Ordered metal oxides superstructures have attracted much more attention in the fields of fuel generation and environmental purification owing to their unique physiochemical characteristics such as large surface area, ...Ordered metal oxides superstructures have attracted much more attention in the fields of fuel generation and environmental purification owing to their unique physiochemical characteristics such as large surface area, fine pore structure, efficient electronic mobility, and good stability. Very recently, TiOmesocrystals（TMCs） having superstructures self-assembled by TiOnanoparticle building blocks, are of considerable interest in current research and application ranging from UV to visible light attributed to their efficient charge separation and superior photocatalytic activity. In this review, we describe the common procedures to prepare unique TMCs and overview of recent developments of TMCs during last 3 years, especially the structure-related or electronic-effected mechanism in photocatalytic reaction. Further, we introduce the characterization and fundamental properties of modified TMCs by the means of single-particle fluorescence microscopy for unraveling the charge transport and photocatalytic properties of individual TMCs and time-resolved diffuse reflectance spectroscopy（TDR） for monitoring the charge transfer dynamics. Finally, various aspects on TMCs are discussed for the future developments of energy and environmental fields.展开更多
CO_(2)electroreduction has been regarded as an appealing strategy for renewable energy storage.Recently,bismuth(Bi)electrocatalysts have attracted much attention due to their excellent formate selectivity.However,many...CO_(2)electroreduction has been regarded as an appealing strategy for renewable energy storage.Recently,bismuth(Bi)electrocatalysts have attracted much attention due to their excellent formate selectivity.However,many reported Bi electrocatalysts suffer from low current densities,which are insufficient for industrial applications.To reach the goal of high current CO_(2)reduction to formate,we fabricate Bi nanosheets(NS)with high activity through edge/terrace control and defect engineering strategy.Bi NS with preferential exposure sites are obtained by topotactic transformation,and the processes are clearly monitored by in-situ Raman and ex-situ X-ray diffraction(XRD).Bi NS-1 with a high fraction of edge sites and defect sites exhibits excellent performance,and the current density is up to ca.870 mA·cm^(−2)in the flow cell,far above the industrially applicable level(100 mA·cm^(−2)),with a formate Faradaic efficiency greater than 90%.In-situ Fourier transform infrared(FT-IR)spectra detect*OCHO,and theoretical calculations reveal that the formation energy of*OCHO on edges is lower than that on terraces,while the defects on edges further reduce the free energy changes(ΔG).The differential charge density spatial distributions reveal that the presence of defects on edges causes charge enrichment around the C–H bond,benefiting the stabilization of the*OCHO intermediate,thus remarkably lowering theΔG.展开更多
Mesocrystals, which are assemblies of crystallographically oriented nanocrystals, have received increasing attention due to their unique properties such as high crystallinity, high porosity, oriented subunit alignment...Mesocrystals, which are assemblies of crystallographically oriented nanocrystals, have received increasing attention due to their unique properties such as high crystallinity, high porosity, oriented subunit alignment, and similarity to highly sophisticated biominerals. However, the controlled synthesis of TiO 2 mesocrystals has not been realized until recently, probably because of the difficulty in accurately controlling the reaction processes that produce TiO 2 crystals. In this review, recent advances in the synthesis and applications of TiO 2 mesocrystals are summarized with particular attention paid to the mechanisms of their formation. Three typical pathways for the preparation of TiO 2 mesocrystals are discussed, namely topotactic transformation, direct synthesis in solution, and growth on supports. The potential applications of TiO 2 mesocrystals in lithium ion batteries, photocatalysis, enzyme immobilization, and antireflection materials are also described.展开更多
基金supported by a grant-in-aid for Scientific Research (Project 25220806 and others) from the Ministry of Education,Culture,Sports,Science and Technology (MEXT) of the Japanese Government
文摘Ordered metal oxides superstructures have attracted much more attention in the fields of fuel generation and environmental purification owing to their unique physiochemical characteristics such as large surface area, fine pore structure, efficient electronic mobility, and good stability. Very recently, TiOmesocrystals（TMCs） having superstructures self-assembled by TiOnanoparticle building blocks, are of considerable interest in current research and application ranging from UV to visible light attributed to their efficient charge separation and superior photocatalytic activity. In this review, we describe the common procedures to prepare unique TMCs and overview of recent developments of TMCs during last 3 years, especially the structure-related or electronic-effected mechanism in photocatalytic reaction. Further, we introduce the characterization and fundamental properties of modified TMCs by the means of single-particle fluorescence microscopy for unraveling the charge transport and photocatalytic properties of individual TMCs and time-resolved diffuse reflectance spectroscopy（TDR） for monitoring the charge transfer dynamics. Finally, various aspects on TMCs are discussed for the future developments of energy and environmental fields.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.22105133 and 22101191)China Postdoctoral Science Foundation(Nos.BX20190222,2019M663490,and 2021M692261)+1 种基金the Fundamental Research Funds for the Central Universities(Nos.20826041E4211,20826041E4258,20826041E4212,2021SCU12150 and 2021SCU12151)the China Scholarship Council,and Sichuan Science and Technology Program(No.2021YJ0405).
文摘CO_(2)electroreduction has been regarded as an appealing strategy for renewable energy storage.Recently,bismuth(Bi)electrocatalysts have attracted much attention due to their excellent formate selectivity.However,many reported Bi electrocatalysts suffer from low current densities,which are insufficient for industrial applications.To reach the goal of high current CO_(2)reduction to formate,we fabricate Bi nanosheets(NS)with high activity through edge/terrace control and defect engineering strategy.Bi NS with preferential exposure sites are obtained by topotactic transformation,and the processes are clearly monitored by in-situ Raman and ex-situ X-ray diffraction(XRD).Bi NS-1 with a high fraction of edge sites and defect sites exhibits excellent performance,and the current density is up to ca.870 mA·cm^(−2)in the flow cell,far above the industrially applicable level(100 mA·cm^(−2)),with a formate Faradaic efficiency greater than 90%.In-situ Fourier transform infrared(FT-IR)spectra detect*OCHO,and theoretical calculations reveal that the formation energy of*OCHO on edges is lower than that on terraces,while the defects on edges further reduce the free energy changes(ΔG).The differential charge density spatial distributions reveal that the presence of defects on edges causes charge enrichment around the C–H bond,benefiting the stabilization of the*OCHO intermediate,thus remarkably lowering theΔG.
基金supported by the National Natural Science Foundation of China (21073005, 21173010, and 51121091)National Basic Research Program of China (973 Program, 2007CB936201)
文摘Mesocrystals, which are assemblies of crystallographically oriented nanocrystals, have received increasing attention due to their unique properties such as high crystallinity, high porosity, oriented subunit alignment, and similarity to highly sophisticated biominerals. However, the controlled synthesis of TiO 2 mesocrystals has not been realized until recently, probably because of the difficulty in accurately controlling the reaction processes that produce TiO 2 crystals. In this review, recent advances in the synthesis and applications of TiO 2 mesocrystals are summarized with particular attention paid to the mechanisms of their formation. Three typical pathways for the preparation of TiO 2 mesocrystals are discussed, namely topotactic transformation, direct synthesis in solution, and growth on supports. The potential applications of TiO 2 mesocrystals in lithium ion batteries, photocatalysis, enzyme immobilization, and antireflection materials are also described.
