Supported Au catalysts have been reported to exhibit high ethylene selectivity in the hydrogenation of acetylene,but the conversion is relatively low.Adding a second metal to Au has proven to be a promising approach t...Supported Au catalysts have been reported to exhibit high ethylene selectivity in the hydrogenation of acetylene,but the conversion is relatively low.Adding a second metal to Au has proven to be a promising approach to enhance its catalytic performance in acetylene hydrogenation.In this work,SiO2‐supported Au‐Ni bimetallic catalysts were synthesized and investigated in the selective hydrogenation of acetylene.The Au‐Ni bimetallic catalysts exhibited much higher catalytic performance than that of the corresponding monometallic Au or Ni catalysts.By tuning the reduction temperature and/or Ni loading,we obtained an Au‐Ni/SiO2catalyst with optimal performance.The results of transmission electron microscopy imaging revealed that the Au‐Ni bimetallic particles were highly dispersed on the SiO2support.Meanwhile,analysis of the bimetallic catalyst by energy‐dispersive X‐ray spectroscopy,high‐resolution transmission electron microscopy,and in situ diffuse reflectance infrared Fourier transform spectroscopy demonstrated the formation of Au‐Ni alloy,which contributed to the synergistic effect between Au and Ni in the hydrogenation of acetylene.展开更多
The heterogeneity of active sites is the main obstacle for selectivity control in heterogeneous catalysis.Single atom catalysts（SACs） with homogeneous isolated active sites are highly desired in chemoselective trans...The heterogeneity of active sites is the main obstacle for selectivity control in heterogeneous catalysis.Single atom catalysts（SACs） with homogeneous isolated active sites are highly desired in chemoselective transformations. In this work, a Pd1/ZnO catalyst with single‐atom dispersion of Pd active sites was achieved by decreasing the Pd loading and reducing the sample at a relatively low temperature. The Pd1/ZnO SAC exhibited excellent catalytic performance in the chemoselective hydrogenation of acetylene with comparable chemoselectivity to that of PdZn intermetallic catalysts and a greatly enhanced utilization of Pd metal. Such unusual behaviors of the Pd1/ZnO SAC in acetylene semi‐hydrogenation were ascribed to the high‐valent single Pd active sites, which could promote electrostatic interactions with acetylene but restrain undesired ethylene hydrogenation via the spatial restrictions of σ‐chemical bonding toward ethylene.展开更多
Cu‐alloyed Pd single‐atom catalysts exhibit excellent catalytic performance for the semi‐hydrogenation of acetylene;however,the limit of the Cu/Pd atomic ratio for forming the alloyed Pd single‐atom catalyst is am...Cu‐alloyed Pd single‐atom catalysts exhibit excellent catalytic performance for the semi‐hydrogenation of acetylene;however,the limit of the Cu/Pd atomic ratio for forming the alloyed Pd single‐atom catalyst is ambiguous.Herein,silica‐supported Cu-Pd bimetallic catalysts with fixed Pd content and varied Cu loadings were synthesized using an incipient wetness co‐impregnation method.The X‐ray absorption spectroscopy results indicated that Pd formed an alloy with Cu after reduction at250°C and that the Pd atoms were completely isolated by Cu for Cu/Pd atomic ratios≥40/1.Notably,increasing the reduction temperature from250to400°C hardly affected the catalytic performances of the Cu-Pd/SiO2catalysts.This finding can be attributed to the similar chemical environments of Pd demonstrated by the X‐ray absorption spectroscopy results.展开更多
乙烯是石油化工重要的工业原料,对经济发展有着重要的影响,乙炔半加氢生产乙烯是重要化工反应。传统的钯催化剂具有较高的活性,由于过度加氢和绿油的生成导致选择性和催化剂的催化周期低。因此,制备出一种高活性及选择性的催化剂并借助...乙烯是石油化工重要的工业原料,对经济发展有着重要的影响,乙炔半加氢生产乙烯是重要化工反应。传统的钯催化剂具有较高的活性,由于过度加氢和绿油的生成导致选择性和催化剂的催化周期低。因此,制备出一种高活性及选择性的催化剂并借助同步辐射技术探究其反应机理变得至关重要。利用沉积-沉淀法制备了二氧化硅负载的钯铋双金属催化剂,在乙炔半加氢反应中与传统催化剂进行催化活性及选择性方面的对比研究。借助X射线吸收精细结构(X-ray Absorption Fine Structure,XAFS)和高角度环形暗场扫描透射电子显微镜(High-Angle Annular Dark-Field Scanning Transmission Electron Microscopy,HAADF-STEM)等多种表征手段,发现独特的PdBi催化剂可以有效抑制PdHx的形成,减弱氢气的裂解速度和乙烯在钯表面的吸附,抑制乙烯的过度加氢产生副产物乙烷。新型钯铋结构催化剂及机理探索为今后制备高效的乙炔加氢制乙烯催化剂提供了一种新的思路和手段。展开更多
基金supported by the National Natural Science Foundation of China (21303194,21476227,21522608,21573232,21690084)Youth Innovation Promotion Association of the Chinese Academy of Sciences (2014163)+2 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB17020100)the National Key Projects for Fundamental Research and Development of China (2016YFA0202801)the Department of Science and Technology of Liaoning Province (2015020086-101)~~
文摘Supported Au catalysts have been reported to exhibit high ethylene selectivity in the hydrogenation of acetylene,but the conversion is relatively low.Adding a second metal to Au has proven to be a promising approach to enhance its catalytic performance in acetylene hydrogenation.In this work,SiO2‐supported Au‐Ni bimetallic catalysts were synthesized and investigated in the selective hydrogenation of acetylene.The Au‐Ni bimetallic catalysts exhibited much higher catalytic performance than that of the corresponding monometallic Au or Ni catalysts.By tuning the reduction temperature and/or Ni loading,we obtained an Au‐Ni/SiO2catalyst with optimal performance.The results of transmission electron microscopy imaging revealed that the Au‐Ni bimetallic particles were highly dispersed on the SiO2support.Meanwhile,analysis of the bimetallic catalyst by energy‐dispersive X‐ray spectroscopy,high‐resolution transmission electron microscopy,and in situ diffuse reflectance infrared Fourier transform spectroscopy demonstrated the formation of Au‐Ni alloy,which contributed to the synergistic effect between Au and Ni in the hydrogenation of acetylene.
基金supported by the National Natural Science Foundation of China(21573232)~~
文摘The heterogeneity of active sites is the main obstacle for selectivity control in heterogeneous catalysis.Single atom catalysts（SACs） with homogeneous isolated active sites are highly desired in chemoselective transformations. In this work, a Pd1/ZnO catalyst with single‐atom dispersion of Pd active sites was achieved by decreasing the Pd loading and reducing the sample at a relatively low temperature. The Pd1/ZnO SAC exhibited excellent catalytic performance in the chemoselective hydrogenation of acetylene with comparable chemoselectivity to that of PdZn intermetallic catalysts and a greatly enhanced utilization of Pd metal. Such unusual behaviors of the Pd1/ZnO SAC in acetylene semi‐hydrogenation were ascribed to the high‐valent single Pd active sites, which could promote electrostatic interactions with acetylene but restrain undesired ethylene hydrogenation via the spatial restrictions of σ‐chemical bonding toward ethylene.
基金supported by the National Natural Science Foundation of China(21303194,21476227,21522608 and 21690084)Youth Innovation Promotion Association of the Chinese Academy of Sciences(2014163)+2 种基金the National Key Projects for Fundamental Research and Development of China(2016YFA0202801)the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB17020100)the department of science and technology of Liaoning province under contract of 2015020086-101~~
文摘Cu‐alloyed Pd single‐atom catalysts exhibit excellent catalytic performance for the semi‐hydrogenation of acetylene;however,the limit of the Cu/Pd atomic ratio for forming the alloyed Pd single‐atom catalyst is ambiguous.Herein,silica‐supported Cu-Pd bimetallic catalysts with fixed Pd content and varied Cu loadings were synthesized using an incipient wetness co‐impregnation method.The X‐ray absorption spectroscopy results indicated that Pd formed an alloy with Cu after reduction at250°C and that the Pd atoms were completely isolated by Cu for Cu/Pd atomic ratios≥40/1.Notably,increasing the reduction temperature from250to400°C hardly affected the catalytic performances of the Cu-Pd/SiO2catalysts.This finding can be attributed to the similar chemical environments of Pd demonstrated by the X‐ray absorption spectroscopy results.
文摘乙烯是石油化工重要的工业原料,对经济发展有着重要的影响,乙炔半加氢生产乙烯是重要化工反应。传统的钯催化剂具有较高的活性,由于过度加氢和绿油的生成导致选择性和催化剂的催化周期低。因此,制备出一种高活性及选择性的催化剂并借助同步辐射技术探究其反应机理变得至关重要。利用沉积-沉淀法制备了二氧化硅负载的钯铋双金属催化剂,在乙炔半加氢反应中与传统催化剂进行催化活性及选择性方面的对比研究。借助X射线吸收精细结构(X-ray Absorption Fine Structure,XAFS)和高角度环形暗场扫描透射电子显微镜(High-Angle Annular Dark-Field Scanning Transmission Electron Microscopy,HAADF-STEM)等多种表征手段,发现独特的PdBi催化剂可以有效抑制PdHx的形成,减弱氢气的裂解速度和乙烯在钯表面的吸附,抑制乙烯的过度加氢产生副产物乙烷。新型钯铋结构催化剂及机理探索为今后制备高效的乙炔加氢制乙烯催化剂提供了一种新的思路和手段。
