Khanam Romana, Rasool Anjumun, Dar Manzoor Ahmad
Department of Chemistry, Islamic University of Science and Technology, Awantipora, Jammu and Kashmir, 192122, India.
Chemphyschem. 2025 Jul 18:e2500167. doi: 10.1002/cphc.202500167.
Design of transition metal-free electrocatalysts for energy conversion processes, such as oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), holds great promise to advance the renewable energy technologies based on fuel cells and metal air batteries. Herein, a series of main group single-atom-doped holey graphyne (hG) systems for catalyzing ORR and OER using density functional theory calculations are investigated. The influence of single-atom dopants on the structure and electronic properties of hG is examined, observing a general decrease in the bandgap due to the presence of defect-like dopant states near the Fermi level, which facilitates enhanced charge transfer from the doped hG systems to the ORR/OER intermediates. The simulated free energy pathways for ORR and OER demonstrate that Ga-doped hG exhibits excellent catalytic activity toward ORR, while Ge-doped hG emerges as a promising candidate for OER. The ORR overpotential correlated very strongly with the adsorption free energy of the *OH intermediate, highlighting its crucial role in modulating ORR activity. These findings provide valuable insights for the rational design and development of high-performance electrocatalysts for energy conversion applications.
用于能量转换过程（如氧还原反应（ORR）和析氧反应（OER））的无过渡金属电催化剂的设计，对于推进基于燃料电池和金属空气电池的可再生能源技术具有巨大的前景。在此，使用密度泛函理论计算研究了一系列用于催化ORR和OER的主族单原子掺杂多孔石墨炔（hG）体系。研究了单原子掺杂剂对hG结构和电子性质的影响，观察到由于费米能级附近存在类缺陷掺杂态，带隙普遍减小，这有利于增强从掺杂hG体系到ORR/OER中间体的电荷转移。ORR和OER的模拟自由能路径表明，Ga掺杂的hG对ORR表现出优异的催化活性，而Ge掺杂的hG成为OER的有希望的候选者。ORR过电位与*OH中间体的吸附自由能密切相关，突出了其在调节ORR活性中的关键作用。这些发现为合理设计和开发用于能量转换应用的高性能电催化剂提供了有价值的见解。
