Wei Shaoqiang, Zhao Ran, Yu Wenbo, Li Lei, Zhang Min
College of Physics and Electronic Information, Inner Mongolia Normal University, Hohhot 010022, China.
Inner Mongolia Key Laboratory for Physics and Chemistry of Functional Materials, Hohhot 010022, China.
Molecules. 2024 Jul 26;29(15):3517. doi: 10.3390/molecules29153517.
Exploring highly active electrocatalysts as platinum (Pt) substitutes for the oxygen reduction reaction (ORR) remains a significant challenge. In this work, single Mn embedded nitrogen-doped graphene (MnN) with and without halogen ligands (F, Cl, Br, and I) modifying were systematically investigated by density functional theory (DFT) calculations. The calculated results indicated that these ligands can transform the and orbitals of Mn atom in MnN near the Fermi-level into dz2 orbital, and shift the -band center away from the Fermi-level to reduce the adsorption capacity for reaction intermediates, thus enhancing the ORR catalytic activity of MnN. Notably, Br and I modified MnN respectively with the lowest overpotentials of 0.41 and 0.39 V, possess superior ORR catalytic activity. This work is helpful for comprehensively understanding the ligand modification mechanism of single-atom catalysts and develops highly active ORR electrocatalysts.
探索高活性电催化剂作为铂（Pt）的替代品用于氧还原反应（ORR）仍然是一项重大挑战。在这项工作中，通过密度泛函理论（DFT）计算系统地研究了有和没有卤素配体（F、Cl、Br和I）修饰的单锰嵌入氮掺杂石墨烯（MnN）。计算结果表明，这些配体可以将费米能级附近的MnN中Mn原子的 和 轨道转变为dz2轨道，并使 -带中心远离费米能级，以降低对反应中间体的吸附能力，从而提高MnN的ORR催化活性。值得注意的是，Br和I修饰的MnN分别具有0.41和0.39 V的最低过电位，具有优异的ORR催化活性。这项工作有助于全面理解单原子催化剂的配体修饰机理，并开发高活性的ORR电催化剂。
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