Viability of transition metal decorated phosphorene nanoflakes as catalysts for carbon dioxide reduction: A theoretical study

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry Pub Date : 2025-07-01 DOI:10.1016/j.comptc.2025.115356

Cesar Gabriel Vera-de la Garza, Daniela Osorio Sandoval, Serguei Fomine

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Abstract

The reduction of CO₂ using transition metal-decorated phosphorene catalysts was investigated via computational methods. Calculations revealed that metal-phosphorene interactions modulate catalytic activity. Phosphorene nanoflakes decorated with metals exhibited Gibbs free binding energies between −73.3 and − 83.2 kcal/mol, with Mn showing the highest binding energy. Reaction pathway studies indicated that CO₂ reduction with H₂ favors HCOOH formation over CO. Subsequent reduction of HCOOH to CH₂O and CH₃OH displayed lower energy barriers for Mn and Fe, while Ni showed inferior efficacy. CH₄ formation from MeOH required high activation energies, becoming viable only under moderate heating (400 K). Results highlighted selectivity toward HCOOH and CH₃OH, avoiding direct CH₄ formation from CH₂O due to prohibitive kinetic barriers. Mn- and Fe-decorated phosphorene systems emerged as promising catalysts for CO₂ reduction, offering high activity and selectivity at ambient or moderately heated conditions, whereas Ni exhibited limitations.

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过渡金属修饰磷烯纳米片作为二氧化碳还原催化剂的可行性：理论研究

用计算方法研究了过渡金属修饰的磷烯催化剂对CO2的还原作用。计算表明，金属-磷烯相互作用调节催化活性。金属修饰的磷烯纳米片的吉布斯自由结合能在- 73.3 ~ - 83.2 kcal/mol之间，其中Mn的结合能最高。反应途径研究表明，CO2与H2的还原比CO更有利于HCOOH的生成。随后HCOOH还原为CH2O和CH3OH对Mn和Fe的能垒较低，而Ni的能垒较差。由MeOH生成CH4需要很高的活化能，只有在中等加热（400 K）下才可行。结果强调了对HCOOH和CH3OH的选择性，避免了CH2O直接生成CH4。Mn和fe修饰的磷烯体系在环境或中等加热条件下具有高活性和选择性，是很有前途的CO2还原催化剂，而Ni则表现出局限性。

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来源期刊

Computational and Theoretical Chemistry CHEMISTRY, PHYSICAL-

CiteScore

4.20

自引率

10.70%

发文量

331

审稿时长

31 days

期刊介绍： Computational and Theoretical Chemistry publishes high quality, original reports of significance in computational and theoretical chemistry including those that deal with problems of structure, properties, energetics, weak interactions, reaction mechanisms, catalysis, and reaction rates involving atoms, molecules, clusters, surfaces, and bulk matter.