Structure-dependence and metal-dependence on atomically dispersed Ir catalysts for efficient n-butane dehydrogenation

Xiaowen Chen; Xuetao Qin; Yueyue Jiao; Mi Peng; Jiangyong Diao; Pengju Ren; Chengyu Li; Dequan Xiao; Xiaodong Wen; Zheng Jiang; Ning Wang; Xiangbin Cai; Hongyang Liu; Ding Ma

doi:10.1038/s41467-023-38361-4

Structure-dependence and metal-dependence on atomically dispersed Ir catalysts for efficient n-butane dehydrogenation

Nat Commun. 2023 May 5;14(1):2588. doi: 10.1038/s41467-023-38361-4.

Authors

Xiaowen Chen^#^{1

2}, Xuetao Qin^#³, Yueyue Jiao^#^{4

5

6}, Mi Peng³, Jiangyong Diao¹, Pengju Ren^{4

5}, Chengyu Li³, Dequan Xiao⁷, Xiaodong Wen^{4

5}, Zheng Jiang⁸, Ning Wang⁹, Xiangbin Cai¹⁰, Hongyang Liu^{11

12}, Ding Ma¹³

Affiliations

¹ Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang, 110016, P. R. China.
² School of Materials Science and Engineering, University of Science and Technology of China, Shenyang, 110016, P. R. China.
³ Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, P. R. China.
⁴ State Key Laboratory of Coal Conversion, Institute Coal Chemistry, Chinese Academy of Sciences, Taiyuan, 030001, P. R. China.
⁵ National Energy Center for Coal to Clean Fuel, Synfuels China Co., Ltd, Beijing, 100871, P. R. China.
⁶ The University of Chinese Academy of Sciences, Beijing, 100049, P.R. China.
⁷ Center for Integrative Materials Discovery, Department of Chemistry and Chemical and Biomedical Engineering, University of New Haven, West Haven, CT, 06516, USA.
⁸ Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, 201204, P. R. China.
⁹ Department of Physics and Center for Quantum Materials, Hong Kong University of Science and Technology, Kowloon, Hong Kong SAR, P. R. China.
¹⁰ Department of Physics and Center for Quantum Materials, Hong Kong University of Science and Technology, Kowloon, Hong Kong SAR, P. R. China. xcaiak@connect.ust.hk.
¹¹ Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang, 110016, P. R. China. liuhy@imr.ac.cn.
¹² School of Materials Science and Engineering, University of Science and Technology of China, Shenyang, 110016, P. R. China. liuhy@imr.ac.cn.
¹³ Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, P. R. China. dma@pku.edu.cn.

^# Contributed equally.

Abstract

Single-site pincer-ligated iridium complexes exhibit the ability for C-H activation in homogeneous catalysis. However, instability and difficulty in catalyst recycling are inherent disadvantages of the homogeneous catalyst, limiting its development. Here, we report an atomically dispersed Ir catalyst as the bridge between homogeneous and heterogeneous catalysis, which displays an outstanding catalytic performance for n-butane dehydrogenation, with a remarkable n-butane reaction rate (8.8 mol·g_Ir^-1·h^-1) and high butene selectivity (95.6%) at low temperature (450 °C). Significantly, we correlate the BDH activity with the Ir species from nanoscale to sub-nanoscale, to reveal the nature of structure-dependence of catalyst. Moreover, we compare Ir single atoms with Pt single atoms and Pd single atoms for in-depth understanding the nature of metal-dependence at the atomic level. From experimental and theoretical calculations results, the isolated Ir site is suitable for both reactant adsorption/activation and product desorption. Its remarkable dehydrogenation capacity and moderate adsorption behavior are the key to the outstanding catalytic activity and selectivity.