The catalytic performance of solid catalysts depends on the properties of the catalytically active sites and their accessibility to reactants, which are significantly affected by the microstructure（morphology, shape,...The catalytic performance of solid catalysts depends on the properties of the catalytically active sites and their accessibility to reactants, which are significantly affected by the microstructure（morphology, shape, size, texture, and surface structure） and surface chemistry（elemental components and chemical states）. The development of facile and efficient methods for tailoring the microstructure and surface chemistry is a hot topic in catalysis. This contribution reviews the state of the art in modulating the microstructure and surface chemistry of carbocatalysts by both bottom‐up and top‐down strategies and their use in the oxidative dehydrogenation（ODH） and direct dehydrogenation（DDH） of hydrocarbons including light alkanes and ethylbenzene to their corresponding olefins, important building blocks and chemicals like oxygenates. A concept of microstructure and surface chemistry tuning of the carbocatalyst for optimized catalytic performance and also for the fundamental understanding of the structure‐performance relationship is discussed. We also highlight the importance and challenges in modulating the microstructure and surface chemistry of carbocatalysts in ODH and DDH reactions of hydrocarbons for the highly‐efficient, energy‐saving,and clean production of their corresponding olefins.展开更多
Low cost,highly selective and efficient electrocatalysts for CO_(2)reduction reaction(CO_(2)RR)is crucial for lowering the global carbon footprint and mitigating energy shortages.Here,we first report a highly selectiv...Low cost,highly selective and efficient electrocatalysts for CO_(2)reduction reaction(CO_(2)RR)is crucial for lowering the global carbon footprint and mitigating energy shortages.Here,we first report a highly selective and efficient electrocatalyst for CO_(2)RR to CO using a surface-regulated Ni nanoparticles supported on N-doped CMK-3(N,O-Ni/CMK3).Compared with most Ni metal catalysts previously reported with severe competitive hydrogen evolution during the CO_(2)RR,the N,O-Ni/CMK3 catalyst presents a superior CO faradaic efficiency of about 97%,a high CO partial current density(13.01 mA cm^(-1))and turnover frequency(4.25 s^(–1)).The comprehensive characterization provides evidence that the N,O co-regulated Ni acts as the active center.Taking advantage of the N,O co-regulated chemical environment,N,O-Ni/CMK3 also displays a decent stability at negative potentials.Our work paves a novel approach for developing transition metal catalysts for CO_(2)RR with enhanced activity and selectivity via regulating surface chemical environment.展开更多
Despite being a promising photoanode material for water splitting,WO_(3) has low conductivity,high onset potential,and sluggish water oxidation kinetics.In this study,we designed Ti-doped WO_(3) nanoplate arrays on fl...Despite being a promising photoanode material for water splitting,WO_(3) has low conductivity,high onset potential,and sluggish water oxidation kinetics.In this study,we designed Ti-doped WO_(3) nanoplate arrays on fluoride-doped tin oxide by a seed-free hydrothermal method,and the effects of doping on the photoelectrochemical performance were investigated.The optimal Ti-doped WO_(3) electrode achieved a photocurrent density of 0.53 mA/cm^(2) at 0.6 V(vs Ag/AgCl),110%higher than that of pure WO_(3) nanoplate arrays.Moreover,a significant cathodic shift in the onset potential was observed after doping.X-ray photoelectron spectroscopy valence band and ultraviolet–visible spectra revealed that the band positions of Ti-doped WO_(3) photoanodes moved upward,yielding a lower onset potential.Furthermore,electrochemical impedance spectroscopy measurements revealed that the conductivities of the WO_(3) photoanodes improved after doping,because of the rapid separation of photo-generated charge carriers.Thus,we report a new design route toward efficient and low-cost photoanodes for photoelectrochemical applications.展开更多
基金supported by the National Natural Science Foundation of China(No.21972124,No.21603041)the Priority Academic Program Development of Jiangsu Higher Education Institution。
基金supported by the National Natural Science Foundation of China(21276041)the Program for New Century Excellent Talents in University of Ministry of Education of China(NCET-12-0079)+1 种基金the Natural Science Foundation of Liaoning Province(2015020200)the Fundamental Research Funds for the Central Universities(DUT15LK41)~~
文摘The catalytic performance of solid catalysts depends on the properties of the catalytically active sites and their accessibility to reactants, which are significantly affected by the microstructure（morphology, shape, size, texture, and surface structure） and surface chemistry（elemental components and chemical states）. The development of facile and efficient methods for tailoring the microstructure and surface chemistry is a hot topic in catalysis. This contribution reviews the state of the art in modulating the microstructure and surface chemistry of carbocatalysts by both bottom‐up and top‐down strategies and their use in the oxidative dehydrogenation（ODH） and direct dehydrogenation（DDH） of hydrocarbons including light alkanes and ethylbenzene to their corresponding olefins, important building blocks and chemicals like oxygenates. A concept of microstructure and surface chemistry tuning of the carbocatalyst for optimized catalytic performance and also for the fundamental understanding of the structure‐performance relationship is discussed. We also highlight the importance and challenges in modulating the microstructure and surface chemistry of carbocatalysts in ODH and DDH reactions of hydrocarbons for the highly‐efficient, energy‐saving,and clean production of their corresponding olefins.
文摘Low cost,highly selective and efficient electrocatalysts for CO_(2)reduction reaction(CO_(2)RR)is crucial for lowering the global carbon footprint and mitigating energy shortages.Here,we first report a highly selective and efficient electrocatalyst for CO_(2)RR to CO using a surface-regulated Ni nanoparticles supported on N-doped CMK-3(N,O-Ni/CMK3).Compared with most Ni metal catalysts previously reported with severe competitive hydrogen evolution during the CO_(2)RR,the N,O-Ni/CMK3 catalyst presents a superior CO faradaic efficiency of about 97%,a high CO partial current density(13.01 mA cm^(-1))and turnover frequency(4.25 s^(–1)).The comprehensive characterization provides evidence that the N,O co-regulated Ni acts as the active center.Taking advantage of the N,O co-regulated chemical environment,N,O-Ni/CMK3 also displays a decent stability at negative potentials.Our work paves a novel approach for developing transition metal catalysts for CO_(2)RR with enhanced activity and selectivity via regulating surface chemical environment.
基金Project(Qian Jiao He KY Zi [2021]257) supported provided by the Natural Science Research Project of Education Department of Guizhou Province,ChinaProject(GZSQCC2019003) supported by the High-level Innovative Talent Cultivation Project of Guizhou Province,ChinaProjects(GZLGXM-01,GZLGXM-08) supported by the Academic New Seedling Cultivation and Innovation Exploration Project of Guizhou Institute of Technology,China。
文摘Despite being a promising photoanode material for water splitting,WO_(3) has low conductivity,high onset potential,and sluggish water oxidation kinetics.In this study,we designed Ti-doped WO_(3) nanoplate arrays on fluoride-doped tin oxide by a seed-free hydrothermal method,and the effects of doping on the photoelectrochemical performance were investigated.The optimal Ti-doped WO_(3) electrode achieved a photocurrent density of 0.53 mA/cm^(2) at 0.6 V(vs Ag/AgCl),110%higher than that of pure WO_(3) nanoplate arrays.Moreover,a significant cathodic shift in the onset potential was observed after doping.X-ray photoelectron spectroscopy valence band and ultraviolet–visible spectra revealed that the band positions of Ti-doped WO_(3) photoanodes moved upward,yielding a lower onset potential.Furthermore,electrochemical impedance spectroscopy measurements revealed that the conductivities of the WO_(3) photoanodes improved after doping,because of the rapid separation of photo-generated charge carriers.Thus,we report a new design route toward efficient and low-cost photoanodes for photoelectrochemical applications.
