Multiple Adsorption of CO Molecules on Transition Metal Substitutional Impurities in Copper Surfaces

IF 3.9 3区 化学 Q2 CHEMISTRY, PHYSICAL
ChemCatChem Pub Date : 2025-07-15 DOI:10.1002/cctc.202500765
Magnus A. H. Christiansen, Wei Wang, Elvar Ö. Jónsson, Giancarlo Cicero, Hannes Jónsson
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Abstract

Copper-based catalysts are of particular interest for electrochemical reduction of (CO2RR) as products beyond CO can form. To improve activity and selectivity, several studies have focused on the addition of other elements as substitutional impurities. Although the adsorption of a single CO molecule has often been used as a descriptor for CO2RR activity, our recent calculations using the RPBE functional showed that multiple CO molecules can bind to first-row transition metal impurities. Here, we extend the study to second-row transition metals and also to a functional that explicitly includes dispersion interaction, BEEF-vdW. The binding energy of the first CO molecule on the impurity atom is found to be significantly larger than on the clean Cu(111) and Cu(100) surfaces, but the differential binding energy generally drops as more CO molecules adsorb. The dispersion interaction is found to make a significant contribution to the binding energy, in particular for the last and weakest bound CO molecule, the one that is most likely to participate in CO2RR. In some cases, four CO admolecules can bind more strongly on the impurity atom than on the clean copper surface. The adsorption of CO causes the position of the impurity atom to shift outwards and in some cases, even escape from the surface layer. The C─O stretch frequencies are calculated in order to identify possible experimental signatures of multiple CO adsorption.

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铜表面过渡金属取代杂质对CO分子的多重吸附
铜基催化剂对电化学还原(CO2RR)特别感兴趣,因为可以形成CO以外的产物。为了提高活性和选择性,一些研究集中在添加其他元素作为替代杂质上。尽管单个CO分子的吸附通常被用作CO2RR活性的描述符,但我们最近使用RPBE函数的计算表明,多个CO分子可以与第一行过渡金属杂质结合。在这里,我们将研究扩展到第二行过渡金属,也扩展到一个明确包括色散相互作用的函数,fe - vdw。杂质原子上的第一个CO分子的结合能明显大于干净的Cu(111)和Cu(100)表面上的结合能,但随着更多CO分子的吸附,其差结合能一般会下降。发现色散相互作用对结合能有显著的贡献,特别是对于最后和最弱的结合CO分子,最可能参与CO2RR。在某些情况下,四个CO分子在杂质原子上的结合比在干净的铜表面上的结合更强。CO的吸附使杂质原子的位置向外移动,在某些情况下,甚至从表层逃逸。计算了C─O拉伸频率,以确定多重CO吸附的可能实验特征。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
ChemCatChem
ChemCatChem 化学-物理化学
CiteScore
8.10
自引率
4.40%
发文量
511
审稿时长
1.3 months
期刊介绍: With an impact factor of 4.495 (2018), ChemCatChem is one of the premier journals in the field of catalysis. The journal provides primary research papers and critical secondary information on heterogeneous, homogeneous and bio- and nanocatalysis. The journal is well placed to strengthen cross-communication within between these communities. Its authors and readers come from academia, the chemical industry, and government laboratories across the world. It is published on behalf of Chemistry Europe, an association of 16 European chemical societies, and is supported by the German Catalysis Society.
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