This study developed a facile approach for in situ synthesis of a Ti3＋ self-doped mesoporous TiO 2photocatalyst by an evaporation-induced self-assembly method using TiC l3,water,and F127 as the titanium precursor,sol...This study developed a facile approach for in situ synthesis of a Ti3＋ self-doped mesoporous TiO 2photocatalyst by an evaporation-induced self-assembly method using TiC l3,water,and F127 as the titanium precursor,solvent,and soft template agent,respectively. The as-prepared samples were investigated by X-ray diffraction,N2 adsorption-desorption measurements,ultraviolet-visible diffuse reflectance spectroscopy,electron paramagnetic resonance,and transmission electron microscopy. The influence of different reaction parameters such as the dosage of F127 and calcination temperature on the photocatalytic performance of the resulting products was evaluated. The optimized product exhibited high photocatalytic activity and stability in the oxidation of nitric oxide in air and photocatalytic degradation of methylene blue. The excellent photocatalytic performance of the Ti3＋ self-doped mesoporous TiO 2 photocatalyst is attributed to the cooperation between the mesoporous structure and self-doped Ti3＋ enhancing light absorption and effectively suppressing the recombination of photogenerated electrons and holes.展开更多
Simultaneously controlling the size of Au nanoparticles and immobilizing their location to specific active sites while hindering migration and sintering at elevated temperatures is a current challenge within materials...Simultaneously controlling the size of Au nanoparticles and immobilizing their location to specific active sites while hindering migration and sintering at elevated temperatures is a current challenge within materials chemistry.Typical methods require the use of protecting agents to control the properties of Au nanoparticles and therefore it is difficult to decouple the influence of the protecting agent and the support material.By functionalizing the internal surface area of mesoporous carbon supports with thiol groups and implementing a simple acid extraction step,we are able to design the resulting materials with precise control over the Au nanoparticle size without the need for the presence of any protecting group,whilst simultaneously confining the nanoparticles to within the internal porous network.Monodispersed Au nanoparticles in the absence of protecting agents were encapsulated into ordered mesoporous carbon at various loading levels via a coordination-assisted self-assembly approach.The X-ray diffractograms and transmission electron microscopy micrographs show that the particles have controlled and well-defined diameters between 3 and 18 nm at concentrations between 1.1 and 9.0 wt%.The Au nanoparticles are intercalated into the pore matrix to different degrees depending on the synthesis conditions and are stable after high temperature treatment at 600 °C.N2 adsorption-desorption isotherms show that the Au functionalized mesoporous carbon catalysts possess high surface areas（1269–1743 m^2/g）,large pore volumes（0.78–1.38 cm^3/g）and interpenetrated,uniform bimodal mesopores with the primary larger mesopore lying in the range of 3.4–5.7 nm and the smaller secondary mesopore having a diameter close to 2 nm.X-ray absorption near extended spectroscopy analysis reveals changes to the electronic properties of the Au nanoparticles as a function of reduced particle size.The predominant factors that significantly determine the end Au nanoparticle size is both the thiol group concentration and subjecting the as-made materials to an additional concentrated sulfuric acid extraction step.展开更多
Au Pd nanoalloys with tunable Pd concentrations have been synthesized and used as model catalysts. They have been directly imaged by high-angle annular dark-field scanning transmission electron microscopy and investig...Au Pd nanoalloys with tunable Pd concentrations have been synthesized and used as model catalysts. They have been directly imaged by high-angle annular dark-field scanning transmission electron microscopy and investigated by thorough analyses of their extended X-ray absorption fine structure, X-ray absorption near-edge structure, X-ray diffraction and X-ray photoelectron spectroscopy measurements. The bimetallic nanoparticles are embedded in a carbonaceous matrix and have almost an identical structure at the atomic level and the same electronic properties as Au Pd bulk alloys with the same compositions. The d-electron increase at surface Pd sites is determined by the Pd concentration of the alloy. Similarly, their activation entropy and catalytic activity for the hydrogenation of quinoline is related to the Pd concentration, with Au50 Pd50 the most active of the alloys investigated. An almost 11 times higher activity was achieved compared to a pure Pd catalyst. The experimentally measurable surface d charge at the Pd sites in the Au Pd was found to linearly correlate with the activation entropy and catalytic activity for the hydrogenation of quinoline. The alloy structure is stable, showing negligible metal segregation, dissolution-redeposition and aggregation during the hydrogenation process which involves strong adsorption.展开更多
基金supported by the National Natural Science Foundation of China(2147707921207090)+2 种基金the Shanghai Rising Star Program(15QA1403300)the Program for Changjiang Scholars and Innovative Research Team(IRT1269)the Specialized Research Fund for the Doctoral Program of Higher Education(20123127120009)~~
文摘This study developed a facile approach for in situ synthesis of a Ti3＋ self-doped mesoporous TiO 2photocatalyst by an evaporation-induced self-assembly method using TiC l3,water,and F127 as the titanium precursor,solvent,and soft template agent,respectively. The as-prepared samples were investigated by X-ray diffraction,N2 adsorption-desorption measurements,ultraviolet-visible diffuse reflectance spectroscopy,electron paramagnetic resonance,and transmission electron microscopy. The influence of different reaction parameters such as the dosage of F127 and calcination temperature on the photocatalytic performance of the resulting products was evaluated. The optimized product exhibited high photocatalytic activity and stability in the oxidation of nitric oxide in air and photocatalytic degradation of methylene blue. The excellent photocatalytic performance of the Ti3＋ self-doped mesoporous TiO 2 photocatalyst is attributed to the cooperation between the mesoporous structure and self-doped Ti3＋ enhancing light absorption and effectively suppressing the recombination of photogenerated electrons and holes.
基金supported by the State Key Basic Research Program of China(2013CB934102)the National Natural Science Foundation of China(21322308,21173149)+2 种基金the Program for Changjiang Scholars and Innovative Research Team in University(PCSIRT-IRT1269)the Research Fund for the Doctoral Program of Higher Education(20123127110004)Shanghai Science&Technology and Education Committee(11JC1409200,DZL123,S30406)~~
文摘Simultaneously controlling the size of Au nanoparticles and immobilizing their location to specific active sites while hindering migration and sintering at elevated temperatures is a current challenge within materials chemistry.Typical methods require the use of protecting agents to control the properties of Au nanoparticles and therefore it is difficult to decouple the influence of the protecting agent and the support material.By functionalizing the internal surface area of mesoporous carbon supports with thiol groups and implementing a simple acid extraction step,we are able to design the resulting materials with precise control over the Au nanoparticle size without the need for the presence of any protecting group,whilst simultaneously confining the nanoparticles to within the internal porous network.Monodispersed Au nanoparticles in the absence of protecting agents were encapsulated into ordered mesoporous carbon at various loading levels via a coordination-assisted self-assembly approach.The X-ray diffractograms and transmission electron microscopy micrographs show that the particles have controlled and well-defined diameters between 3 and 18 nm at concentrations between 1.1 and 9.0 wt%.The Au nanoparticles are intercalated into the pore matrix to different degrees depending on the synthesis conditions and are stable after high temperature treatment at 600 °C.N2 adsorption-desorption isotherms show that the Au functionalized mesoporous carbon catalysts possess high surface areas（1269–1743 m^2/g）,large pore volumes（0.78–1.38 cm^3/g）and interpenetrated,uniform bimodal mesopores with the primary larger mesopore lying in the range of 3.4–5.7 nm and the smaller secondary mesopore having a diameter close to 2 nm.X-ray absorption near extended spectroscopy analysis reveals changes to the electronic properties of the Au nanoparticles as a function of reduced particle size.The predominant factors that significantly determine the end Au nanoparticle size is both the thiol group concentration and subjecting the as-made materials to an additional concentrated sulfuric acid extraction step.
文摘Au Pd nanoalloys with tunable Pd concentrations have been synthesized and used as model catalysts. They have been directly imaged by high-angle annular dark-field scanning transmission electron microscopy and investigated by thorough analyses of their extended X-ray absorption fine structure, X-ray absorption near-edge structure, X-ray diffraction and X-ray photoelectron spectroscopy measurements. The bimetallic nanoparticles are embedded in a carbonaceous matrix and have almost an identical structure at the atomic level and the same electronic properties as Au Pd bulk alloys with the same compositions. The d-electron increase at surface Pd sites is determined by the Pd concentration of the alloy. Similarly, their activation entropy and catalytic activity for the hydrogenation of quinoline is related to the Pd concentration, with Au50 Pd50 the most active of the alloys investigated. An almost 11 times higher activity was achieved compared to a pure Pd catalyst. The experimentally measurable surface d charge at the Pd sites in the Au Pd was found to linearly correlate with the activation entropy and catalytic activity for the hydrogenation of quinoline. The alloy structure is stable, showing negligible metal segregation, dissolution-redeposition and aggregation during the hydrogenation process which involves strong adsorption.
