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The Effect of Organic Additives on the Activity and Selectivity of CO 2 Electroreduction: The Role of Functional Groups
Author(s) -
Xu Wenbin,
Qiu Yanling,
Zhang Taotao,
Li Xianfeng,
Zhang Huamin
Publication year - 2018
Publication title -
chemsuschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.412
H-Index - 157
eISSN - 1864-564X
pISSN - 1864-5631
DOI - 10.1002/cssc.201801458
Subject(s) - selectivity , chemistry , catalysis , density functional theory , electrochemistry , molecule , transition metal , electron transfer , electrocatalyst , metal , computational chemistry , electrode , organic chemistry
Electrochemical reduction of CO 2 (ERC) to useful chemicals is an environmentally and technologically significant process. The process is confronted with significant challenges to simultaneously enhance the catalyst activity and product selectivity. In this paper, the effects of organic additives on the ERC process were systematically investigated by using DFT to screen additives with different functional groups for enhanced activity and selectivity. In particular, the additives with −NH 3 + and −SO 3 H groups had a remarkably positive effect on the ERC activity and hydrocarbon selectivity, which were predicted to impart a positive shift on onset potential of approximately 162 and 108 mV, respectively. Importantly, the additive can accelerate the electron transfer of the intermediate and tune the electronic structure of the catalyst surface, resulting in a clear deviation from transition‐metal scaling lines. Combining bonding energy of crucial intermediates with partial atomic charge analysis, we rationalized the negative effect of high concentration additives and confirmed the proposed electron transfer model. Furthermore, additive molecules containing functional groups with positive charges and maximizing the deviation from transition‐metal scaling lines are meaningful strategies to design and choose organic additives to enhance activity and selectivity of ERC.