The sustainable development of the chemical industry requires novel and efficient catalysts and catalytic processes,especially eco-friendly and intrinsically safe processes.The idea is to improve the selectivity,activ...The sustainable development of the chemical industry requires novel and efficient catalysts and catalytic processes,especially eco-friendly and intrinsically safe processes.The idea is to improve the selectivity,activity,and stability of the catalyst in an appropriate reactor.Therefore,it is of great academic and industrial significance to conduct in-situ characterization of a working catalyst while testing its catalytic performance.This is beneficial for a comprehensive study on the dynamic evolution of the catalyst structure under real conditions,deepening the understanding of the structure-performance relationship of catalysts,and providing a scientific basis for the development of future generation catalytic technology.Thus far,it is still a great challenge to realize full life cycle characterization of heterogeneous catalysts from catalyst formation and function to deactivation under real world conditions.In this mini review,we summarize the characterization strategies for heterogeneous catalysts,using zeolite,metal,and metal oxide catalysts as typical examples.The research strategies for the approximation of industrial conditions,multi-scale in-situ characterization devices,and computational modeling of realistic conditions should provide insight for the research and development of industrial catalysis.展开更多
The cleavage of the alkoxy(Ar-O-R) ether bond present in anisole is an interesting hydrodeoxygenation(HDO) reaction, since this asymmetric group contains two different C–O bonds, Caryl–O or Calkyl–O, which could po...The cleavage of the alkoxy(Ar-O-R) ether bond present in anisole is an interesting hydrodeoxygenation(HDO) reaction, since this asymmetric group contains two different C–O bonds, Caryl–O or Calkyl–O, which could potentially cleave. Recent work on the HDO of anisole over Pt, Ru, and Fe catalysts has shown that a common phenoxy surface intermediate is formed on all three metals. The subsequent reaction path of this intermediate varies from metal to metal, depending on the metal oxophilicity. Over the less oxophilic Pt, phenol is the only primary product. By contrast, on the more oxophilic Fe catalyst, the sole primary product is benzene instead of phenol. On Ru, with intermediate oxophilicity, both benzene and phenol are primary products. In this contribution, we have investigated Rh catalysts of varying surface nanostructures. A combination of experimental measurements and computational calculations was used to explore the effects of varying metal coordination number, an additional parameter that can be used to control the oxophilicity of a metal. The results confirm that metal oxophilicity is a good descriptor for HDO performance of metal catalysts and it can be controlled via selection of metal type and/or metal extent of coordination. Small Rh metal clusters with low coordination metal sites are more active for the deoxygenation pathway but also quickly deactivated while large clusters with high coordination sites are more active toward hydrogenation and more stable.展开更多
In this work, we fabricated the poly（N-vinyl-2-pyrrolidone） （PVP）-stabilized ruthenium（0） nanoclusters by reduction of RuC13 using different reducing agents, and studied their catalytic activity in hydrogen gene...In this work, we fabricated the poly（N-vinyl-2-pyrrolidone） （PVP）-stabilized ruthenium（0） nanoclusters by reduction of RuC13 using different reducing agents, and studied their catalytic activity in hydrogen generation from the decomposition of formic acid. It was demonstrated that N-vinyl-2-pyrrolidone （NVP）, which is a monomer of PVP, could promote the reaction by coordination with Ru nanoparticles. The Ru nanoparticles catalyst reduced by sodium borohydride （NaBH4） exhibited highest catalytic activity for the decomposition of formic acid into H2 and CO2. The turnover of numenber （TOF） value could reach 26113 h-1 at 80 ℃. We believe that the effective catalysts have potential of application in hydrogen storage by formic acid.展开更多
文摘The sustainable development of the chemical industry requires novel and efficient catalysts and catalytic processes,especially eco-friendly and intrinsically safe processes.The idea is to improve the selectivity,activity,and stability of the catalyst in an appropriate reactor.Therefore,it is of great academic and industrial significance to conduct in-situ characterization of a working catalyst while testing its catalytic performance.This is beneficial for a comprehensive study on the dynamic evolution of the catalyst structure under real conditions,deepening the understanding of the structure-performance relationship of catalysts,and providing a scientific basis for the development of future generation catalytic technology.Thus far,it is still a great challenge to realize full life cycle characterization of heterogeneous catalysts from catalyst formation and function to deactivation under real world conditions.In this mini review,we summarize the characterization strategies for heterogeneous catalysts,using zeolite,metal,and metal oxide catalysts as typical examples.The research strategies for the approximation of industrial conditions,multi-scale in-situ characterization devices,and computational modeling of realistic conditions should provide insight for the research and development of industrial catalysis.
基金supported by the U.S.Department of Energy,DOE/EPSCOR(Grant DESC0004600)
文摘The cleavage of the alkoxy(Ar-O-R) ether bond present in anisole is an interesting hydrodeoxygenation(HDO) reaction, since this asymmetric group contains two different C–O bonds, Caryl–O or Calkyl–O, which could potentially cleave. Recent work on the HDO of anisole over Pt, Ru, and Fe catalysts has shown that a common phenoxy surface intermediate is formed on all three metals. The subsequent reaction path of this intermediate varies from metal to metal, depending on the metal oxophilicity. Over the less oxophilic Pt, phenol is the only primary product. By contrast, on the more oxophilic Fe catalyst, the sole primary product is benzene instead of phenol. On Ru, with intermediate oxophilicity, both benzene and phenol are primary products. In this contribution, we have investigated Rh catalysts of varying surface nanostructures. A combination of experimental measurements and computational calculations was used to explore the effects of varying metal coordination number, an additional parameter that can be used to control the oxophilicity of a metal. The results confirm that metal oxophilicity is a good descriptor for HDO performance of metal catalysts and it can be controlled via selection of metal type and/or metal extent of coordination. Small Rh metal clusters with low coordination metal sites are more active for the deoxygenation pathway but also quickly deactivated while large clusters with high coordination sites are more active toward hydrogenation and more stable.
基金supported by the Recruitment Program of Global Youth Experts of China, Chinese Academy of Sciences (KJCX2.YW.H30)the National Natural Science Foundation of China (21533011, 21321063)
文摘In this work, we fabricated the poly（N-vinyl-2-pyrrolidone） （PVP）-stabilized ruthenium（0） nanoclusters by reduction of RuC13 using different reducing agents, and studied their catalytic activity in hydrogen generation from the decomposition of formic acid. It was demonstrated that N-vinyl-2-pyrrolidone （NVP）, which is a monomer of PVP, could promote the reaction by coordination with Ru nanoparticles. The Ru nanoparticles catalyst reduced by sodium borohydride （NaBH4） exhibited highest catalytic activity for the decomposition of formic acid into H2 and CO2. The turnover of numenber （TOF） value could reach 26113 h-1 at 80 ℃. We believe that the effective catalysts have potential of application in hydrogen storage by formic acid.
