Ag II ‐Mediated Electrocatalytic Ambient CH 4 Functionalization Inspired by HSAB Theory
Ag II ‐Mediated Electrocatalytic Ambient CH 4 Functionalization Inspired by HSAB Theory
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Ag II — 受 HSAB 理论启发的介导电催化环境 CH 4 功能化
DOI：
10.1002/anie.202104217
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发表时间：
2021
期刊：
影响因子：
--
通讯作者：
Liu, Chong
中科院分区：
文献类型：
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作者：
Xiang, Danlei;Iñiguez, Jesus A.;Deng, Jiao;Guan, Xun;Martinez, Antonio;Liu, Chong
尽管大多数 (b) 类过渡金属已针对 CH4 活化进行了研究，但二价银 (AgII) 可能由于其反应性质，是唯一尚未报道表现出对 CH4 活化反应性的 (b) 类高价过渡金属中心。我们现在报道，在环境条件下，在 98% H2SO4 中，电化学生成的 AgII 金属自由基很容易将 CH4 官能化为硫酸氢甲酯 (CH3OSO3H)。实验机理研究揭示了 13.1 kcal mol−1 的低活化能、室温下高达 2.8×103h−1 的 CH4 活化准一级速率常数和 85 psi 的 CH4 压力，以及两种相对于溶剂氧化更适合 CH4 活化的竞争反应途径。反应动力学数据表明，在室温下，超过 180 psi CH4 时，法拉第效率超过 99 %，可利用广泛分布的天然气资源进行潜在的化学生产，同时对基础设施的依赖最小。
Although most class (b) transition metals have been studied in regard to CH4activation, divalent silver (AgII), possibly owing to its reactive nature, is the only class (b) high‐valent transition metal center that is not yet reported to exhibit reactivities towards CH4activation. We now report that electrochemically generated AgIImetalloradical readily functionalizes CH4into methyl bisulfate (CH3OSO3H) at ambient conditions in 98 % H2SO4. Mechanistic investigation experimentally unveils a low activation energy of 13.1 kcal mol−1, a high pseudo‐first‐order rate constant of CH4activation up to 2.8×103h−1at room temperature and a CH4pressure of 85 psi, and two competing reaction pathways preferable towards CH4activation over solvent oxidation. Reaction kinetic data suggest a Faradaic efficiency exceeding 99 % beyond 180 psi CH4at room temperature for potential chemical production from widely distributed natural gas resources with minimal infrastructure reliance.