Gallium nitride catalyzed the direct hydrogenation of carbon dioxide to dimethyl ether as primary product

Chang Liu; Jincan Kang; Zheng-Qing Huang; Yong-Hong Song; Yong-Shan Xiao; Jian Song; Jia-Xin He; Chun-Ran Chang; Han-Qing Ge; Ye Wang; Zhao-Tie Liu; Zhong-Wen Liu

doi:10.1038/s41467-021-22568-4

Gallium nitride catalyzed the direct hydrogenation of carbon dioxide to dimethyl ether as primary product

Nat Commun. 2021 Apr 16;12(1):2305. doi: 10.1038/s41467-021-22568-4.

Authors

Affiliations

¹ Key Laboratory of Syngas Conversion of Shaanxi Province, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an, China.
² State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, National Engineering Laboratory for Green Chemical Productions of Alcohols, Ethers and Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, China.
³ Shaanxi Key Laboratory of Energy Chemical Process Intensification, School of Chemical Engineering and Technology, Xi'an Jiaotong University, Xi'an, China.
⁴ Shaanxi Key Laboratory of Energy Chemical Process Intensification, School of Chemical Engineering and Technology, Xi'an Jiaotong University, Xi'an, China. changcr@mail.xjtu.edu.cn.
⁵ State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, National Engineering Laboratory for Green Chemical Productions of Alcohols, Ethers and Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, China. wangye@xmu.edu.cn.
⁶ Key Laboratory of Syngas Conversion of Shaanxi Province, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an, China. zwliu@snnu.edu.cn.

Abstract

The selective hydrogenation of CO₂ to value-added chemicals is attractive but still challenged by the high-performance catalyst. In this work, we report that gallium nitride (GaN) catalyzes the direct hydrogenation of CO₂ to dimethyl ether (DME) with a CO-free selectivity of about 80%. The activity of GaN for the hydrogenation of CO₂ is much higher than that for the hydrogenation of CO although the product distribution is very similar. The steady-state and transient experimental results, spectroscopic studies, and density functional theory calculations rigorously reveal that DME is produced as the primary product via the methyl and formate intermediates, which are formed over different planes of GaN with similar activation energies. This essentially differs from the traditional DME synthesis via the methanol intermediate over a hybrid catalyst. The present work offers a different catalyst capable of the direct hydrogenation of CO₂ to DME and thus enriches the chemistry for CO₂ transformations.

Abstract

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