Electrocatalytic Methane Functionalization with d 0 Early Transition Metals Under Ambient Conditions
Electrocatalytic Methane Functionalization with d 0 Early Transition Metals Under Ambient Conditions
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环境条件下 d 0 早期过渡金属的电催化甲烷功能化
DOI：
10.1002/anie.202107720
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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：
Deng, Jiao;Lin, Sheng‐Chih;Fuller, III, Jack T.;Zandkarimi, Borna;Chen, Hao Ming;Alexandrova, Anastassia N.;Liu, Chong
偏远地区甲烷（CH 4）的不希望的损失欢迎在现场环境中功能化CH 4而无需大量基础设施投资的方法。最近，我们发现钒（V）-氧与硫酸氢盐配体的电化学氧化导致在环境条件下CH 4活化。关键问题是这样的观察是一次性的巧合还是电催化剂设计的一般策略。在此，建立了一个一般的方案，电催化活化CH 4与d 0早期过渡金属。以钛（IV）、钒（V）和铬（VI）物种作为模型系统，详细介绍了预催化剂的分子结构、电催化动力学和机理。 在限制转换的单电子电化学氧化之后，产生的配体中心的阳离子自由基以低活化能和高选择性活化CH 4。反应性在第4 ~ 6周期的早过渡金属中具有普遍性，不同的早过渡金属的反应性趋势与其d轨道能量在周期表中的分布有关。我们的研究结果为开发天然气的先进环境电催化剂提供了新的化学见解。
The undesirable loss of methane (CH4) at remote locations welcomes approaches that ambiently functionalize CH4on‐site without intense infrastructure investment. Recently, we found that electrochemical oxidation of vanadium(V)‐oxo with bisulfate ligand leads to CH4activation at ambient conditions. The key question is whether such an observation is a one‐off coincidence or a general strategy for electrocatalyst design. Here, a general scheme of electrocatalytic CH4activation with d0early transition metals is established. The pre‐catalysts’ molecular structure, electrocatalytic kinetics, and mechanism were detailed for titanium (IV), vanadium (V), and chromium (VI) species as model systems. After a turnover‐limiting one‐electron electrochemical oxidation, the yielded ligand‐centered cation radicals activate CH4with low activation energy and high selectivity. The reactivities are universal among early transition metals from Period 4 to 6, and the reactivities trend for different early transition metals correlate with their d orbital energies across periodic table. Our results offer new chemical insights towards developing advanced ambient electrocatalysts of natural gas.