Hu Dongxiong, Wang Yongjie, Chen Weiheng, Jiang Zhongqing, Deng Binglu, Jiang Zhong-Jie
Guangzhou Key Laboratory for Surface Chemistry of Energy Materials, Guangdong Engineering and Technology Research Center for Surface Chemistry of Energy Materials, College of Environment and Energy, South China University of Technology, Guangzhou, 510006, P. R. China.
Guangdong Provincial Key Laboratory of Semiconductor Optoelectronic Materials and Intelligent Photonic Systems, Harbin Institute of Technology, Shenzhen, 518055, P. R. China.
Small. 2024 Oct;20(40):e2402652. doi: 10.1002/smll.202402652. Epub 2024 Jun 4.
The optimization of metal-support interactions is used to fabricate noble metal-based nanoclusters with high activity for hydrogen evolution reaction (HER) in acid media. Specifically, the oxygen-defective MnO nanosheets supported Pt nanoclusters of ≈1.71 nm in diameter (Pt/V·-MnO NSs) are synthesized through the controlled solvothermal reaction. The Pt/V·-MnO NSs show a superior activity and excellent stability for the HER in the acidic media. They only require an overpotential of 19 mV to drive -10 mA cm and show negligible activity loss at -10 and -250 mA cm for >200 and >60 h, respectively. Their Pt mass activity is 12.4 times higher than that of the Pt/C and even higher than those of many single-atom based Pt catalysts. DFT calculations show that their high HER activity arises mainly from the strong metal-support interaction between Pt and MnO. It can facilitate the charge transfer from MnO to Pt, optimizing the H adsorption on the catalyst surface and promoting the evolution of H through the Volmer-Tafel mechanism. The oxygen vacancies in the V·-MnO NSs are found to be inconducive to the high activity of the Pt/V·-MnO NSs, highlighting the great importance to reduce the vacancy levels in V·-MnO NSs.
通过优化金属-载体相互作用来制备在酸性介质中对析氢反应（HER）具有高活性的贵金属基纳米团簇。具体而言，通过可控的溶剂热反应合成了直径约为1.71 nm的氧缺陷MnO纳米片负载的Pt纳米团簇（Pt/V·-MnO NSs）。Pt/V·-MnO NSs在酸性介质中对HER表现出优异的活性和稳定性。它们驱动-10 mA cm⁻²仅需19 mV的过电位，并且在-10和-250 mA cm⁻²下分别超过200和60 h时活性损失可忽略不计。其Pt质量活性比Pt/C高12.4倍，甚至高于许多单原子基Pt催化剂。密度泛函理论计算表明，它们的高HER活性主要源于Pt与MnO之间强烈的金属-载体相互作用。这可以促进电荷从MnO转移到Pt，优化催化剂表面的H吸附，并通过Volmer-Tafel机制促进H的析出。发现V·-MnO NSs中的氧空位不利于Pt/V·-MnO NSs的高活性，突出了降低V·-MnO NSs中空位水平的重要性。
