Yang Hongyu, Xia Xin, An Shijie, Huang Moujie, Ma Hao, Ye Feng, Peng Chuang, Xu Chao
Beijing Laboratory of New Energy Storage Technology, North China Electric Power University Beijing 102206 China
School of Resource and Environmental Science, Wuhan University Wuhan 430072 China.
RSC Adv. 2025 Mar 10;15(10):7682-7692. doi: 10.1039/d4ra09113b. eCollection 2025 Mar 6.
Exploring high-performance catalysts for the hydrogen evolution reaction (HER) is essential for the development of clean hydrogen energy. Single atom catalysts (SACs) have garnered significant attention due to their maximum atomic efficiency, high catalytic performance and excellent selectivity. In this work, we systematically investigated the HER activity of Ru and Fe SACs on nitrogen-doped graphene using density functional theory (DFT) calculations. Various nitrogen defect configurations (N to 4N) were examined to access their impact on structural stability and catalytic performance. The results indicate that lower N-coordinated moieties, particularly N_pyrrolic and 2N, exhibit superior HER activity, while high N-coordinated moieties (4N) demonstrate greater stability. Volcano plot analysis reveals that catalytic performance is highly sensitive to metal-support interactions, which can be effectively described using binding energy and metal charge state. Ru SACs@N_pyrrolic and Fe SACs@2N achieve the most favorable performance, with additional active sites and low overpotentials of approximately 0.26 V and 0.23 V, respectively. Bader charge analysis further confirms that moderate positive charge states enhance electronic metal-support interactions, optimizing hydrogen adsorption and desorption. These findings highlight the critical role of nitrogen coordination in tuning the electronic and energetic properties of SACs on N doped graphene, providing valuable insights into the rational design of Pt-free SACs for highly efficient HER catalysis.
探索用于析氢反应（HER）的高性能催化剂对于清洁氢能的发展至关重要。单原子催化剂（SACs）因其最大原子效率、高催化性能和出色的选择性而备受关注。在这项工作中，我们使用密度泛函理论（DFT）计算系统地研究了Ru和Fe单原子催化剂在氮掺杂石墨烯上的析氢反应活性。研究了各种氮缺陷构型（从N到4N）以了解它们对结构稳定性和催化性能的影响。结果表明，较低的N配位部分，特别是吡咯氮和2N，表现出优异的析氢反应活性，而高N配位部分（4N）表现出更高的稳定性。火山图分析表明，催化性能对金属-载体相互作用高度敏感，这可以使用结合能和金属电荷状态有效地描述。Ru单原子催化剂@吡咯氮和Fe单原子催化剂@2N实现了最有利的性能，分别具有额外的活性位点和约0.26 V和0.23 V的低过电位。巴德电荷分析进一步证实，适度的正电荷状态增强了电子金属-载体相互作用，优化了氢的吸附和解吸。这些发现突出了氮配位在调节氮掺杂石墨烯上单原子催化剂的电子和能量性质方面的关键作用，为高效析氢反应催化的无Pt单原子催化剂的合理设计提供了有价值的见解。
