Visible-Light-Mediated Methane Activation for Steam Methane Reforming under Mild Conditions: A Case Study of Rh/TiO2 Catalysts,ACS Catalysis

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Visible-Light-Mediated Methane Activation for Steam Methane Reforming under Mild Conditions: A Case Study of Rh/TiO2 Catalysts
ACS Catalysis ( IF 11.3 ) Pub Date : 2018-07-09 00:00:00 , DOI: 10.1021/acscatal.8b01787
Hui Song _{1,

2} , Xianguang Meng _{2,

3} , Zhou-jun Wang _{2,

4} , Zhuan Wang ₅ , Hailong Chen ₅ , Yuxiang Weng _{5,

6} , Fumihiko Ichihara _{1,

2} , Mitsutake Oshikiri ₇ , Tetsuya Kako ₂ , Jinhua Ye _{1,

2,

8,

9}

Affiliation

Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo 060-0814, Japan
International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan
Hebei Provincial Key Laboratory of Inorganic Nonmetallic Materials, College of Materials Science and Engineering, North China University of Science and Technology, Tangshan 063210, P. R. China
State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, 15 Beisanhuan East Road, Beijing 100029, China
Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, P. R. China
School of Physical Sciences, University of Chinese Academy of Sciences, Beijing 100049, P. R. China
International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science (NIMS), 3-13 Sakura, Tsukuba, Ibaraki 305-0003, Japan
TJU-NIMS International Collaboration Laboratory, School of Material Science and Engineering, Tianjin University, Tianjin 300072, P. R. China
Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, P. R. China

Hot-carrier-induced molecular activation over photoexcited 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 °C) with an ∼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^δ+ 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.

中文翻译：

轻度条件下可见光介导的甲烷活化用于蒸汽甲烷重整：Rh / TiO ₂催化剂的案例研究

光激发金属纳米结构上热载流子诱导的分子活化是太阳能转化为化学能的重要研究领域。在这里，我们报道了可见光照明的TiO ₂负载的Rh纳米颗粒可以在温和的操作温度（低于300°C）下显着增强蒸汽甲烷重整中的甲烷（CH ₄）活化，与表观活化能相比，其表观活化能降低约50％。纯热过程。飞秒时间分辨的红外光谱测量和密度泛函理论计算表明，Rh-TiO ₂界面上的热载流子超快分离，从而导致连续CH ₄在表面上形成电子缺乏的Rhδ ⁺态。在低温下活化。波长依赖性活性和动力学同位素实验证明，Rh纳米粒子中的光激发热载流子在促进速率确定步骤（即CH _4中C–H键的裂解）中起关键作用。通过活性纳米金属光催化剂的构建，这项研究为C–H键活化化学开辟了一条有希望的途径。

更新日期：2018-07-09

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