Mu Wen-Lei, Luo Yu-Ting, Xia Peng-Kun, Jia Yong-Lei, Wang Pu, Pei Yong, Liu Chao
College of Advanced Interdisciplinary Studies, National University of Defense Technology, Changsha 410073, China.
College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, P. R. China.
Inorg Chem. 2024 Apr 15;63(15):6767-6775. doi: 10.1021/acs.inorgchem.4c00077. Epub 2024 Apr 3.
Electrolytic hydrogen production via water splitting holds significant promise for the future of the energy revolution. The design of efficient and abundant catalysts, coupled with a comprehensive understanding of the hydrogen evolution reaction (HER) mechanism, is of paramount importance. In this study, we propose a strategy to craft an atomically precise cluster catalyst with superior HER performance by cocoupling a MoO structural unit and a Cu(I) alkynyl cluster into a structured framework. The resulting bimetallic cluster, , encapsulates a distinctive structure [MoOCu(TC4A)(PhC≡C)], comprising a binuclear MoO subunit and a {Cu(TC4A)(PhC≡C)} cluster, both shielded by thiacalix[4]arene (TC4A) and phenylacetylene (PhC≡CH). Expanding our exploration, we synthesized two homoleptic Cu alkynyl clusters coprotected by the TC4A and PhC≡C ligands: and . Remarkably, demonstrates superior HER efficiency compared to its counterparts, achieving a current density of 10 mA cm in alkaline solution with an overpotential as low as 120 mV, significantly outperforming (178 mV) and (214 mV) nanoclusters. DFT calculations illuminate the catalytic mechanism and indicate that the intrinsically higher activity of may be attributed to the synergistic MoO-Cu(I) coupling.
通过水分解进行电解制氢对能源革命的未来具有重大前景。设计高效且丰富的催化剂，并全面了解析氢反应（HER）机理至关重要。在本研究中，我们提出了一种策略，通过将MoO结构单元和Cu（I）炔基簇共偶联到一个结构化框架中，来制备具有优异HER性能的原子精确簇催化剂。所得的双金属簇， ，封装了一种独特的结构[MoOCu(TC4A)(PhC≡C)]，其包含一个双核MoO亚基和一个{Cu(TC4A)(PhC≡C)}簇，二者均被硫代杯[4]芳烃（TC4A）和苯乙炔（PhC≡CH）屏蔽。进一步拓展我们的探索，我们合成了由TC4A和PhC≡C配体共保护的两个同配Cu炔基簇： 和 。值得注意的是， 与其同类相比表现出优异的HER效率，在碱性溶液中实现了10 mA cm的电流密度，过电位低至120 mV，显著优于 （178 mV）和 （214 mV）纳米簇。密度泛函理论（DFT）计算阐明了催化机理，并表明 的固有较高活性可能归因于协同的MoO-Cu（I）偶联。
