In Situ Electrochemistry of Formate on Cu Thin Films Using ATR-FTIR Spectroscopy and X-ray Photoelectron Spectroscopy

被引:4
|
作者
Hsu, Jason [1 ]
Houache, Mohamed S. E. [2 ]
Abu-Lebdeh, Yaser [2 ]
Patton, Reagan A. [3 ]
Guzman, Marcelo I. [3 ]
Al-Abadleh, Hind A. [1 ]
机构
[1] Wilfrid Laurier Univ, Dept Chem & Biochem, Waterloo, ON K1A 0R6, Canada
[2] Natl Res Council Canada, Energy Min & Environm, Ottawa, ON K1A 0R6, Canada
[3] Univ Kentucky, Dept Chem, Lexington, KY 40506 USA
基金
美国国家科学基金会; 加拿大自然科学与工程研究理事会;
关键词
INFRARED-ABSORPTION SPECTROSCOPY; CO2; REDUCTION; ADSORPTION;
D O I
10.1021/acs.langmuir.3c03660
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Formate (HCOO-) is the most dominant intermediate identified during carbon dioxide electrochemical reduction (CO2ER). While previous studies showed that copper (Cu)-based materials that include Cu(0), Cu2O, and CuO are ideal catalysts for CO2ER, challenges to scalability stem from low selectivity and undesirable products in the -1.0-1.0 V range. There are few studies on the binding mechanism of intermediates and products for these systems as well as on changes to surface sites upon applying potential. Here, we use an in situ approach to study the redox surface chemistry of formate on Cu thin films deposited on Si wafers using a VeeMAX III spectroelectrochemical (SEC) cell compatible with attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR). Spectra for surface species were collected in real time as a function of applied potential during cyclic voltammetry (CV) experiments. Results showed the reproducibility of CV curves on freshly prepared Cu/Si wafers with relatively high signal-to-noise ATR-FTIR absorbance features of surface species during these electrochemical experiments. The oxidation reaction of HCOO- to bicarbonate (HCO3-) was observed using ATR-FTIR at a voltage of 0.27 V. Samples were then subjected to reduction in the CV, and the aqueous phase products below the detection limit of the SEC-ATR-FTIR were identified using ion chromatography (IC). We report the formation of glycolate (H3C2O3-) and glyoxylate (HC2O3-) with trace amounts of oxalate (C2O42-), indicating that C-C coupling reactions proceed in these systems. Changes to the oxidation state of surface Cu were measured using X-ray photoelectron spectroscopy, which showed a reduction in Cu(0) and an increase in Cu(OH)(2), indicating surface oxidation.
引用
收藏
页码:2377 / 2384
页数:8
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