Water-participated mild oxidation of ethane to acetaldehyde

Bin Li; Jiali Mu; Guifa Long; Xiangen Song; Ende Huang; Siyue Liu; Yao Wei; Fanfei Sun; Siquan Feng; Qiao Yuan; Yutong Cai; Jian Song; Wenrui Dong; Weiqing Zhang; Xueming Yang; Li Yan; Yunjie Ding

doi:10.1038/s41467-024-46884-7

Water-participated mild oxidation of ethane to acetaldehyde

Nat Commun. 2024 Mar 22;15(1):2555. doi: 10.1038/s41467-024-46884-7.

Authors

Bin Li^#^{1

2}, Jiali Mu^#¹, Guifa Long^#³, Xiangen Song⁴, Ende Huang^{1

2}, Siyue Liu^{1

2}, Yao Wei⁵, Fanfei Sun⁵, Siquan Feng¹, Qiao Yuan^{1

2}, Yutong Cai^{1

2}, Jian Song^{1

2}, Wenrui Dong^{6

7}, Weiqing Zhang⁶, Xueming Yang^{8

9}, Li Yan¹, Yunjie Ding^{10

11}

Affiliations

¹ Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China.
² University of Chinese Academy of Sciences, Beijing, China.
³ Guangxi Key Laboratory of Chemistry and Engineering of Forest Products, School of Chemistry and Chemical Engineering, Guangxi Minzu University, Nanning, China.
⁴ Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China. xiangensong@dicp.ac.cn.
⁵ Shanghai Synchrotron Radiation Facility, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai, China.
⁶ State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China.
⁷ Hefei National Laboratory, Hefei, China.
⁸ State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China. xmyang@dicp.ac.cn.
⁹ Department of Chemistry, Southern University of Science and Technology, Shenzhen, China. xmyang@dicp.ac.cn.
¹⁰ Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China. dyj@dicp.ac.cn.
¹¹ State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China. dyj@dicp.ac.cn.

^# Contributed equally.

Abstract

The direct conversion of low alkane such as ethane into high-value-added chemicals has remained a great challenge since the development of natural gas utilization. Herein, we achieve an efficient one-step conversion of ethane to C₂ oxygenates on a Rh₁/AC-SNI catalyst under a mild condition, which delivers a turnover frequency as high as 158.5 h^-1. ¹⁸O isotope-GC-MS shows that the formation of ethanol and acetaldehyde follows two distinct pathways, where oxygen and water directly participate in the formation of ethanol and acetaldehyde, respectively. In situ formed intermediate species of oxygen radicals, hydroxyl radicals, vinyl groups, and ethyl groups are captured by laser desorption ionization/time of flight mass spectrometer. Density functional theory calculation shows that the activation barrier of the rate-determining step for acetaldehyde formation is much lower than that of ethanol, leading to the higher selectivity of acetaldehyde in all the products.