Hu Qi, Cao Jianyong, Qi Shuai, Meng Na, Zhao Jingwen, Huang Tianchi, You Jiao, Liang Taiyu, Shang Chunyan, Yu Jiaying, Yang Hengpan, He Chuanxin
College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen, Guangdong, People's Republic of China.
College of Integrated Circuits and Optoelectronic Chips, Shenzhen Technology University, 518118, Shenzhen, Guangdong, China.
Angew Chem Int Ed Engl. 2025 Jan 21;64(4):e202416402. doi: 10.1002/anie.202416402. Epub 2024 Nov 2.
Recently, Ru single atoms supported on carbon nanomaterials have demonstrated ultrahigh activity for acid hydrogen evolution reaction (HER), however their neutral HER activity remains low due to the sluggish kinetics for both the water dissociation step to generate H* intermediates and subsequent H* recombination in neutral electrolytes. Here, we synthesize ordered low-coordinated Ru atom arrays confined in Mn oxides (i.e., LiMnO) for concurrently boosting the water dissociation and H* recombination, thus achieving a 6-fold HER activity enhancement than commercial Pt/C in neutral media. Control experiments indicate that low-coordinated Ru atoms with strong affinity to oxygen atoms of water molecules facilitate the water dissociation to rapidly generate H*. More importantly, both electrochemical and theoretic results uncover that the array-like structure allows the activation of two water molecules on two adjacent Ru atoms for enabling direct H*-H* recombination via the Tafel step, while isolated Ru atoms can only activate water one by one for recombining H* via the sluggish Heyrovsky step. Clearly, this work paves new avenues to boosting the electrocatalytic activity by constructing ordered metal atoms assembles with controllable coordination environments.
最近，负载在碳纳米材料上的钌单原子对酸性析氢反应（HER）表现出超高活性，然而，由于在中性电解质中生成H中间体的水解离步骤以及随后的H复合动力学缓慢，它们的中性HER活性仍然较低。在此，我们合成了限制在锰氧化物（即LiMnO）中的有序低配位钌原子阵列，以同时促进水解离和H复合，从而在中性介质中实现了比商业Pt/C高6倍的HER活性增强。对照实验表明，与水分子中的氧原子具有强亲和力的低配位钌原子促进了水解离以快速生成H。更重要的是，电化学和理论结果都揭示出，阵列状结构允许在两个相邻的钌原子上激活两个水分子，从而通过塔菲尔步骤实现直接的H*-H复合，而孤立的钌原子只能逐个激活水分子以通过缓慢的海洛夫斯基步骤复合H。显然，这项工作为通过构建具有可控配位环境的有序金属原子组装体来提高电催化活性开辟了新途径。
