Ab Initio Study of the C–O Bond Dissociation in CO2 Reduction by Redox and Carboxyl Routes on 3d Transition Metal Systems,The Journal of Physical Chemistry C

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Ab Initio Study of the C–O Bond Dissociation in CO2 Reduction by Redox and Carboxyl Routes on 3d Transition Metal Systems
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2021-11-24 , DOI: 10.1021/acs.jpcc.1c05468
Vivianne K. Ocampo-Restrepo ₁ , Lucas G. Verga ₁ , Juarez L. F. Da Silva ₁

Affiliation

The C–O bond dissociation of the CO₂ molecule via the reverse water gas shift reaction is crucial for several reactions used as renewable alternatives for fuel synthesis. However, our atomistic understanding of this process on transition metal (TM) clusters, where quantum-size effects might play a significant role, is far from complete. Here, we addressed the C–O bond dissociation by redox and carboxyl routes on 13-atom TM (Fe, Co, Ni, Cu) clusters using density functional theory calculations and the climbing image nudged elastic band algorithm. From the potential energy profiles, we found that CO₂ is prone to dissociate into adsorbed CO via the redox route with lower activation energies, E_a’s, than the carboxyl route on all studied TM₁₃ systems. Our results suggested that the smaller activation barrier found on the Co₁₃ cluster is due to the stronger adsorption exhibited for both CO₂ and O. By increasing the d-state occupation (from Fe to Cu), the E_a differences between CO₂ dissociation and COOH formation decrease. We associated this behavior with a decrease in the (CO₂ + H) adsorption energy from Fe₁₃ to Cu₁₃ that facilitates the COO–H bond formation and H–TM bond cleavage, i.e., favoring the carboxyl route. Also, our analyses indicate that the adsorption energies of the CO₂ and trans-COOH species are the best descriptors for the C–O bond dissociation via the redox and carboxyl routes, respectively.

中文翻译：

在 3d 过渡金属系统上通过氧化还原和羧基途径还原 CO2 中 C-O 键离解的 Ab Initio 研究

CO ₂分子通过反向水煤气变换反应的 C-O 键解离对于用作燃料合成的可再生替代品的几种反应至关重要。然而，我们对过渡金属 (TM) 簇（其中量子尺寸效应可能起重要作用）的这一过程的原子理解还远未完成。在这里，我们使用密度泛函理论计算和爬升图像轻推弹力带算法，通过氧化还原和羧基路线在 13 原子 TM（Fe、Co、Ni、Cu）簇上解决了 C-O 键解离。从势能分布中，我们发现 CO ₂易于通过氧化还原途径分解成吸附的 CO，其活化能E _a比所有研究的 TM 上的羧基途径都低_13个系统。我们的结果表明，在 Co ₁₃簇上发现的较小活化势垒是由于对 CO ₂和 O表现出更强的吸附。通过增加 d 态占据（从 Fe 到 Cu），CO ₂解离之间的E _a差异和 COOH 形成减少。我们将此行为与从 Fe ₁₃到 Cu ₁₃的 (CO ₂ + H) 吸附能的降低相关联，这促进了 COO-H 键的形成和 H-TM 键的断裂，即有利于羧基路线。此外，我们的分析表明，CO ₂和反式的吸附能-COOH 物质分别是通过氧化还原和羧基途径进行 C-O 键解离的最佳描述词。

更新日期：2021-12-09

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