气氛环境下原位研究催化剂的烧结行为,能够为理解催化剂在预处理以及反应条件下的烧结机理和高稳定催化剂的设计提供重要的实验依据。本文以Au/CeO_(2)模型纳米催化剂为研究对象,利用环境透射电子显微镜原位观察其在O_(2)与CO气氛下的...气氛环境下原位研究催化剂的烧结行为,能够为理解催化剂在预处理以及反应条件下的烧结机理和高稳定催化剂的设计提供重要的实验依据。本文以Au/CeO_(2)模型纳米催化剂为研究对象,利用环境透射电子显微镜原位观察其在O_(2)与CO气氛下的高温动态烧结过程。实验发现,负载在CeO_(2)上的Au纳米颗粒在O_(2)与CO气氛环境中表现出不同的烧结行为,其在O_(2)气氛下具有较高的烧结速度,同时存在颗粒迁移与聚集长大(particle migration and coalescence,PMC)和奥斯特瓦尔德熟化(Ostwald ripening,OR)两种烧结过程;在CO气氛下烧结速度较慢,烧结过程以OR为主。对比不同气氛环境下烧结后催化剂的表面结构可知,CO增加了CeO_(2)表面台阶的数量以及表面氧空位浓度,增强了载体对Au颗粒的锚定作用,从而提升Au/CeO_(2)催化剂的稳定性。展开更多
The dynamic and kinetic evolution of supported metal particles in the presence of reactants is decisive in shaping the nature of the catalytic active sites and the deactivation process. Ostwald ripening of FeO/Pt(111)...The dynamic and kinetic evolution of supported metal particles in the presence of reactants is decisive in shaping the nature of the catalytic active sites and the deactivation process. Ostwald ripening of FeO/Pt(111) supported Au particles in the presence of carbon monoxide is addressed here by firstprinciples kinetics. It is found that CO stabilizes the ripening monomer(Au atom) by forming favorable Au carbonyls with lower total activation energy, and corresponding phase diagram at wide range of temperature and CO pressures is constructed. Evolution of particle number, dispersion and particle size distribution of supported Au particles are explored. Great influence of CO promotion on ripening kinetics is revealed and explored in details, and mbar range of CO can lower the onset temperature of ripening by a few hundred kelvins. The present work reveals the crucial role of the metal-reactant complexes formed under reaction conditions on ripening of metal catalysts.展开更多
The direct electron transfer of hemoglobin at the PAMAM-MWNTs-AuNPs composite film modified glassy carbon electrode was studied. In a phosphate buffer solution（PBS, pH=7.0）, the formal potential（E^0） of Hb was -0....The direct electron transfer of hemoglobin at the PAMAM-MWNTs-AuNPs composite film modified glassy carbon electrode was studied. In a phosphate buffer solution（PBS, pH=7.0）, the formal potential（E^0） of Hb was -0.105 V versus SCE, the electron transfer rate constant was 4.66 s-1. E^0＇ of Hb at the modified electrode was linearly varied in a pH range of 5.0-8.0 with a slope of-49.2 mV/pH. The Hb/PAMAM-MWNTs-AuNPs/GCE gave an excellent electrocatalytic response to the reduction of hydrogen peroxide. The catalytic current increased linearly with H2O2 concentration in a range of 1.0× 10^-6 to 2.2× 10^-3 mol/L. The detection limit was 2.0× 10^-7 mol/L at a signal to noise ratio of 3. The Michaelis-Menten constant（Km^app） was 2.95 mmol/L.展开更多
文摘气氛环境下原位研究催化剂的烧结行为,能够为理解催化剂在预处理以及反应条件下的烧结机理和高稳定催化剂的设计提供重要的实验依据。本文以Au/CeO_(2)模型纳米催化剂为研究对象,利用环境透射电子显微镜原位观察其在O_(2)与CO气氛下的高温动态烧结过程。实验发现,负载在CeO_(2)上的Au纳米颗粒在O_(2)与CO气氛环境中表现出不同的烧结行为,其在O_(2)气氛下具有较高的烧结速度,同时存在颗粒迁移与聚集长大(particle migration and coalescence,PMC)和奥斯特瓦尔德熟化(Ostwald ripening,OR)两种烧结过程;在CO气氛下烧结速度较慢,烧结过程以OR为主。对比不同气氛环境下烧结后催化剂的表面结构可知,CO增加了CeO_(2)表面台阶的数量以及表面氧空位浓度,增强了载体对Au颗粒的锚定作用,从而提升Au/CeO_(2)催化剂的稳定性。
基金supported by the National Key R&D Program of China(2017YB0602205)the National Natural Science Foundation of China(91645202)the Chinese Academy of Sciences(QYZDJSSW-SLH054)
文摘The dynamic and kinetic evolution of supported metal particles in the presence of reactants is decisive in shaping the nature of the catalytic active sites and the deactivation process. Ostwald ripening of FeO/Pt(111) supported Au particles in the presence of carbon monoxide is addressed here by firstprinciples kinetics. It is found that CO stabilizes the ripening monomer(Au atom) by forming favorable Au carbonyls with lower total activation energy, and corresponding phase diagram at wide range of temperature and CO pressures is constructed. Evolution of particle number, dispersion and particle size distribution of supported Au particles are explored. Great influence of CO promotion on ripening kinetics is revealed and explored in details, and mbar range of CO can lower the onset temperature of ripening by a few hundred kelvins. The present work reveals the crucial role of the metal-reactant complexes formed under reaction conditions on ripening of metal catalysts.
基金Supported by the National Natural Science Foundation of China(No.20605009)
文摘The direct electron transfer of hemoglobin at the PAMAM-MWNTs-AuNPs composite film modified glassy carbon electrode was studied. In a phosphate buffer solution（PBS, pH=7.0）, the formal potential（E^0） of Hb was -0.105 V versus SCE, the electron transfer rate constant was 4.66 s-1. E^0＇ of Hb at the modified electrode was linearly varied in a pH range of 5.0-8.0 with a slope of-49.2 mV/pH. The Hb/PAMAM-MWNTs-AuNPs/GCE gave an excellent electrocatalytic response to the reduction of hydrogen peroxide. The catalytic current increased linearly with H2O2 concentration in a range of 1.0× 10^-6 to 2.2× 10^-3 mol/L. The detection limit was 2.0× 10^-7 mol/L at a signal to noise ratio of 3. The Michaelis-Menten constant（Km^app） was 2.95 mmol/L.
