The development of active, durable, and earth-abundant multifunctional electrocatalysts is of importance for hydrogen energy conversion and storage. Here, we report a facile strategy to synthesize earth-abundant nickel boride nanoparticles supported on reduced graphene oxide (Ni₃B/rGO) as multifunctional electrocatalysts for both hydrogen oxidation reaction and overall water splitting. The Ni₃B/rGO catalysts produce a hydrogen oxidation reaction current density of 2.39 mA cm⁻² at an overpotential of 100 mV vs. reversible hydrogen electrode, being comparable to commercial Pt/C (2.95 mA cm⁻²) and 60 times as high as bare Ni/rGO (0.04 mA cm⁻²). In addition, the Ni₃B/rGO-based alkali electrolyzer affords 100 mA cm⁻² at a cell voltage input of 1.85 V for electrocatalytic overall water splitting. Density functional theory calculations further demonstrate that the Ni₃B/rGO catalysts possess optimal adsorption energies of both H∗ and OH∗ intermediates, which are favorable to electrocatalytic hydrogen electrochemistry in an alkaline medium. This work opens a new avenue toward the rational design of high-performance platinum group metal-free multifunctional electrocatalysts for the hydrogen economy.

开发活性、耐用、储量丰富的多功能电催化剂对于氢能转换和储存具有重要意义。在这里，我们报告了一种简单的策略来合成负载在还原氧化石墨烯 (Ni ₃ B/rGO)上的地球丰富的硼化镍纳米粒子作为用于氢氧化反应和整体水分解的多功能电催化剂。与可逆氢电极相比，Ni ₃ B/rGO 催化剂在 100 mV 的过电位下产生 2.39 mA cm ^-2的氢氧化反应电流密度，与商业 Pt/C (2.95 mA cm ^-2 )相当，是其60 倍高达裸 Ni/rGO (0.04 mA cm ^-2 )。此外，Ni ₃基于 B/rGO 的碱性电解槽在 1.85 V 的电池电压输入下提供 100 mA cm ^-2的电流，用于电催化整体水分解。密度泛函理论计算进一步表明，Ni ₃ B/rGO 催化剂对 H∗ 和 OH∗ 中间体均具有最佳吸附能，这有利于碱性介质中的电催化氢电化学。这项工作为合理设计用于氢经济的高性能无铂族金属多功能电催化剂开辟了一条新途径。