Abstract：
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.
摘要：
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，这归因于关键Ru-H/Ru-OH中间体的强键合强度和活性Ru位点上缓慢的水解离速率。在这里，通过水凝胶密封-热解-蚀刻策略引入了注入钌纳米簇（Ru/FNPC）的半离子F修饰的N掺杂多孔碳，以实现高效的pH通用氢气生成。受益于Ru纳米簇(RuNCs)和分层F之间的协同效应，N-共掺杂多孔碳载体，这种合成的催化剂在所有pH水平下显示出优异的HER反应性和耐久性。在碱性条件下，在10mAcm-2的电流密度下，最佳的8Ru/FNPC可提供17.8、71.2和53.8mV的超低超电势，中性,和酸性介质，分别。密度泛函理论（DFT）计算表明，支撑RuNC的F掺杂衬底削弱了Ru位点上H和OH的吸附能，并降低了HER基本步骤的能垒，从而增强Ru位点的内在活性并加速HER动力学。这项工作为通过注入超细金属NC的多孔碳基底设计先进的电催化剂提供了新的视角，用于能量转换应用。
