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Nat Commun. 2019 Apr 23;10(1):1885. doi: 10.1038/s41467-019-09918-z.

Optimizing reaction paths for methanol synthesis from CO2 hydrogenation via metal-ligand cooperativity.

Author information

1
Hefei National Laboratory for Physical Sciences at the Microscale, Key Laboratory of Strongly-Coupled Quantum Matter Physics of Chinese Academy of Sciences, National Synchrotron Radiation Laboratory, Key Laboratory of Surface and Interface Chemistry and Energy Catalysis of Anhui Higher Education Institutes, Department of Chemical Physics, University of Science and Technology of China, 230026, Hefei, Anhui, People's Republic of China.
2
Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, 201204, Shanghai, People's Republic of China.
3
Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, 201204, Shanghai, People's Republic of China. sirui@sinap.ac.cn.
4
Hefei National Laboratory for Physical Sciences at the Microscale, Key Laboratory of Strongly-Coupled Quantum Matter Physics of Chinese Academy of Sciences, National Synchrotron Radiation Laboratory, Key Laboratory of Surface and Interface Chemistry and Energy Catalysis of Anhui Higher Education Institutes, Department of Chemical Physics, University of Science and Technology of China, 230026, Hefei, Anhui, People's Republic of China. zengj@ustc.edu.cn.

Abstract

As diversified reaction paths exist over practical catalysts towards CO2 hydrogenation, it is highly desiderated to precisely control the reaction path for developing efficient catalysts. Herein, we report that the ensemble of Pt single atoms coordinated with oxygen atoms in MIL-101 (Pt1@MIL) induces distinct reaction path to improve selective hydrogenation of CO2 into methanol. Pt1@MIL achieves the turnover frequency number of 117 h-1 in DMF under 32 bar at 150 °C, which is 5.6 times that of Ptn@MIL. Moreover, the selectivity for methanol is 90.3% over Pt1@MIL, much higher than that (13.3%) over Ptn@MIL with CO as the major product. According to mechanistic studies, CO2 is hydrogenated into HCOO* as the intermediate for Pt1@MIL, whereas COOH* serves as the intermediate for Ptn@MIL. The unique reaction path over Pt1@MIL not only lowers the activation energy for the enhanced catalytic activity, but also contributes to the high selectivity for methanol.

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