Scholarlink

<p>This study employs density functional theory (DFT) to investigate Rh and N-doped coronene (RhN<sub>4</sub>–Cor) and its carboxyl-functionalized analogue (RhN<sub>4</sub>–Cor(COOH)<sub>6</sub>) as bifunctional catalysts for the oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER). Ab initio molecular dynamics (ADMP) simulations at 300&#xa0;K confirmed structural stability. Structural, DOS, and HOMO–LUMO analyses showed that Rh, N, and COOH substitutions activate the coronene surface, while XAS revealed Rh<sup>3+</sup> with a low-spin d<sup>6</sup> configuration, enabling strong O<sub>2</sub> and intermediate binding. NBO analysis indicated strong metal–ligand interactions that enhance charge transfer. RhN<sub>4</sub>–Cor(COOH)<sub>6</sub> favors the 2e⁻ ORR pathway due to the low *O<sub>2</sub> → OOH barrier and exhibits a favorable HER mechanism (ΔG<sub>H*</sub> =  − 0.18&#xa0;eV) that proceeds predominantly via the Volmer–Heyrovsky pathway. Low overpotentials (η<sup>ORR</sup> = 0.63&#xa0;V, η<sup>HER</sup> =  − 0.18&#xa0;V) and a calculated Faradaic efficiency of 100% under ideal conditions enumerates its high catalytic performance, making RhN<sub>4</sub>–Cor(COOH)<sub>6</sub> a promising bifunctional electrocatalyst.</p>

错误：搜索内容不能为空，请输入英文关键词
错误：关键词超出字数限制，请精简
高级检索

Edge carboxyl group functionalized RhN4-coronene as a catalyst for oxygen reduction and hydrogen evolution reactions: a DFT study

  • 期刊论文

  • 发表日期：

    2025年10月29日

查看全文
  • Angappan Kausalya,
  • Senthilkumar Lakshmipathi

摘要

This study employs density functional theory (DFT) to investigate Rh and N-doped coronene (RhN4–Cor) and its carboxyl-functionalized analogue (RhN4–Cor(COOH)6) as bifunctional catalysts for the oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER). Ab initio molecular dynamics (ADMP) simulations at 300 K confirmed structural stability. Structural, DOS, and HOMO–LUMO analyses showed that Rh, N, and COOH substitutions activate the coronene surface, while XAS revealed Rh3+ with a low-spin d6 configuration, enabling strong O2 and intermediate binding. NBO analysis indicated strong metal–ligand interactions that enhance charge transfer. RhN4–Cor(COOH)6 favors the 2e⁻ ORR pathway due to the low *O2 → OOH barrier and exhibits a favorable HER mechanism (ΔGH* =  − 0.18 eV) that proceeds predominantly via the Volmer–Heyrovsky pathway. Low overpotentials (ηORR = 0.63 V, ηHER =  − 0.18 V) and a calculated Faradaic efficiency of 100% under ideal conditions enumerates its high catalytic performance, making RhN4–Cor(COOH)6 a promising bifunctional electrocatalyst.