دورية أكاديمية
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The Solvation-Induced Onsager Reaction Field Rather than the Double-Layer Field Controls CO 2 Reduction on Gold.

التفاصيل البيبلوغرافية
العنوان: The Solvation-Induced Onsager Reaction Field Rather than the Double-Layer Field Controls CO 2 Reduction on Gold.
المؤلفون: Zhu Q; Department of Chemistry and Biochemistry, The Ohio State University, Columbus, Ohio 43210, United States., Wallentine SK; Department of Chemistry and Biochemistry, The Ohio State University, Columbus, Ohio 43210, United States., Deng GH; Department of Chemistry and Biochemistry, The Ohio State University, Columbus, Ohio 43210, United States., Rebstock JA; Department of Chemistry and Biochemistry, The Ohio State University, Columbus, Ohio 43210, United States., Baker LR; Department of Chemistry and Biochemistry, The Ohio State University, Columbus, Ohio 43210, United States.
المصدر: JACS Au [JACS Au] 2022 Jan 28; Vol. 2 (2), pp. 472-482. Date of Electronic Publication: 2022 Jan 28 (Print Publication: 2022).
نوع المنشور: Journal Article
اللغة: English
بيانات الدورية: Publisher: American Chemical Society Country of Publication: United States NLM ID: 101775714 Publication Model: eCollection Cited Medium: Internet ISSN: 2691-3704 (Electronic) Linking ISSN: 26913704 NLM ISO Abbreviation: JACS Au Subsets: PubMed not MEDLINE
أسماء مطبوعة: Original Publication: Washington, DC : American Chemical Society, [2021]-
مستخلص: The selectivity and activity of the carbon dioxide reduction (CO 2 R) reaction are sensitive functions of the electrolyte cation. By measuring the vibrational Stark shift of in situ-generated CO on Au in the presence of alkali cations, we quantify the total electric field present at catalytic active sites and deconvolute this field into contributions from (1) the electrochemical Stern layer and (2) the Onsager (or solvation-induced) reaction field. Contrary to recent theoretical reports, the CO 2 R kinetics does not depend on the Stern field but instead is closely correlated with the strength of the Onsager reaction field. These results show that in the presence of adsorbed (bent) CO 2 , the Onsager field greatly exceeds the Stern field and is primarily responsible for CO 2 activation. Additional measurements of the cation-dependent water spectra using vibrational sum frequency generation spectroscopy show that interfacial solvation strongly influences the CO 2 R activity. These combined results confirm that the cation-dependent interfacial water structure and its associated electric field must be explicitly considered for accurate understanding of CO 2 R reaction kinetics.
Competing Interests: The authors declare no competing financial interest.
(© 2022 The Authors. Published by American Chemical Society.)
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تواريخ الأحداث: Date Created: 20220307 Latest Revision: 20220308
رمز التحديث: 20240829
مُعرف محوري في PubMed: PMC8889607
DOI: 10.1021/jacsau.1c00512
PMID: 35252996
قاعدة البيانات: MEDLINE
الوصف
تدمد:2691-3704
DOI:10.1021/jacsau.1c00512