A series of novel carbon nanofibers(CNFs)based Cu-ZrO2 catalysts were synthesized by deposition precipitation method.To investigate the influence of promoter,catalysts were loaded with 1,2,3 and 4 wt%ZnO and character...A series of novel carbon nanofibers(CNFs)based Cu-ZrO2 catalysts were synthesized by deposition precipitation method.To investigate the influence of promoter,catalysts were loaded with 1,2,3 and 4 wt%ZnO and characterized by ICP-OES,HRTEM,BET,N2O chemisorption,TPR,XPS and CO2-TPD techniques.The results revealed that physicochemical properties of the catalysts were strongly influenced by incorporation of ZnO to the parent catalyst.Copper surface area(SCu)and dispersion(DCu)were slightly decreased by incorporation of ZnO promoter.Nevertheless,SCuand DCuwere remarkably decreased when ZnO content was exceeded beyond 3 wt%.The catalytic performance was evaluated by using autoclave slurry reactor at a pressure and temperature of 30 bar and 180℃,respectively.The promotion of CuZrO2/CNFs catalyst with 3 wt%of ZnO enhanced methanol synthesis rate from 32 to 45 g kg^-1 h^-1.Notably,with the ZnO promotion the selectivity to methanol was enhanced to 92%compared to 78%of the un-promoted Cu-ZrO2/CNFs catalyst at the expense of a lowered CO2 conversion.In addition,the catalytic activity of this novel catalyst system for CO2 hydrogenation to methanol was compared with the recent literature data.展开更多
METHANOL is a chemical manufactured world-wide and its production is of interest from bothindustrial and academic points of view. It is used as gasoline extenders and in the manufac-ture of methyl tetra-butyl ether wh...METHANOL is a chemical manufactured world-wide and its production is of interest from bothindustrial and academic points of view. It is used as gasoline extenders and in the manufac-ture of methyl tetra-butyl ether which is used as an octane enhancer in gasoline. The search forpotential additives has been carried out since the discovery of the promoting effect. In thisnote, we report the promoting effect of Mn on Cu-Zn-Al catalyst. The results indicated展开更多
Methanol synthesis is one of the most important industrially-viable approaches for carbon dioxide(CO_(2)) utilization, as the produced methanol can be used as a platform chemical for manufacturing green fuels and chem...Methanol synthesis is one of the most important industrially-viable approaches for carbon dioxide(CO_(2)) utilization, as the produced methanol can be used as a platform chemical for manufacturing green fuels and chemicals. The In_(2)O_(3) catalysts are ideal for sustainable methanol synthesis and have received considerable attention. Herein, Co-, Ni-and Cu-modified In_(2)O_(3) catalysts were fabricated with high dispersion and high stability to improve the hydrogenation performance. The Ni-promoted In_(2)O_(3) catalyst in the form of high dispersion possessed the largest amount of oxygen vacancies and the strongest ability for H_(2) activation, leading to the highest CO_(2) conversion and space time yield of methanol of 0.390 g_(Me OH)g_(cat)^(-1)h^(-1) with CH_(3)OH selectivity of 68.7%. In addition, the catalyst exhibits very stable performance over 120 h on stream, which suggests the promising prospect for industrial applications. Further experimental and theoretical studies demonstrate that surface Ni doping promotes the formation of oxygen defects on the In_(2)O_(3) catalyst, although it also results in lower methanol selectivity. Surprisingly, subsurface Ni dopants are found to be more beneficial for methanol formation than surface Ni dopants, so the Nipromoted In_(2)O_(3)catalyst with a lower surface Ni content at the similar Ni loading can reach higher methanol selectivity and productivity. This work thus provides theoretical guidance for significantly improving the CO_(2) reactivity of In_(2)O_(3)-based catalysts while maintaining high methanol selectivity.展开更多
基金the Ministry of Higher Education Malaysia for providing financial support to this work via FRGS No:FRGS/1/2011/SG/UTP/02/13Universiti Teknologi PETRONAS
文摘A series of novel carbon nanofibers(CNFs)based Cu-ZrO2 catalysts were synthesized by deposition precipitation method.To investigate the influence of promoter,catalysts were loaded with 1,2,3 and 4 wt%ZnO and characterized by ICP-OES,HRTEM,BET,N2O chemisorption,TPR,XPS and CO2-TPD techniques.The results revealed that physicochemical properties of the catalysts were strongly influenced by incorporation of ZnO to the parent catalyst.Copper surface area(SCu)and dispersion(DCu)were slightly decreased by incorporation of ZnO promoter.Nevertheless,SCuand DCuwere remarkably decreased when ZnO content was exceeded beyond 3 wt%.The catalytic performance was evaluated by using autoclave slurry reactor at a pressure and temperature of 30 bar and 180℃,respectively.The promotion of CuZrO2/CNFs catalyst with 3 wt%of ZnO enhanced methanol synthesis rate from 32 to 45 g kg^-1 h^-1.Notably,with the ZnO promotion the selectivity to methanol was enhanced to 92%compared to 78%of the un-promoted Cu-ZrO2/CNFs catalyst at the expense of a lowered CO2 conversion.In addition,the catalytic activity of this novel catalyst system for CO2 hydrogenation to methanol was compared with the recent literature data.
文摘METHANOL is a chemical manufactured world-wide and its production is of interest from bothindustrial and academic points of view. It is used as gasoline extenders and in the manufac-ture of methyl tetra-butyl ether which is used as an octane enhancer in gasoline. The search forpotential additives has been carried out since the discovery of the promoting effect. In thisnote, we report the promoting effect of Mn on Cu-Zn-Al catalyst. The results indicated
基金financially supported by the National Natural Science Foundation of China (22293023, 22293025, 22172189,22172188)CAS Youth Interdisciplinary Team,Program of Shanghai Academic Research Leader (22XD1424100)+4 种基金Science and Technology Commission of Shanghai Municipality (23ZR1481700)Shanghai Sailing Program from the Science and Technology Commission of Shanghai Municipality (23YF1453400)Joint Fund of the Yulin University and the Dalian National Laboratory for Clean Energy (Grant. YLU-DNL Fund 2022001)Qinchuangyuan “Scientists+Engineers” Team Construction Program of Shaanxi Province (2023KXJ-276)the research program from Shaanxi Beiyuan Chemical Industry Group Co.,Ltd.(2023413611014)。
文摘Methanol synthesis is one of the most important industrially-viable approaches for carbon dioxide(CO_(2)) utilization, as the produced methanol can be used as a platform chemical for manufacturing green fuels and chemicals. The In_(2)O_(3) catalysts are ideal for sustainable methanol synthesis and have received considerable attention. Herein, Co-, Ni-and Cu-modified In_(2)O_(3) catalysts were fabricated with high dispersion and high stability to improve the hydrogenation performance. The Ni-promoted In_(2)O_(3) catalyst in the form of high dispersion possessed the largest amount of oxygen vacancies and the strongest ability for H_(2) activation, leading to the highest CO_(2) conversion and space time yield of methanol of 0.390 g_(Me OH)g_(cat)^(-1)h^(-1) with CH_(3)OH selectivity of 68.7%. In addition, the catalyst exhibits very stable performance over 120 h on stream, which suggests the promising prospect for industrial applications. Further experimental and theoretical studies demonstrate that surface Ni doping promotes the formation of oxygen defects on the In_(2)O_(3) catalyst, although it also results in lower methanol selectivity. Surprisingly, subsurface Ni dopants are found to be more beneficial for methanol formation than surface Ni dopants, so the Nipromoted In_(2)O_(3)catalyst with a lower surface Ni content at the similar Ni loading can reach higher methanol selectivity and productivity. This work thus provides theoretical guidance for significantly improving the CO_(2) reactivity of In_(2)O_(3)-based catalysts while maintaining high methanol selectivity.
