Ambient methane functionalization initiated by electrochemical oxidation of a vanadium (V)-oxo dimer
Ambient methane functionalization initiated by electrochemical oxidation of a vanadium (V)-oxo dimer
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DOI：
10.1038/s41467-020-17494-w
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发表时间：
2020-07
影响因子：
16.6
通讯作者：
Jiao Deng;Sheng-Chih Lin;Jack T Fuller;Jesus A. Iñiguez;Danlei Xiang;Di Yang;Gary Chan;Hao Ming Che
中科院分区：
文献类型：
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作者：
Jiao Deng;Sheng-Chih Lin;Jack T Fuller;Jesus A. Iñiguez;Danlei Xiang;Di Yang;Gary Chan;Hao Ming Che
丰富而广泛分布的甲烷资源需要有效地将甲烷转化为液体化学品，而具有最小基础设施支持的环境选择性过程仍有待证明。本文报道了以钒（V）-氧代二聚体为分子催化剂，在常压和室温下选择性电化学氧化CH 4制备硫酸氢甲酯（CH 3 OSO 3 H）的反应。这种耐水性、地球资源丰富的催化剂具有低活化能（10.8 kcal mol/L）和高转换频率（在1巴和3巴纯CH 4下分别为483和1336 hr-1）。该催化系统在环境条件下将天然气混合物电化学转化为液体产品超过240小时，法拉第效率为90%，周转次数超过100，000。这种初步提出的机制适用于其他d 0 early过渡金属物种，并代表了一种新的可扩展的方法，有助于减轻偏远地区天然气的燃烧或直接排放。
The abundant yet widely distributed methane resources require efficient conversion of methane into liquid chemicals, whereas an ambient selective process with minimal infrastructure support remains to be demonstrated. Here we report selective electrochemical oxidation of CH4to methyl bisulfate (CH3OSO3H) at ambient pressure and room temperature with a molecular catalyst of vanadium (V)-oxo dimer. This water-tolerant, earth-abundant catalyst possesses a low activation energy (10.8 kcal mol‒1) and a high turnover frequency (483 and 1336 hr−1at 1-bar and 3-bar pure CH4, respectively). The catalytic system electrochemically converts natural gas mixture into liquid products under ambient conditions over 240 h with a Faradaic efficiency of 90% and turnover numbers exceeding 100,000. This tentatively proposed mechanism is applicable to other d0early transition metal species and represents a new scalable approach that helps mitigate the flaring or direct emission of natural gas at remote locations.