DOI: 10.1073/pnas.1900761116
论文题名: Hydrogen bonding steers the product selectivity of electrocatalytic CO reduction
作者: Li J. ; Li X. ; Gunathunge C.M. ; Waegele M.M.
刊名: Proceedings of the National Academy of Sciences of the United States of America
ISSN: 0027-8424
出版年: 2019
卷: 116, 期: 19 起始页码: 9220
结束页码: 9229
语种: 英语
英文关键词: Carbon dioxide
; Catalytic selectivity
; Cation effects
; Electrocatalysis
; Hydrogen bonding
; Reduction
Scopus关键词: carbon monoxide
; cation
; copper
; electrolyte
; ethylene
; hydrocarbon
; quaternary ammonium derivative
; water
; absorption spectroscopy
; adsorption
; Article
; catalysis
; chemical interaction
; controlled study
; electric field
; hydrogen bond
; hydrogenation
; mass spectrometry
; molecular interaction
; priority journal
; static electricity
; surface property
英文摘要: The product selectivity of many heterogeneous electrocatalytic processes is profoundly affected by the liquid side of the electrocatalytic interface. The electrocatalytic reduction of CO to hydrocarbons on Cu electrodes is a prototypical example of such a process. However, probing the interactions of surface-bound intermediates with their liquid reaction environment poses a formidable experimental challenge. As a result, the molecular origins of the dependence of the product selectivity on the characteristics of the electrolyte are still poorly understood. Herein, we examined the chemical and electrostatic interactions of surface-adsorbed CO with its liquid reaction environment. Using a series of quaternary alkyl ammonium cations (methyl4N+, ethyl4N+, propyl4N+, and butyl4N+), we systematically tuned the properties of this environment. With differential electrochemical mass spectrometry (DEMS), we show that ethylene is produced in the presence of methyl4N+ and ethyl4N+ cations, whereas this product is not synthesized in propyl4N+- and butyl4N+-containing electrolytes. Surface-enhanced infrared absorption spectroscopy (SEIRAS) reveals that the cations do not block CO adsorption sites and that the cation-dependent interfacial electric field is too small to account for the observed changes in selectivity. However, SEIRAS shows that an intermolecular interaction between surface-adsorbed CO and interfacial water is disrupted in the presence of the two larger cations. This observation suggests that this interaction promotes the hydrogenation of surface-bound CO to ethylene. Our study provides a critical molecular-level insight into how interactions of surface species with the liquid reaction environment control the selectivity of this complex electrocatalytic process. © 2019 National Academy of Sciences. All rights reserved. Citation statistics:
资源类型: 期刊论文
标识符: http://119.78.100.158/handle/2HF3EXSE/163559
Appears in Collections: 气候变化与战略
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作者单位: Li, J., Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, MA 02467, United States; Li, X., Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, MA 02467, United States; Gunathunge, C.M., Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, MA 02467, United States; Waegele, M.M., Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, MA 02467, United States
Recommended Citation:
Li J.,Li X.,Gunathunge C.M.,et al. Hydrogen bonding steers the product selectivity of electrocatalytic CO reduction[J]. Proceedings of the National Academy of Sciences of the United States of America,2019-01-01,116(19)