The rational design and construction of inexpensive and highly active electrocatalysts for hydrogen evolution reaction (HER) is of great importance for water splitting. Herein, we develop a facile approach for preparation of porous carbon-confined Ru-doped Cu nanoparticles (denoted as Ru-Cu@C) by direct pyrolysis of the Ru-exchanged Cu-BTC metal–organic framework. When served as the electrocatalyst for HER, strikingly, the obtained Ru-Cu@C catalyst exhibits an ultralow overpotential (only 20 mV at 10 mA cm⁻²) with a small Tafel slope of 37 mV dec⁻¹ in alkaline electrolyte. The excellent performance is comparable or even superior to that of commercial Pt/C catalyst. Density functional theory (DFT) calculations confirm that introducing Ru atoms into Cu nanocrystals can significantly alter the desorption of H₂ to achieve a close-to-zero hydrogen adsorption energy and thereby boost the HER process. This strategy gives a fresh impetus to explore low-cost and high-performance catalysts for HER in alkaline media.

合理设计和构建廉价且高活性的析氢反应（HER）电催化剂对于水分解具有重要意义。在此，我们开发了一种简便的方法，通过直接热解 Ru 交换的 Cu-BTC 金属有机骨架来制备多孔碳限制的 Ru 掺杂 Cu 纳米粒子（表示为 Ru-Cu@C）。当用作 HER 的电催化剂时，令人惊讶的是，所获得的 Ru-Cu@C 催化剂表现出超低的过电位（在 10 mA cm ^{-2时仅为 20 mV）和 37 mV dec -1}的小 Tafel 斜率在碱性电解液中。其优异性能可媲美甚至优于商用Pt/C催化剂。密度泛函理论 (DFT) 计算证实，将 Ru 原子引入 Cu 纳米晶体可以显着改变 H ₂的解吸，从而实现接近于零的氢吸附能，从而促进 HER 过程。这一策略为探索碱性介质中 HER 的低成本和高性能催化剂提供了新的动力。