Cheng Fanpeng, Peng Xianyun, Hu Lingzi, Yang Bin, Li Zhongjian, Dong Chung-Li, Chen Jeng-Lung, Hsu Liang-Ching, Lei Lecheng, Zheng Qiang, Qiu Ming, Dai Liming, Hou Yang
Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou, 310027, China.
Institute of Zhejiang University - Quzhou, Quzhou, 324000, China.
Nat Commun. 2022 Oct 30;13(1):6486. doi: 10.1038/s41467-022-34278-6.
Two-dimensional metal-organic frameworks (MOFs) have been explored as effective electrocatalysts for hydrogen evolution reaction (HER). However, the sluggish water activation kinetics and structural instability under ultrahigh-current density hinder their large-scale industrial applications. Herein, we develop a universal ligand regulation strategy to build well-aligned Ni-benzenedicarboxylic acid (BDC)-based MOF nanosheet arrays with S introducing (S-NiBDC). Benefiting from the closer p-band center to the Fermi level with strong electron transferability, S-NiBDC array exhibits a low overpotential of 310 mV to attain 1.0 A cm with high stability in alkaline electrolyte. We speculate the newly-constructed triangular "Ni-S" motif as the improved HER active region based on detailed mechanism analysis and structural characterization, and the enhanced covalency of Ni-O bonds by S introducing stabilizes S-NiBDC structure. Experimental observations and theoretical calculations elucidate that such Ni sites in "Ni-S" center distinctly accelerate the water activation kinetics, while the S site readily captures the H atom as the optimal HER active site, boosting the whole HER activity.
二维金属有机框架（MOFs）已被探索用作析氢反应（HER）的有效电催化剂。然而，缓慢的水活化动力学以及在超高电流密度下的结构不稳定性阻碍了它们的大规模工业应用。在此，我们开发了一种通用的配体调控策略，以构建具有S引入（S-NiBDC）的排列良好的基于镍-苯二甲酸（BDC）的MOF纳米片阵列。受益于更接近费米能级且具有强电子转移能力的p带中心，S-NiBDC阵列在碱性电解质中表现出310 mV的低过电位，以达到1.0 A cm且具有高稳定性。基于详细的机理分析和结构表征，我们推测新构建的三角形“Ni-S”基序为改进的HER活性区域，并且通过引入S增强的Ni-O键的共价性稳定了S-NiBDC结构。实验观察和理论计算表明，“Ni-S”中心的此类Ni位点显著加速了水活化动力学，而S位点容易捕获H原子作为最佳的HER活性位点，从而提高了整体HER活性。
