Developing high electroactivity ruthenium (Ru)‐based electrocatalysts for pH‐universal hydrogen evolution reaction (HER) is challenging due to the strong bonding strengths of key Ru─H/Ru─OH intermediates and sluggish water dissociation rates on active Ru sites. Herein, a semi‐ionic F‐modified N‐doped porous carbon implanted with ruthenium nanoclusters (Ru/FNPC) is introduced by a hydrogel sealing‐pyrolying‐etching strategy toward highly efficient pH‐universal hydrogen generation. Benefiting from the synergistic effects between Ru nanoclusters (Ru NCs) and hierarchically F, N‐codoped porous carbon support, such synthesized catalyst displays exceptional HER reactivity and durability at all pH levels. The optimal 8Ru/FNPC affords ultralow overpotentials of 17.8, 71.2, and 53.8 mV at the current density of 10 mA cm−2 in alkaline, neutral, and acidic media, respectively. Density functional theory (DFT) calculations elucidate that the F‐doped substrate to support Ru NCs weakens the adsorption energies of H and OH on Ru sites and reduces the energy barriers of elementary steps for HER, thus enhancing the intrinsic activity of Ru sites and accelerating the HER kinetics. This work provides new perspectives for the design of advanced electrocatalysts by porous carbon substrate implanted with ultrafine metal NCs for energy conversion applications.

中文翻译：

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注入钌纳米团簇的半离子 F 改性氮掺杂多孔碳可实现高效 pH 通用制氢


由于关键 Ru─H/Ru─OH 中间体的强键合强度和活性 Ru 位点上水解离速率缓慢，开发用于 pH 通用析氢反应 (HER) 的高电活性钌 (Ru) 基电催化剂具有挑战性。在此，通过水凝胶密封-热解-蚀刻策略引入了植入钌纳米团簇的半离子F改性N掺杂多孔碳（Ru/FNPC），以实现高效pH通用氢生成。受益于Ru纳米团簇（Ru NCs）和分级F、N共掺杂多孔碳载体之间的协同效应，这种合成的催化剂在所有pH水平下都表现出优异的HER反应性和耐久性。最佳的 8Ru/FNPC 在碱性、中性和酸性介质中在 10 mA cm−2 的电流密度下分别提供 17.8、71.2 和 53.8 mV 的超低过电势。密度泛函理论（DFT）计算表明，负载Ru NCs的F掺杂基质削弱了Ru位点上H和OH的吸附能，降低了HER基本步骤的能垒，从而增强了Ru位点的本征活性并加速了HER 动力学。这项工作为通过植入超细金属NC的多孔碳基底设计用于能量转换应用的先进电催化剂提供了新的视角。