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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.
Abstract:
Electrocatalytic conversion of CH4 to CH3Cl offers a sustainable route for inert alkane valorization. The core challenge is the tension between activating the initial C─H bond and suppressing sequential dehydrogenation, which critically depends on the electrogenerated *Cl mediators. Here, we construct a silver single-atom electrocatalyst on graphitic carbon nitride (Ag1/C3N4) that enables *Cl generation at the C site of the C3N4 support, markedly facilitating the *Cl generation and selective methane chlorination. In a flow cell with saturated NaCl at ambient conditions, Ag1/C3N4 attains a benchmark CH3Cl yield of 1784.5 mmol g-1 h-1 with 88.0% selectivity at 1.8 V vs. Ag/AgCl. Combined experimental and computational insights reveal that the electrogenerated *Cl locally restructures the Ag1-C3N4 interface to contribute to a synergistic Ag─N─C─*Cl site that promotes CH4 activation and chlorination. This *Cl-induced metal-support synergy markedly lowers the energy demand for initial C─H cleavage (from 1.32 to 0.67 eV) and CH3Cl formation (from 1.52 to 0.83 eV), with a low CH3Cl desorption energy (0.27 eV) to suppress over-dehydrogenation. This work establishes a *Cl-mediated dual-site pathway for electrocatalytic methane valorization, offering a promising strategy for mediator-guided active site engineering in challenging inert-alkane valorization.
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