Hydroxyl-Promoted C─C Coupling for Selective Methane Conversion into Ethane on Cerium Oxide Photocatalyst
Dr. Lei Luo
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Zhongshan Road 457, Dalian, 116023 P.R. China
Both authors contributed equally to this work.
Search for more papers by this authorDr. Rong Wang
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Zhongshan Road 457, Dalian, 116023 P.R. China
Both authors contributed equally to this work.
Search for more papers by this authorZongxu Wu
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Zhongshan Road 457, Dalian, 116023 P.R. China
Search for more papers by this authorDr. Yejun Xiao
State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023 P.R. China
Search for more papers by this authorJiangnan Li
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Zhongshan Road 457, Dalian, 116023 P.R. China
Search for more papers by this authorProf. Zhaochi Feng
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Zhongshan Road 457, Dalian, 116023 P.R. China
Search for more papers by this authorCorresponding Author
Prof. Dr. Fuxiang Zhang
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Zhongshan Road 457, Dalian, 116023 P.R. China
E-mail: [email protected]
Search for more papers by this authorDr. Lei Luo
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Zhongshan Road 457, Dalian, 116023 P.R. China
Both authors contributed equally to this work.
Search for more papers by this authorDr. Rong Wang
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Zhongshan Road 457, Dalian, 116023 P.R. China
Both authors contributed equally to this work.
Search for more papers by this authorZongxu Wu
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Zhongshan Road 457, Dalian, 116023 P.R. China
Search for more papers by this authorDr. Yejun Xiao
State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023 P.R. China
Search for more papers by this authorJiangnan Li
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Zhongshan Road 457, Dalian, 116023 P.R. China
Search for more papers by this authorProf. Zhaochi Feng
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Zhongshan Road 457, Dalian, 116023 P.R. China
Search for more papers by this authorCorresponding Author
Prof. Dr. Fuxiang Zhang
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Zhongshan Road 457, Dalian, 116023 P.R. China
E-mail: [email protected]
Search for more papers by this authorGraphical Abstract
Surface hydroxyl modification on noble-metal-free photocatalysts enhances CH4 chemisorption, reducing the energy barrier for C─C coupling and effectively suppressing over-oxidation to CO2, thereby achieving approximately 97% selectivity over a 200-h flow operation.
Abstract
Converting methane into high-value chemicals under mild conditions offers substantial environmental and energy benefits but is challenged by the difficulty of activating C─H bonds and preventing over-oxidation. In this study, the pivotal role of hydroxyl-rich surfaces on noble-metal-free photocatalysts is demonstrated in directing selective C─C coupling of methane. These surface hydroxyls not only enhance methane chemisorption and improve charge separation, but also promote favorable interactions with molecular oxygen, collectively boosting catalytic performance. Furthermore, the hydroxyl groups lower the energy barrier for ethane formation while suppressing its over-oxidation to CO2, resulting in significantly improved selectivity. Under ambient conditions in a flow-reactor system, the catalyst achieves a continuous ethane production rate of 187 µmol·g−1·h−1 with approximately 97% selectivity over an extended operation period (>200 h), surpassing previous noble-metal-free photocatalytic systems. This work provides critical insights into the role of hydroxyl-modified local environment in methane valorization, paving the way for the development of sustainable and efficient catalytic systems.
Conflict of Interests
The authors declare no conflict of interest.
Open Research
Data Availability Statement
The data that support the findings of this study are available from the corresponding author upon reasonable request.
Supporting Information
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| anie202510032-sup-0001-SuppMat.docx4.8 MB | Supporting Information |
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