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<p>Ni porphyrins possess exceptional catalytic versatility due to their electronically active metal coordination centers. To evaluate the effects of peripheral substituents on the catalytic efficacy of Ni porphyrins, the oxidative catalytic performance of Ni porphyrin derivatives has been investigated using density functional theory (DFT). The results reveal that the O-2p in H<sub>2</sub>O + O* is strongly hybridized with Ni-d, which promotes oxygen activation. The carboxylic acid group stabilizes the charged intermediates (OH*/OOH*). For TPTBP, the polybenzene ring enhances the stability of OOH*/HOOH*. The electron-withdrawing effect of TCPP synergizes with structural flexibility to achieve dissociation pathways with low energy barriers. TPYP-O is the only efficient 2e-ORR catalyst. TPTBP has a strong adsorption-conjugation synergy effect, and path 1 (O<sub>2</sub> → OOH* → H<sub>2</sub>O + O* → H<sub>2</sub>O + OH*) has no energy barriers of adsorption. It will provide theoretical references for the application of Ni-based metalloporphyrins as catalysts.</p>

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Density functional theory calculations on the interaction between adsorption redox intermediates and typical Ni porphyrin derivatives

  • 期刊论文

  • 发表日期：

    2025年9月13日

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  • Shu-qi Yang,
  • Hao-bo Zhai,
  • Zhi Li

摘要

Ni porphyrins possess exceptional catalytic versatility due to their electronically active metal coordination centers. To evaluate the effects of peripheral substituents on the catalytic efficacy of Ni porphyrins, the oxidative catalytic performance of Ni porphyrin derivatives has been investigated using density functional theory (DFT). The results reveal that the O-2p in H2O + O* is strongly hybridized with Ni-d, which promotes oxygen activation. The carboxylic acid group stabilizes the charged intermediates (OH*/OOH*). For TPTBP, the polybenzene ring enhances the stability of OOH*/HOOH*. The electron-withdrawing effect of TCPP synergizes with structural flexibility to achieve dissociation pathways with low energy barriers. TPYP-O is the only efficient 2e-ORR catalyst. TPTBP has a strong adsorption-conjugation synergy effect, and path 1 (O2 → OOH* → H2O + O* → H2O + OH*) has no energy barriers of adsorption. It will provide theoretical references for the application of Ni-based metalloporphyrins as catalysts.