Abstract The hydrogenation of CO2 to formic acid is an important reaction in environmental catalysis, which can both alleviate the greenhouse effect and produce useful chemicals. Platinum element catalysts need to be investigated to realize large-scale development due to the expensive and scarce features. In this work, CO2 hydrogenation to formic acid over Pt4 cluster doped single-vacancy graphene was investigated using density functional theory. Catalyst configuration was optimized to perform corresponding gas adsorption and reduction reaction. Four reaction pathways were explored according to the reaction mechanism of Langmuir-Hinshelwood (L-H), Eley-Rideal (E-R) and termolecular Eley-Rideal (TER). Kinetic analysis was used to evaluate the reaction rate of different processes under the given temperature range, and the potential effect of CO molecule was also considered to better understand the feasibility. Results showed that Pt4/SV was a stable and high activity catalyst. The minimum activation energy among different pathways was 0.56 eV and TER could be the dominant reaction mechanism of CO2 hydrogenation. This work not only provides a promising catalyst but also gives a more deep understanding of CO2 reduction technology and the future applicability of platinum metal catalysts.

中文翻译：

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铂簇掺杂缺陷石墨烯上的 CO2 氢化成甲酸：DFT 研究

摘要 CO2加氢制甲酸是环境催化中的一个重要反应，既可以缓解温室效应，又可以生产有用的化学品。铂元素催化剂由于价格昂贵且稀缺，需要研究以实现大规模开发。在这项工作中，使用密度泛函理论研究了在 Pt4 簇掺杂的单空位石墨烯上 CO2 氢化成甲酸。优化催化剂配置以进行相应的气体吸附和还原反应。根据Langmuir-Hinshelwood（LH）、Eley-Rideal（ER）和分子分子Eley-Rideal（TER）的反应机理，探索了四种反应途径。动力学分析用于评估在给定温度范围内不同过程的反应速率，并且还考虑了 CO 分子的潜在影响，以更好地了解可行性。结果表明，Pt4/SV 是一种稳定且高活性的催化剂。不同途径中的最小活化能为0.56 eV，TER可能是CO2加氢的主要反应机制。这项工作不仅提供了一种有前景的催化剂，而且使人们对二氧化碳还原技术和铂金属催化剂的未来适用性有了更深入的了解。