Rh/InGaN1-xOx nanoarchitecture for light-driven methane reforming with carbon dioxide toward syngas

Yixin Li; Jinglin Li; Tianqi Yu; Liang Qiu; Syed M Najib Hasan; Lin Yao; Hu Pan; Shamsul Arafin; Sharif Md Sadaf; Lei Zhu; Baowen Zhou

doi:10.1016/j.scib.2024.02.020

Rh/InGaN_1-_xO_x nanoarchitecture for light-driven methane reforming with carbon dioxide toward syngas

Sci Bull (Beijing). 2024 Feb 12:S2095-9273(24)00106-3. doi: 10.1016/j.scib.2024.02.020. Online ahead of print.

Authors

Yixin Li¹, Jinglin Li¹, Tianqi Yu¹, Liang Qiu¹, Syed M Najib Hasan², Lin Yao³, Hu Pan¹, Shamsul Arafin⁴, Sharif Md Sadaf⁵, Lei Zhu¹, Baowen Zhou⁶

Affiliations

¹ Key Laboratory for Power Machinery and Engineering of Ministry of Education, Research Center for Renewable Synthetic Fuel, School of Mechanical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China.
² Department of Electrical and Computer Engineering, The Ohio State University, Columbus, OH, 43210, USA.
³ China-UK Low Carbon College, Shanghai Jiao Tong University, Shanghai 201306, China. Electronic address: yaol@sjtu.edu.cn.
⁴ Department of Electrical and Computer Engineering, The Ohio State University, Columbus, OH, 43210, USA. Electronic address: arafin.1@osu.edu.
⁵ Centre Energie, Matériaux et Télécommunications, Institut National de la Recherche Scientifique (INRS)-Université du Québec, Varennes J3X 1E4, Canada. Electronic address: sharif.sadaf@inrs.ca.
⁶ Key Laboratory for Power Machinery and Engineering of Ministry of Education, Research Center for Renewable Synthetic Fuel, School of Mechanical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China. Electronic address: zhoubw@sjtu.edu.cn.

PMID: 38402030
DOI: 10.1016/j.scib.2024.02.020

Abstract

Light-driven dry reforming of methane toward syngas presents a proper solution for alleviating climate change and for the sustainable supply of transportation fuels and chemicals. Herein, Rh/InGaN_1-_xO_x nanowires supported by silicon wafer are explored as an ideal platform for loading Rh nanoparticles, thus assembling a new nanoarchitecture for this grand topic. In combination with the remarkable photo-thermal synergy, the O atoms in Rh/InGaN_1-_xO_x can significantly lower the apparent activation energy of dry reforming of methane from 2.96 eV downward to 1.70 eV. The as-designed Rh/InGaN_1-_xO_x NWs nanoarchitecture thus demonstrates a measurable syngas evolution rate of 180.9 mmol g_cat^-1 h^-1 with a marked selectivity of 96.3% under concentrated light illumination of 6 W cm^-2. What is more, a high turnover number (TON) of 4182 mol syngas per mole Rh has been realized after six reuse cycles without obvious activity degradation. The correlative ¹⁸O isotope labeling experiments, in-situ irradiated X-ray photoelectron spectroscopy (ISI-XPS) and in-situ diffuse reflectance Fourier transform infrared spectroscopy characterizations, as well as density functional theory calculations reveal that under light illumination, Rh/InGaN_1-_xO_x NWs facilitate releasing *CH₃ and H⁺ from CH₄ by holes, followed by H₂ evolution from H⁺ reduction with electrons. Subsequently, the O atoms in Rh/InGaN_1-_xO_x can directly participate in CO generation by reacting with the *C species from CH₄ dehydrogenation and contributes to the coke elimination, in concurrent formation of O vacancies. The resultant O vacancies are then replenished by CO₂, showing an ideal chemical loop. This work presents a green strategy for syngas production via light-driven dry reforming of methane.

Keywords: Dry reforming of methane; Photo-thermal catalysis; Rh/InGaN(1−)(x)O(x) nanowires.