The unbefitting binding energy for H*/OH* with Ni sites greatly restrains the electrochemical activity of Ni for the hydrogen evolution reaction (HER). Herein, Ni nanograins incorporated with trace Rh (denoted as 3D RhNi) are synthesized through combining a facile ion-absorption and subsequent thermal reduction treatment, in which Rh increases the local charge density of Ni sites, dramatically accelerating the electrochemical kinetics of HER. Experimentally, the Rh–Ni catalyst with only 0.1 at. % Rh element exhibits superior HER activity among the reported Ni-based materials, whose overpotential is only 37 mV and 18 mV at 10 mA/cm² in 1.0 M KOH and 0.5 M H₂SO₄, respectively. DFT calculations further identify that the resultant catalyst possesses appropriate intermediate binding energy in both acidic and alkaline conditions toward HER. This study provides a strategy to manipulate the local electronic structure for significantly improving the activity in surface catalysis.

中文翻译：

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痕量 Rh 通过增加局部电荷激活表面镍，实现高效的 pH 通用氢气生成


H*/OH* 与 Ni 位点不合适的结合能极大地抑制了 Ni 对析氢反应 （HER） 的电化学活性。在此，掺入痕量 Rh 的 Ni 纳米晶（表示为 3D RhNi）是通过结合简单的离子吸收和随后的热还原处理合成的，其中 Rh 增加了 Ni 位点的局部电荷密度，显着加速了 HER 的电化学动力学。实验上，Rh-Ni 催化剂的 Rt-Ni 含量仅为 0.1 at。在已报道的镍基材料中，% Rh 元素表现出优异的 HER 活性，在 1.0 M KOH 和 0.5 M H₂SO₄ 中，其过电位在 10 mA/cm² 时分别仅为 37 mV 和 18 mV。DFT 计算进一步确定，所得催化剂在酸性和碱性条件下都具有适当的与 HER 的中间结合能。本研究提供了一种操纵局部电子结构的策略，以显着提高表面催化的活性。