PdCu nanoalloy decorated photocatalysts for efficient and selective oxidative coupling of methane in flow reactors

Xiyi Li; Chao Wang; Jianlong Yang; Youxun Xu; Yi Yang; Jiaguo Yu; Juan J Delgado; Natalia Martsinovich; Xiao Sun; Xu-Sheng Zheng; Weixin Huang; Junwang Tang

doi:10.1038/s41467-023-41996-y

PdCu nanoalloy decorated photocatalysts for efficient and selective oxidative coupling of methane in flow reactors

Nat Commun. 2023 Oct 10;14(1):6343. doi: 10.1038/s41467-023-41996-y.

Authors

Xiyi Li¹, Chao Wang¹, Jianlong Yang², Youxun Xu¹, Yi Yang³, Jiaguo Yu⁴, Juan J Delgado^{5

6}, Natalia Martsinovich⁷, Xiao Sun⁸, Xu-Sheng Zheng⁹, Weixin Huang⁸, Junwang Tang^{10

11}

Affiliations

¹ Department of Chemical Engineering, University College London, London, WC1E 7JE, UK.
² Key Lab of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, the Energy and Catalysis Hub, College of Chemistry and Materials Science, Northwest University, Xi'an, P. R. China.
³ State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan, 430070, China.
⁴ Laboratory of Solar Fuel, Faculty of Materials Science and Chemistry, China University of Geosciences, 388 Lumo Road, Wuhan, 430074, China.
⁵ Departamento de Ciencia de los Materiales e Ingeniería Metalúrgica y Química Inorgánica, Facultad de Ciencias, Universidad de Cádiz, Campus Rio San Pedro, 11510, Puerto Real, Cádiz, Spain.
⁶ IMEYMAT, Instituto de Microscopía Electrónica y Materiales, Puerto Real, 11510, Spain.
⁷ Department of Chemistry, University of Sheffield, Sheffield, S3 7HF, UK.
⁸ Hefei National Research Center for Physical Sciences at the Microscale, iChEM, Key Laboratory of Surface and Interface Chemistry and Energy Catalysis of Anhui Higher Education Institutes, School of Chemistry and Materials Science, University of Science and Technology of China, 230026, Hefei, China.
⁹ National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, 230029, Anhui, China.
¹⁰ Department of Chemical Engineering, University College London, London, WC1E 7JE, UK. junwang.tang@ucl.ac.uk.
¹¹ Industrial Catalysis Center, Department of Chemical Engineering, Tsinghua University, Beijing, 100084, China. junwang.tang@ucl.ac.uk.

Abstract

Methane activation by photocatalysis is one of the promising sustainable technologies for chemical synthesis. However, the current efficiency and stability of the process are moderate. Herein, a PdCu nanoalloy (~2.3 nm) was decorated on TiO₂, which works for the efficient, stable, and selective photocatalytic oxidative coupling of methane at room temperature. A high methane conversion rate of 2480 μmol g^-1 h^-1 to C₂ with an apparent quantum efficiency of ~8.4% has been achieved. More importantly, the photocatalyst exhibits the turnover frequency and turnover number of 116 h^-1 and 12,642 with respect to PdCu, representing a record among all the photocatalytic processes (λ > 300 nm) operated at room temperature, together with a long stability of over 112 hours. The nanoalloy works as a hole acceptor, in which Pd softens and weakens C-H bond in methane and Cu decreases the adsorption energy of C₂ products, leading to the high efficiency and long-time stability.

Abstract

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