Rajbongshi Bhargav, Tripathi Pragyan, Singh Abhishek Kumar, Shaijumon Manikoth M
School of Physics and Centre for Advanced Materials Research with International Engagement (CAMRIE), Indian Institute of Science Education and Research Thiruvananthapuram, Maruthamala PO, Thiruvananthapuram, Kerala, 695551, India.
Materials Research Centre, Indian Institute of Science, Bangalore, Karnataka, 560012, India.
Small. 2025 Jun 22:e2504300. doi: 10.1002/smll.202504300.
Implantation of foreign elements into a host lattice can enhance catalytic activity by modulating electronic properties. Copper (Cu), a low-cost and abundant material, shows great potential in energy conversion applications. However, its high water dissociation energy barrier limits its catalytic performance in alkaline hydrogen evolution reactions (HER). Herein, a highly scalable co-electrodeposition method is presented to enhance the electrocatalytic performance of copper for alkaline HER by incorporating rhenium (Re) into the copper lattice. The incorporated Re improves electrocatalytic activity by promoting exothermic water dissociation and enhancing water adsorption. The optimized catalyst, CuRe-10/CP, achieves an overpotential of 46 mV to drive a current density of 10 mA cm, demonstrating excellent electrochemical stability for 450 h at 50 mA cm in an alkaline medium (1.0 m KOH). Additionally, the electrochemical activity of the CuRe-10/CP is evaluated in simulated seawater and alkaline seawater, where it exhibited exceptional activity and stability. Electrochemical impedance spectroscopy (EIS), electrochemical surface area measurement (ECSA), and turnover frequency (TOF) analyses confirm the significant enhancement in catalytic performance following Re incorporation. Furthermore, in situ Raman spectroscopy, EIS, and density functional theory (DFT) studies reveal that the Re incorporation into the copper lattice significantly improves the water dissociation and intermediate adsorption. This study gives a scalable strategy for designing platinum group element free electrocatalysts for alkaline hydrogen evolution.
将外来元素植入主体晶格可以通过调节电子性质来提高催化活性。铜（Cu）作为一种低成本且储量丰富的材料，在能量转换应用中显示出巨大潜力。然而，其较高的水解离能垒限制了它在碱性析氢反应（HER）中的催化性能。在此，我们提出了一种高度可扩展的共电沉积方法，通过将铼（Re）掺入铜晶格中来提高铜在碱性HER中的电催化性能。掺入的Re通过促进放热的水解离和增强水吸附来提高电催化活性。优化后的催化剂CuRe-10/CP在驱动10 mA cm的电流密度时过电位为46 mV，在碱性介质（1.0 m KOH）中50 mA cm下表现出450 h的优异电化学稳定性。此外，还在模拟海水和碱性海水中评估了CuRe-10/CP的电化学活性，其表现出卓越的活性和稳定性。电化学阻抗谱（EIS）分析、电化学表面积测量（ECSA）和周转频率（TOF）分析证实了掺入Re后催化性能的显著增强。此外，原位拉曼光谱、EIS和密度泛函理论（DFT）研究表明，将Re掺入铜晶格显著改善了水解离和中间体吸附。本研究为设计用于碱性析氢的无铂族元素电催化剂提供了一种可扩展的策略。
