Hefei National Laboratory for Physical Sciences at the Microscale and Department of Chemistry, University of Science & Technology of China, 230026, Hefei, Anhui, China.
National Synchrotron Radiation Laboratory, University of Science & Technology of China, 230029, Hefei, China.
Nat Commun. 2019 Mar 14;10(1):1217. doi: 10.1038/s41467-019-09210-0.
Molybdenum disulfide is naturally inert for alkaline hydrogen evolution catalysis, due to its unfavorable water adsorption and dissociation feature originated from the unsuitable orbital orientation. Herein, we successfully endow molybdenum disulfide with exceptional alkaline hydrogen evolution capability by carbon-induced orbital modulation. The prepared carbon doped molybdenum disulfide displays an unprecedented overpotential of 45 mV at 10 mA cm, which is substantially lower than 228 mV of the molybdenum disulfide and also represents the best alkaline hydrogen evolution catalytic activity among the ever-reported molybdenum disulfide catalysts. Fine structural analysis indicates the electronic and coordination structures of molybdenum disulfide have been significantly changed with carbon incorporation. Moreover, theoretical calculation further reveals carbon doping could create empty 2p orbitals perpendicular to the basal plane, enabling energetically favorable water adsorption and dissociation. The concept of orbital modulation could offer a unique approach for the rational design of hydrogen evolution catalysts and beyond.
二硫化钼由于其不合适的轨道取向导致对碱性析氢催化的水吸附和离解特性不利，因此在本质上是惰性的。在此，我们通过碳诱导的轨道调制成功赋予二硫化钼优异的碱性析氢性能。所制备的碳掺杂二硫化钼在 10 mA cm 下表现出前所未有的 45 mV 的过电势，远低于二硫化钼的 228 mV，并且在已报道的二硫化钼催化剂中代表了最佳的碱性析氢催化活性。精细结构分析表明，碳的掺入显著改变了二硫化钼的电子和配位结构。此外，理论计算进一步表明，掺杂碳可以在垂直于基面的方向上创建空的 2p 轨道，从而有利于能量上有利的水吸附和离解。轨道调制的概念为合理设计析氢催化剂及其他领域提供了一种独特的方法。
