期刊
ACS CATALYSIS
卷 8, 期 8, 页码 7556-7565出版社
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.8b01787
关键词
CH4 activation; Rh; TiO2; hot carrier; ultrafast separation; apparent activation energy
资金
- World Premier International Research Center Initiative (WPI Initiative) on Materials Nanoarchitectonics (MANA)
- MEXT (Japan)
- National Basic Research Program of China (973 Program) [2014CB239301]
- National Natural Science Foundation of China [21633004]
- JSPS KAKENHI [JP18H02065]
- State Scholarship Fund by China Scholarship Council (CSC) [201606320239, 201706885023]
Hot-carrier-induced molecular activation over photo excited metal nanostructures is an important research field in solar to -chemical energy conversion. Here, we report that visible light illuminated TiO2-supported Rh nanoparticles could significantly enhance methane (CH4) activation in steam methane reforming at mild operating temperature (below 300 degrees C) with an similar to 50% decrease in apparent activation energy compared to that of the pure thermal process. Femtosecond time-resolved infrared spectroscopic measurement and density functional theory calculations show an ultrafast separation of hot carriers at the Rh-TiO2 interface, resulting in the formation of an electron-deficient state of Rh delta+ at the surface for successive CH4 activation at low temperatures. Wavelength-dependent activities and kinetic isotope experiments validate that the photoexcited hot carriers in the Rh nanoparticles play a critical role in facilitating the rate-determining steps, i.e., the cleavage of the C-H bond in CH4. This study opens a promising pathway toward C-H bond activation chemistry by the construction of active nanometal photocatalysts.
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