Abstract

Understanding the mechanism and selectivity of CO₂ catalytic conversion by H₂ on a specific catalyst is of great significance in the context of renewable energy storage from a societal and technological point of view. In this paper, based on the density functional theory calculations, the possible reaction networks of CO₂ hydrogenation on the Ni₁₃ cluster are studied systematically. The adsorption energies of the reaction intermediates at various possible adsorption sites, the reaction energies and the activation energies of each elementary reaction are calculated. The results suggest that the adsorption properties of the CO₂ and the intermediates on the Ni₁₃ cluster are different from the specific crystal plane such as Ni(111) surface, and the intermediates are highly activated on the Ni₁₃ surface. The most advantageous pathways for the production of HCOOH, CH₃OH, and CH₄ are determined, and the activation barrier of the corresponding rate-determining step is 1.63 eV, 1.55 eV, and 1.55 eV, respectively. This indicates that the Ni₁₃ cluster has higher activity towards CO₂ catalytic conversion compared with other catalysts such as Cu(111), Ni(111), and Pt/Ni(111) surface. Furthermore, the H₃CO* hydrogenation or the dissociation is demonstrated to be the crucial step in determining the selectivity for CH₃OH and CH₄.

Graphic Abstract

The mechanism of CO₂ hydrogenation on Ni₁₃ cluster was determined by density functional theory calculation.

中文翻译：

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Ni 13团簇上H 2催化CO 2催化转化的DFT研究

摘要

从社会和技术的观点来看，在可再生能源存储的背景下，了解H ₂在特定催化剂上催化CO ₂催化转化的机理和选择性具有重要意义。本文基于密度泛函理论计算，系统研究了Ni ₁₃团簇上CO ₂加氢反应的可能网络。计算了在各种可能的吸附位点上反应中间体的吸附能，各基本反应的反应能和活化能。结果表明，CO ₂和中间体对Ni ₁₃的吸附性能团簇与特定的晶面（例如Ni（111）表面）不同，并且中间体在Ni ₁₃表面上高度活化。确定了产生HCOOH，CH ₃ OH和CH ₄的最有利途径，相应的速率确定步骤的活化势垒分别为1.63 eV，1.55 eV和1.55 eV。这表明与其他催化剂（例如Cu（111），Ni（111）和Pt / Ni（111）表面）相比，Ni ₁₃簇具有更高的CO ₂催化转化活性。此外，H ₃ CO *氢化或离解被证明是确定CH ₃选择性的关键步骤OH和CH ₄。

图形摘要

通过密度泛函理论计算确定了Ni ₁₃团簇上CO ₂加氢的机理。