The chemical transformation of CO_(2)not only mitigates CO_(2)released into the atmosphere but also produces fuels and chemicals with important additional value.The activation of stable CO_(2)molecules is the key diff...The chemical transformation of CO_(2)not only mitigates CO_(2)released into the atmosphere but also produces fuels and chemicals with important additional value.The activation of stable CO_(2)molecules is the key difficulty for the efficient conversion of CO_(2).Herein,we designed a ternary catalyst containing Cu,ZnO,and CeO_(x)and dispersed them in SBA-15 using incipient wetness impregnation.展开更多
Electrocatalytic urea synthesis,as an emerging carbon-neutral technology,aims to directly synthesize urea from CO_(2) and NO_(3)−under mild conditions,which is of great significance for achieving sustainable energy de...Electrocatalytic urea synthesis,as an emerging carbon-neutral technology,aims to directly synthesize urea from CO_(2) and NO_(3)−under mild conditions,which is of great significance for achieving sustainable energy development and environmental governance.However,its large-scale application is restricted by competitive side reactions,low C-N coupling efficiency and an unclear reaction mechanism.Various metal catalysts have been developed and extensively studied to address these challenges.Cu-based catalysts have demonstrated great potential in this field due to their unique electronic structure,adjustable valence states,and excellent coupling ability for key reaction intermediates.This review systematically summarizes the research progress of Cu-based catalysts in electrocatalytic urea synthesis in recent years,and elaborates on the basic reaction mechanism of urea electrosynthesis.Furthermore,the modification strategies of different Cu-based catalysts are discussed in detail.Through in situ characterization and theoretical calculation,the influence rules of the intermediates produced during the reaction on the C-N coupling efficiency and selectivity are deeply analyzed.Finally,in view of the current challenges in this field,such as the need to improve Faraday efficiency and yield,this review offers guidance for the design of the next generation of high-performance urea electrosynthesis catalysts.展开更多
In this study,the preparation of economical Cu-based catalysts for Pd-free coupling and oxidation reactions was demonstrated.For the preparation of the Cu-based catalyst,first,a Cu-BTC MOF was prepared under ambient c...In this study,the preparation of economical Cu-based catalysts for Pd-free coupling and oxidation reactions was demonstrated.For the preparation of the Cu-based catalyst,first,a Cu-BTC MOF was prepared under ambient conditions.The Cu-BTC MOF was then carbonized in N_(2) to obtain Cu-Cu_(2)O-supported carbon materials.Moreover,the Cu-Cu_(2)O-supported carbon material was subjected to heating in O_(2) to obtain the CuO-Cu_(2)O-supported carbon material.Formation of Cu-BTC-MOF,Cu-Cu_(2)O,and CuO-Cu_(2)O was confirmed via powder X-ray diffraction(XRD)and X-ray photoelectron spectroscopy(XPS).The amount and types of carbon present in the catalyst were confirmed using thermogravimetric analysis and Raman spectroscopy,respectively.The textural properties of the materials were determined using N_(2)-sorption measurement.The morphology,porosity,and elemental composition were confirmed via the scanning and transmission electron microscopy images.The Cu-Cu_(2)O-supported carbon material successfully catalyzed the Sonogashira cross-coupling(C-C cross-coupling reaction),Ullmann amination(C-N coupling reaction),and A^(3) coupling(decarboxylative C-C and C-N coupling)reactions;moreover,the CuO-Cu_(2)O-supported carbon material successfully oxidized diphenylmethane in O_(2) at 1 atm.The catalysts were found to be stable and recyclable.Heterogeneity of the reaction was confirmed via the CS_(2) poisoning and hot-filtration tests.The presence of the optimum amount and the suitable oxidation state of Cu in the stable nanoporous carbon matrix having graphitic conducting nature were responsible for the excellent activity and recyclability.The results demonstrate that the applications of these Cu-based catalysts can be extended to several catalytic reactions that are known to be catalyzed using Pd and other costly metals.展开更多
基金supported by the NSFC(21878162,21603107,U1403293)the NSFT(16YFZCGX00020)+2 种基金the MOE(IRT-13R30 and 113016A)the Research Fund for 111 Project(B12015)the Fundamental Research Funds for the Central Universities,and dedicated to the 100th anniversary of Nankai University.
文摘The chemical transformation of CO_(2)not only mitigates CO_(2)released into the atmosphere but also produces fuels and chemicals with important additional value.The activation of stable CO_(2)molecules is the key difficulty for the efficient conversion of CO_(2).Herein,we designed a ternary catalyst containing Cu,ZnO,and CeO_(x)and dispersed them in SBA-15 using incipient wetness impregnation.
基金supported by the National Natural Science Foundation of China(52272222)Taishan Scholar Young Talent Program(tsqn201909114 and tsqn201909123)University Youth Innovation Team of Shandong Province(202201010318).
文摘Electrocatalytic urea synthesis,as an emerging carbon-neutral technology,aims to directly synthesize urea from CO_(2) and NO_(3)−under mild conditions,which is of great significance for achieving sustainable energy development and environmental governance.However,its large-scale application is restricted by competitive side reactions,low C-N coupling efficiency and an unclear reaction mechanism.Various metal catalysts have been developed and extensively studied to address these challenges.Cu-based catalysts have demonstrated great potential in this field due to their unique electronic structure,adjustable valence states,and excellent coupling ability for key reaction intermediates.This review systematically summarizes the research progress of Cu-based catalysts in electrocatalytic urea synthesis in recent years,and elaborates on the basic reaction mechanism of urea electrosynthesis.Furthermore,the modification strategies of different Cu-based catalysts are discussed in detail.Through in situ characterization and theoretical calculation,the influence rules of the intermediates produced during the reaction on the C-N coupling efficiency and selectivity are deeply analyzed.Finally,in view of the current challenges in this field,such as the need to improve Faraday efficiency and yield,this review offers guidance for the design of the next generation of high-performance urea electrosynthesis catalysts.
文摘In this study,the preparation of economical Cu-based catalysts for Pd-free coupling and oxidation reactions was demonstrated.For the preparation of the Cu-based catalyst,first,a Cu-BTC MOF was prepared under ambient conditions.The Cu-BTC MOF was then carbonized in N_(2) to obtain Cu-Cu_(2)O-supported carbon materials.Moreover,the Cu-Cu_(2)O-supported carbon material was subjected to heating in O_(2) to obtain the CuO-Cu_(2)O-supported carbon material.Formation of Cu-BTC-MOF,Cu-Cu_(2)O,and CuO-Cu_(2)O was confirmed via powder X-ray diffraction(XRD)and X-ray photoelectron spectroscopy(XPS).The amount and types of carbon present in the catalyst were confirmed using thermogravimetric analysis and Raman spectroscopy,respectively.The textural properties of the materials were determined using N_(2)-sorption measurement.The morphology,porosity,and elemental composition were confirmed via the scanning and transmission electron microscopy images.The Cu-Cu_(2)O-supported carbon material successfully catalyzed the Sonogashira cross-coupling(C-C cross-coupling reaction),Ullmann amination(C-N coupling reaction),and A^(3) coupling(decarboxylative C-C and C-N coupling)reactions;moreover,the CuO-Cu_(2)O-supported carbon material successfully oxidized diphenylmethane in O_(2) at 1 atm.The catalysts were found to be stable and recyclable.Heterogeneity of the reaction was confirmed via the CS_(2) poisoning and hot-filtration tests.The presence of the optimum amount and the suitable oxidation state of Cu in the stable nanoporous carbon matrix having graphitic conducting nature were responsible for the excellent activity and recyclability.The results demonstrate that the applications of these Cu-based catalysts can be extended to several catalytic reactions that are known to be catalyzed using Pd and other costly metals.
