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Precisely Constructing Ag1/C3N4 Dual-Site for Highly Efficient Chlorine-Mediated Electrocatalytic Methane
Hehe Qian1,2,3, Tinghui Ma1,3, Yumin Mao1,2
1State Key Laboratory of Soil Pollution Control and Safety, College of Environmental and Resource Sciences, Zhejiang University, Hangzhou, P. R. China.
This study introduces a novel silver single-atom electrocatalyst for converting methane to methyl chloride, achieving high yield and selectivity. The catalyst utilizes electrogenerated chlorine mediators to enable efficient and sustainable methane valorization.
Area of Science:
- Electrochemistry
- Catalysis
- Materials Science
Background:
- Electrocatalytic conversion of methane (CH4) to methyl chloride (CH3Cl) presents a sustainable pathway for utilizing inert alkanes.
- A key challenge lies in balancing initial C-H bond activation with preventing over-dehydrogenation, which is influenced by electrogenerated chlorine (*Cl) mediators.
Purpose of the Study:
- To develop a novel electrocatalyst for efficient and selective methane chlorination.
- To investigate the mechanism of *Cl mediator generation and its role in methane activation and conversion.
Main Methods:
- Fabrication of a silver single-atom electrocatalyst supported on graphitic carbon nitride (Ag1/C3N4).
- Electrochemical characterization in a flow cell using saturated NaCl solution.
- Computational modeling (DFT) to elucidate reaction mechanisms and energy barriers.
Main Results:
- The Ag1/C3N4 catalyst achieved a high CH3Cl yield of 1784.5 mmol g-1 h-1 with 88.0% selectivity at 1.8 V vs. Ag/AgCl.
- Electrogenerated *Cl mediators were observed to facilitate *Cl generation at the C site of C3N4, enhancing selectivity.
- Computational analysis revealed a synergistic Ag-N-C-*Cl active site that lowers activation energy for CH4 cleavage and CH3Cl formation, while suppressing over-dehydrogenation.
Conclusions:
- The Ag1/C3N4 catalyst demonstrates a promising *Cl-mediated dual-site pathway for electrocatalytic methane valorization.
- This work highlights the potential of mediator-guided active site engineering for inert alkane conversion.
- The findings offer a sustainable strategy for transforming methane into valuable chemicals.
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