https://scholars.lib.ntu.edu.tw/handle/123456789/606875
標題: | Electrocatalytic Methane Functionalization with d0 Early Transition Metals Under Ambient Conditions | 作者: | Deng J Lin S.-C Fuller J.T III, Zandkarimi B Chen H.M Alexandrova A.N Liu C. HAO MING CHEN |
關鍵字: | ambient conditions;d0 electronic structure;early transition metals;electrocatalysis;methane functionalization;Activation energy;Chromium compounds;Electrocatalysis;Electrocatalysts;Investments;Ligands;Methane;Titanium compounds;Transition metals;Ambient conditions;CH 4;D0 electronic structure;Early-transition metals;Electrocatalytic;Electronic.structure;Infrastructure investment;Methane functionalization;Precatalysts;Remote location;Electronic structure | 公開日期: | 2021 | 卷: | 60 | 期: | 51 | 起(迄)頁: | 26630-26638 | 來源出版物: | Angewandte Chemie - International Edition | 摘要: | The undesirable loss of methane (CH4) at remote locations welcomes approaches that ambiently functionalize CH4 on-site without intense infrastructure investment. Recently, we found that electrochemical oxidation of vanadium(V)-oxo with bisulfate ligand leads to CH4 activation 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 CH4 activation with d0 early 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 CH4 with 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. ? 2021 Wiley-VCH GmbH |
URI: | https://www.scopus.com/inward/record.uri?eid=2-s2.0-85118806134&doi=10.1002%2fanie.202107720&partnerID=40&md5=5ea51d1a910f675a34022535b3870928 https://scholars.lib.ntu.edu.tw/handle/123456789/606875 |
ISSN: | 14337851 | DOI: | 10.1002/anie.202107720 |
顯示於: | 化學系 |
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