A core shell structured C@MoxTi1-xO2-δnanocrystal with a functionalized interface(C@MTNC-FI)was fabricated via the hydrothermal method with subsequent annealing derived from tetrabutyl orthotitanate.The formation of ...A core shell structured C@MoxTi1-xO2-δnanocrystal with a functionalized interface(C@MTNC-FI)was fabricated via the hydrothermal method with subsequent annealing derived from tetrabutyl orthotitanate.The formation of anatase TiO2 was inhibited by the simultaneous presence of the hydrothermal etching/regrowth process,infiltration of Mo dopants and carbon coating,which endows the C@MTNC-FI with an ultrafine crystalline architecture that has a Mo-functionalized interface and carbon-coated shell.Pt Ru nanoparticles(NPs)were supported on C@MTNC-FI by employing a microwave-assisted polyol process(MAPP).The obtained Pt Ru/C@MTNC-FI catalyst has 2.68 times higher mass activity towards methanol electrooxidation than that of the un-functionalized catalyst(Pt Ru/C@TNC)and 1.65 times higher mass activity than that of Pt Ru/C catalyst with over 25%increase in durability.The improved catalytic performance is due to several aspects including ultrafine crystals of TiO2 with abundant grain boundaries,Mofunctionalized interface with enhanced electron interactions,and core shell architecture with excellent electrical transport properties.This work suggests the potential application of an interface-functionalized crystalline material as a sustainable and clean energy solution.展开更多
Catalytic hydrogenation of CO_(2) using renewable hydrogen not only reduces greenhouse gas emissions,but also provides industrial chemicals.Herein,a Co-Fe bimetallic catalyst was developed by a facile reactive ball-mi...Catalytic hydrogenation of CO_(2) using renewable hydrogen not only reduces greenhouse gas emissions,but also provides industrial chemicals.Herein,a Co-Fe bimetallic catalyst was developed by a facile reactive ball-milling method for highly active and selective hydrogenation of CO_(2) to value-added hydrocarbons.When reacted at 320℃,1.0 MPa and 9600 mL h^(-1) g_(cat)^(-1),the selectivity to light olefin(C_(2)^(=)-C_(4)^(=)) and C_(5)+ species achieves 57.3% and 22.3%,respectively,at a CO_(2) co nversion of 31.4%,which is superior to previous Fe-based catalysts.The CO_(2) activation can be promoted by the CoFe phase formed by reactive ball milling of the Fe-Co_(3)O_(4) mixture,and the in-situ Co_(2)C and Fe_(5)C_(2) formed during hydrogenation are beneficial for the C-C coupling reaction.The initial C-C coupling is related to the combination of CO species with the surface carbon of Fe/Co carbides,and the sustained C-C coupling is maintained by self-recovery of defective carbides.This new strategy contributes to the development of efficient catalysts for the hydrogenation of CO_(2) to value-added hydrocarbons.展开更多
Extremely small PtRu/C nanocatalysts were prepared via a carbonyl route. A thorough in situ reduction X-ray structural characterization of these catalysts was performed. After synthesis and storage under ambient condi...Extremely small PtRu/C nanocatalysts were prepared via a carbonyl route. A thorough in situ reduction X-ray structural characterization of these catalysts was performed. After synthesis and storage under ambient condi- tions, the diffraction patterns of PtRu/C catalysts were seriously modified, indicating the surface oxide formation. In the reduced state, the particle size is around 2 nm. The observed relative fluctuations of lattice constants are 3%, which is far too large to be explained by a compositional fluctuation. Their origin is attributed to strong but isotropic strains and is related to the alloy formation. The annealing experiments show all the catalysts present an exceptional thermal stability when annealed in inert ambient, especially that of the Pt1Ru1/C catalyst. Besides, it is interesting to note that there is no thermal expansion evidence from the patterns.展开更多
基金the National Natural Science Foundation of China (Grant Nos. 21273058, 21673064, 51802059 and 21503059)China Postdoctoral Science Foundation (Grant Nos. 2018M631938, 2018T110307 and 2017M621284)+1 种基金Heilongjiang Postdoctoral Fund (LBH-Z17074)Fundamental Research Funds for the Central Universities (Grant No. HIT. NSRIF. 2019040 and 2019041)
文摘A core shell structured C@MoxTi1-xO2-δnanocrystal with a functionalized interface(C@MTNC-FI)was fabricated via the hydrothermal method with subsequent annealing derived from tetrabutyl orthotitanate.The formation of anatase TiO2 was inhibited by the simultaneous presence of the hydrothermal etching/regrowth process,infiltration of Mo dopants and carbon coating,which endows the C@MTNC-FI with an ultrafine crystalline architecture that has a Mo-functionalized interface and carbon-coated shell.Pt Ru nanoparticles(NPs)were supported on C@MTNC-FI by employing a microwave-assisted polyol process(MAPP).The obtained Pt Ru/C@MTNC-FI catalyst has 2.68 times higher mass activity towards methanol electrooxidation than that of the un-functionalized catalyst(Pt Ru/C@TNC)and 1.65 times higher mass activity than that of Pt Ru/C catalyst with over 25%increase in durability.The improved catalytic performance is due to several aspects including ultrafine crystals of TiO2 with abundant grain boundaries,Mofunctionalized interface with enhanced electron interactions,and core shell architecture with excellent electrical transport properties.This work suggests the potential application of an interface-functionalized crystalline material as a sustainable and clean energy solution.
基金supported by the National Natural Science Foundation of China (22008098, 21978156, 42002040)the Program for Innovative Research Team (in Science and Technology) in University of Henan Province (21IRTSTHN004)+1 种基金the Program for Science & Technology Innovation Talents in Universities of Henan Province (22HASTIT008)the Foundation of State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering (2022-K34)。
文摘Catalytic hydrogenation of CO_(2) using renewable hydrogen not only reduces greenhouse gas emissions,but also provides industrial chemicals.Herein,a Co-Fe bimetallic catalyst was developed by a facile reactive ball-milling method for highly active and selective hydrogenation of CO_(2) to value-added hydrocarbons.When reacted at 320℃,1.0 MPa and 9600 mL h^(-1) g_(cat)^(-1),the selectivity to light olefin(C_(2)^(=)-C_(4)^(=)) and C_(5)+ species achieves 57.3% and 22.3%,respectively,at a CO_(2) co nversion of 31.4%,which is superior to previous Fe-based catalysts.The CO_(2) activation can be promoted by the CoFe phase formed by reactive ball milling of the Fe-Co_(3)O_(4) mixture,and the in-situ Co_(2)C and Fe_(5)C_(2) formed during hydrogenation are beneficial for the C-C coupling reaction.The initial C-C coupling is related to the combination of CO species with the surface carbon of Fe/Co carbides,and the sustained C-C coupling is maintained by self-recovery of defective carbides.This new strategy contributes to the development of efficient catalysts for the hydrogenation of CO_(2) to value-added hydrocarbons.
基金Supported by the National Natural Science Foundation of China(No.21073219)the Youth’s Innovation Fund of the Shanghai Institute of Microsystem and Information Technology,China(No.2010)
文摘Extremely small PtRu/C nanocatalysts were prepared via a carbonyl route. A thorough in situ reduction X-ray structural characterization of these catalysts was performed. After synthesis and storage under ambient condi- tions, the diffraction patterns of PtRu/C catalysts were seriously modified, indicating the surface oxide formation. In the reduced state, the particle size is around 2 nm. The observed relative fluctuations of lattice constants are 3%, which is far too large to be explained by a compositional fluctuation. Their origin is attributed to strong but isotropic strains and is related to the alloy formation. The annealing experiments show all the catalysts present an exceptional thermal stability when annealed in inert ambient, especially that of the Pt1Ru1/C catalyst. Besides, it is interesting to note that there is no thermal expansion evidence from the patterns.
