Oxynitride-surface engineering of rhodium-decorated gallium nitride for efficient thermocatalytic hydrogenation of carbon dioxide to carbon monoxide

Jinglin Li; Bowen Sheng; Yiqing Chen; Sharif Md Sadaf; Jiajia Yang; Ping Wang; Hu Pan; Tao Ma; Lei Zhu; Jun Song; He Lin; Xinqiang Wang; Zhen Huang; Baowen Zhou

doi:10.1038/s42004-022-00728-x

Oxynitride-surface engineering of rhodium-decorated gallium nitride for efficient thermocatalytic hydrogenation of carbon dioxide to carbon monoxide

Commun Chem. 2022 Sep 6;5(1):107. doi: 10.1038/s42004-022-00728-x.

Authors

Jinglin Li^#¹, Bowen Sheng^#², Yiqing Chen^#³, Sharif Md Sadaf⁴, Jiajia Yang², Ping Wang², Hu Pan¹, Tao Ma⁵, Lei Zhu¹, Jun Song⁶, He Lin¹, Xinqiang Wang^{7

8

9}, Zhen Huang¹⁰, Baowen Zhou¹¹

Affiliations

¹ Key Laboratory for Power Machinery and Engineering of Ministry of Education, School of Mechanical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240, China.
² State Key Laboratory of Artificial Microstructure and Mesoscopic Physics, School of Physics, Nano-Optoelectronics Frontier Center of Ministry of Education (NFC-MOE), Peking University, Beijing, 10087, China.
³ Department of Mining and Materials Engineering, McGill University, 3610 University Street, Montreal, QC, H3A0C9, Canada.
⁴ Centre Energie, Matériaux et Télécommunications, Institut National de la Recherche Scientifique (INRS)-Université du Québec, 1650 Boulevard Lionel-Boulet, Varennes, QC, J3X1S2, Canada.
⁵ Michigan Center for Materials and Characterization, University of Michigan, 2800 Plymouth Rd, Ann Arbor, MI, 48109, USA.
⁶ Department of Mining and Materials Engineering, McGill University, 3610 University Street, Montreal, QC, H3A0C9, Canada. jun.song2@mcgill.ca.
⁷ State Key Laboratory of Artificial Microstructure and Mesoscopic Physics, School of Physics, Nano-Optoelectronics Frontier Center of Ministry of Education (NFC-MOE), Peking University, Beijing, 10087, China. wangshi@pku.edu.cn.
⁸ Peking University Yangtze Delta Institute of Optoelectronics, Nantong, Jiangsu, 226010, China. wangshi@pku.edu.cn.
⁹ Collaborative Innovation Center of Quantum Matter, School of Physics, Peking University, Beijing, 100871, China. wangshi@pku.edu.cn.
¹⁰ Key Laboratory for Power Machinery and Engineering of Ministry of Education, School of Mechanical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240, China. z-huang@sjtu.edu.cn.
¹¹ Key Laboratory for Power Machinery and Engineering of Ministry of Education, School of Mechanical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240, China. zhoubw@sjtu.edu.cn.

^# Contributed equally.

Abstract

Upcycling of carbon dioxide towards fuels and value-added chemicals poses an opportunity to overcome challenges faced by depleting fossil fuels and climate change. Herein, combining highly controllable molecular beam epitaxy growth of gallium nitride (GaN) under a nitrogen-rich atmosphere with subsequent air annealing, a tunable platform of gallium oxynitride (GaN_1-xO_x) nanowires is built to anchor rhodium (Rh) nanoparticles for carbon dioxide hydrogenation. By correlatively employing various spectroscopic and microscopic characterizations, as well as density functional theory calculations, it is revealed that the engineered oxynitride surface of GaN works in synergy with Rh to achieve a dramatically reduced energy barrier. Meanwhile, the potential-determining step is switched from *COOH formation into *CO desorption. As a result, significantly improved CO activity of 127 mmol‧g_cat^-1‧h^-1 is achieved with high selectivity of >94% at 290 °C under atmospheric pressure, which is three orders of magnitude higher than that of commercial Rh/Al₂O₃. Furthermore, capitalizing on the high dispersion of the Rh species, the architecture illustrates a decent turnover frequency of 270 mol CO per mol Rh per hour over 9 cycles of operation. This work presents a viable strategy for promoting CO₂ refining via surface engineering of an advanced support, in collaboration with a suitable metal cocatalyst.