Jiang Yongzhen, Zou Wenxu, Li Yadong, Cai Yingxiang
Department of Physics, Nanchang University, Jiangxi, Nanchang 330031, P. R. China.
Phys Chem Chem Phys. 2022 Jan 4;24(2):975-981. doi: 10.1039/d1cp03340a.
Single-atom catalysis is the new frontier of heterogeneous catalysis and has attracted considerable attention as it exhibits great potential in hydrogen evolution to mitigate energy crisis and environmental issues. The support materials for single-atom catalysts (SACs) play a significant role in stabilizing the metal atoms, preventing their aggregation, and enhancing the catalytic activity. Two-dimensional sp hybridized PHE-graphene might be a real support for SACs due to the potential energy well induced by its enneagon, hexagon and pentagon carbon rings. In this study, eleven transition metal (TM) atoms adsorbed on PHE-graphene (TM@PHEs) are taken into account based on density functional theory (DFT) and PHE-graphene is proved to be an ideal single-atom carrier for water splitting. In particular, the TM@PHEs (TM = Fe, Ni, Ru, and Pd) exhibit high catalytic activity toward the hydrogen evolution reaction (HER). The reaction path of water splitting is also determined. Due to their much lower energy barrier, both Fe@PHE and Ru@PHE are more promising SACs. In addition, the charge density difference, Bader charge analysis and spin projected density of states (PDOS) are investigated.
单原子催化是多相催化的新前沿领域，因其在析氢方面展现出缓解能源危机和环境问题的巨大潜力而备受关注。单原子催化剂（SACs）的载体材料在稳定金属原子、防止其聚集以及提高催化活性方面发挥着重要作用。二维sp杂化的菲石墨烯（PHE-石墨烯）可能是一种理想的单原子催化剂载体，这是由于其九边形、六边形和五边形碳环所诱导的势能阱。在本研究中，基于密度泛函理论（DFT）考虑了吸附在PHE-石墨烯上的11种过渡金属（TM）原子（TM@PHEs），并证明PHE-石墨烯是一种理想的用于水分解的单原子载体。特别地，TM@PHEs（TM = Fe、Ni、Ru和Pd）对析氢反应（HER）表现出高催化活性。同时还确定了水分解的反应路径。由于其较低的能垒，Fe@PHE和Ru@PHE都是更有前景的单原子催化剂。此外，还研究了电荷密度差、巴德电荷分析和自旋投影态密度（PDOS）。
