This paper attempts to understand the Pt-like catalytic activity of transition metal carbide Ta4C_(3) for IRR(I_(3)^(-)reduction reaction)based on the correlation of adsorption energy to d-band center(εd).Ta4C_(3) wa...This paper attempts to understand the Pt-like catalytic activity of transition metal carbide Ta4C_(3) for IRR(I_(3)^(-)reduction reaction)based on the correlation of adsorption energy to d-band center(εd).Ta4C_(3) was prepared by carbothermal reduction method with a template.Its photoelectrochemical properties were investigated as a CE(counter electrode)in DSSC(dye-sensitized solar cell).Its surface electronic structures,including DOS(density of state)andεd,and adsorption energy were computed by first-principle DFT(density functional theory).In TMC(transition metal carbide)Ta4C_(3),the interaction between Ta and C atoms makes the d-band of Ta broaden and results in the downward shift of itsεd.A moderate absorption energy corresponding to theεd is achieved,which is the nature of the Pt-like catalytic activity of Ta4C_(3).Appropriate change of adsorption energy by adjustingεd is a promising strategy to improve catalytic activity.This work is of great significance to the fundamental and application researches.展开更多
High activity catalyst with simple low-cost synthesis is essential for fuel cell commercialization. In this study, a facile procedure for the synthesis of cube-like Pt nanoparticle （PtCube） composites with high surf...High activity catalyst with simple low-cost synthesis is essential for fuel cell commercialization. In this study, a facile procedure for the synthesis of cube-like Pt nanoparticle （PtCube） composites with high surface area carbon supports is developed by mixing precursor of Pt with carbon supports in organic batches, hence, one pot synthesis. The PtCube grow with Vulcan XC-72 or Ketjen black, respectively, and then treated for 5.5 h at 185℃ （i.e., Ptcube5.5/V and PtcubeS.5/K）. The resulting particle sizes and shapes are similar; however, Ptcube5.5/K has a larger electrochemical active surface area （EASA） and a remarkably better formic acid （FA） oxidation performance. Optimization of the PtCube/K composites leads to Ptcubelo/K that has been treated for 10 h at 185℃. With a larger EASA, Ptcubelo/K is also more active in FA oxidation than the other Ptcube/K composites. Impedance spectroscopy analysis of the temperature treated and asprepared （i.e., untreated） Ptcube/K composites indicates that PtCube10/K is less resistive, and has the highest limiting capacitance among the PtCube/K electrodes. Consistently, the voltammetric EASA is the largest for Ptcube 10/K. Furthermore, PtCube10/K is compared with two commercial Pt/C catalysts, Tanaka Kikinzoku Kogyo （TKK）, and Johnson Matthey （JM）Pt/C catalysts. The TKK Pt/C has a higher EASA than Ptcube10/K, as expected from their relative particles sizes （3-4 nm vs. 6-7 nm for PtcubelO/K）, however, Ptcube10/K has a significantly better FA oxidation activity.展开更多
A novel Ultrasonic Assisted Membrane Reduction （UAMR）-hydrothermal method was used to prepare flower-like Pt/CeO2 catalysts. The texture, physical/chemical properties, and reducibility of the flower-like Pt/CeO2 cat...A novel Ultrasonic Assisted Membrane Reduction （UAMR）-hydrothermal method was used to prepare flower-like Pt/CeO2 catalysts. The texture, physical/chemical properties, and reducibility of the flower-like Pt/CeO2 catalysts were characterized by X-Ray Diffraction （XRD）, Scanning Electron Microscope （SEM）, Transmission Electron Microscope （TEM）, N2 adsorption, and hydrogen temperature programmed reduction （HE-TPR） techniques. The catalytic performance of the catalysts for treating automobile emission was studied relative to samples prepared by the conventional wetness impregnation method. The Pt/CeO2 catalysts fabricated by this novel method showed high specific surface area and metal dispersion, excellent three-way catalytic activity, and good thermal stability. The strong interaction between the Pt nanoparticles and CeO2 improved the thermal stability. The Ce4＋ ions were incorporated into the surfactant chains and the Pt nanoparticles were stabilized through an exchange reaction of the surface hydroxyl groups. The SEM results demonstrated that the Pt/CeO2 catalysts had a typical three-dimensional （3D） hierarchical porous struc- ture, which was favorable for surface reaction and enhanced the exposure degree of the Pt nanoparticles. In brief, the flower-like Pt/CeO2 catalysts prepared by UAMR-hydrothermal method exhibited a higher Pt metal dispersion, smaller particle size, better three-way catalytic activity, and improved thermal stability versus conven- tional materials.展开更多
基金Financial support for this work was provided by Key Research and Development Projects of Shanxi Province(201703D121023).
文摘This paper attempts to understand the Pt-like catalytic activity of transition metal carbide Ta4C_(3) for IRR(I_(3)^(-)reduction reaction)based on the correlation of adsorption energy to d-band center(εd).Ta4C_(3) was prepared by carbothermal reduction method with a template.Its photoelectrochemical properties were investigated as a CE(counter electrode)in DSSC(dye-sensitized solar cell).Its surface electronic structures,including DOS(density of state)andεd,and adsorption energy were computed by first-principle DFT(density functional theory).In TMC(transition metal carbide)Ta4C_(3),the interaction between Ta and C atoms makes the d-band of Ta broaden and results in the downward shift of itsεd.A moderate absorption energy corresponding to theεd is achieved,which is the nature of the Pt-like catalytic activity of Ta4C_(3).Appropriate change of adsorption energy by adjustingεd is a promising strategy to improve catalytic activity.This work is of great significance to the fundamental and application researches.
基金National Key Research and Development Project(2017YFB0310600)Shanghai International Science and Technology Cooperation Fund(17520711700,18520744200)。
文摘High activity catalyst with simple low-cost synthesis is essential for fuel cell commercialization. In this study, a facile procedure for the synthesis of cube-like Pt nanoparticle （PtCube） composites with high surface area carbon supports is developed by mixing precursor of Pt with carbon supports in organic batches, hence, one pot synthesis. The PtCube grow with Vulcan XC-72 or Ketjen black, respectively, and then treated for 5.5 h at 185℃ （i.e., Ptcube5.5/V and PtcubeS.5/K）. The resulting particle sizes and shapes are similar; however, Ptcube5.5/K has a larger electrochemical active surface area （EASA） and a remarkably better formic acid （FA） oxidation performance. Optimization of the PtCube/K composites leads to Ptcubelo/K that has been treated for 10 h at 185℃. With a larger EASA, Ptcubelo/K is also more active in FA oxidation than the other Ptcube/K composites. Impedance spectroscopy analysis of the temperature treated and asprepared （i.e., untreated） Ptcube/K composites indicates that PtCube10/K is less resistive, and has the highest limiting capacitance among the PtCube/K electrodes. Consistently, the voltammetric EASA is the largest for Ptcube 10/K. Furthermore, PtCube10/K is compared with two commercial Pt/C catalysts, Tanaka Kikinzoku Kogyo （TKK）, and Johnson Matthey （JM）Pt/C catalysts. The TKK Pt/C has a higher EASA than Ptcube10/K, as expected from their relative particles sizes （3-4 nm vs. 6-7 nm for PtcubelO/K）, however, Ptcube10/K has a significantly better FA oxidation activity.
基金The authors are grateful for the National Natural Science Foundation of China （Grant Nos. 20877006 and 20833011）, National Industrial Project of Rare Earth and Rare Metal New Materials and the Project funding for Academic Human Resources Development in Institutions of Higher Learning under the Jurisdiction of Beijing Municipality （Nos. PHR201107104 and PHR200907105）. We also thank Mining and Metallurgy Research Institute of Beijing for the TEM access.
文摘A novel Ultrasonic Assisted Membrane Reduction （UAMR）-hydrothermal method was used to prepare flower-like Pt/CeO2 catalysts. The texture, physical/chemical properties, and reducibility of the flower-like Pt/CeO2 catalysts were characterized by X-Ray Diffraction （XRD）, Scanning Electron Microscope （SEM）, Transmission Electron Microscope （TEM）, N2 adsorption, and hydrogen temperature programmed reduction （HE-TPR） techniques. The catalytic performance of the catalysts for treating automobile emission was studied relative to samples prepared by the conventional wetness impregnation method. The Pt/CeO2 catalysts fabricated by this novel method showed high specific surface area and metal dispersion, excellent three-way catalytic activity, and good thermal stability. The strong interaction between the Pt nanoparticles and CeO2 improved the thermal stability. The Ce4＋ ions were incorporated into the surfactant chains and the Pt nanoparticles were stabilized through an exchange reaction of the surface hydroxyl groups. The SEM results demonstrated that the Pt/CeO2 catalysts had a typical three-dimensional （3D） hierarchical porous struc- ture, which was favorable for surface reaction and enhanced the exposure degree of the Pt nanoparticles. In brief, the flower-like Pt/CeO2 catalysts prepared by UAMR-hydrothermal method exhibited a higher Pt metal dispersion, smaller particle size, better three-way catalytic activity, and improved thermal stability versus conven- tional materials.
