved CO2 conversion. As a result, an effective synergy between the active Ni sites and surface oxygen vacancies on In2O3 causes a superior catalytic performance for CO2 hydrogenation with high methanol selectivity. Carbon monoxide is the only by product detected. The formation of methane can be ignored. When the reaction temperature is lower than 225 ℃,the selectivity of methanol is 100%. It is higher than 64% at the temperature range between 225 ℃ and 275 ℃. The methanol selectivity is still higher than 54% at 300 ℃ with a CO2 conversion of 18.47% and a methanol yield of 0.55 gMeOHg-1cath-1(at 5 MPa). The activity of Ni/In2O3 is higher than most of the reported In2O3-based catalysts.展开更多
文摘A novel coprecipitation-reduction process has been proposed for preparing highly selective Cu/ZnO/Al 2O 3 catalysts for methanol synthesis from CO 2 hydrogenation. Compared to the catalysts prepared by the conventional method, the new catalysts prepared via the new method exhibit much higher BET surface area and pore size, much smaller crystallite size and higher catalytic activity and selectivity in CO 2 hydrogenation to methanol. It is also found that the molar ratio of Cu + to Cu 0 on the surface of the catalyst obtained by coprecipitation-reduction is much higher than that on the reduced catalyst obtained by the conventional method, which could be crucial for its high activity and selectivity for catalytic hydrogenation of CO 2 to methanol.
基金financially supported by the National Natural Science Foundation of China (21577014, 21876019, 21825203, 21688102)Programme of Introducing Talents of Discipline to Universities (B13012)the fund of the State Key Laboratory of Catalysis in DICP (Y401010502)
文摘Copper-based catalysts for CO2 hydrogenation to methanol are supported on ZrO2 and CeO2,respectively.Reaction results at 3.0 MPa and temperatures between 200 and 300°C reveal that Cu catalysts supported on ZrO2 and CeO2 exhibit better activity and selectivity than pure Cu catalyst due to Cu-support(ZrO2 and CeO2)interaction.Combining the structural characterizations with in-situ diffuse reflectance infrared Fourier transform spectroscopy(in-situ DRIFTS),Cu/CeO2 shows the higher methanol selectivity due to the formation of main carbonates intermediates,which are closely related with the oxygen vacancies over Cu/CeO2.In contrast,bicarbonate and carboxyl species are observed on Cu/ZrO2,which originates from the hydroxyl groups presented on catalyst surfaces.Difference in CO2 adsorption intermediates results in the distinct methanol selectivity over the two catalysts.
基金the National Natural Science Foundation of China(No.21536008 and 21621004)。
文摘An In2O3 supported nickel catalyst has been prepared by wet chemical reduction with sodium borohydride(NaBH4) as a reducing agent for selective hydrogenation of carbon dioxide to methanol. Highly dispersed Ni species with intense Ni-In2O3 interaction and enhanced oxygen vacancies have been achieved.The highly dispersed Ni species serve as the active sites for hydrogen activation and hydrogen spillover.Abundant H adatoms are thereby generated for the oxygen vacancy creation on the In2O3 surface. The enhanced surface oxygen vacancies further lead to improved CO2 conversion. As a result, an effective synergy between the active Ni sites and surface oxygen vacancies on In2O3 causes a superior catalytic performance for CO2 hydrogenation with high methanol selectivity. Carbon monoxide is the only by product detected. The formation of methane can be ignored. When the reaction temperature is lower than 225 ℃,the selectivity of methanol is 100%. It is higher than 64% at the temperature range between 225 ℃ and 275 ℃. The methanol selectivity is still higher than 54% at 300 ℃ with a CO2 conversion of 18.47% and a methanol yield of 0.55 gMeOHg-1cath-1(at 5 MPa). The activity of Ni/In2O3 is higher than most of the reported In2O3-based catalysts.
