Probing the Local Reaction Environment During High Turnover Carbon Dioxide Reduction with Ag-Based Gas Diffusion Electrodes

Overview

Journal Chemistry

Specialty Chemistry

Date 2021 Feb 2

PMID 33527522

Citations 11

Authors

Stefan Dieckhofer

Denis Ohl

Joao R C Junqueira

Thomas Quast

Thomas Turek

Wolfgang Schuhmann

Affiliations

Soon will be listed here.

Abstract

Discerning the influence of electrochemical reactions on the electrode microenvironment is an unavoidable topic for electrochemical reactions that involve the production of OH and the consumption of water. That is particularly true for the carbon dioxide reduction reaction (CO RR), which together with the competing hydrogen evolution reaction (HER) exert changes in the local OH and H O activity that in turn can possibly affect activity, stability, and selectivity of the CO RR. We determine the local OH and H O activity in close proximity to a CO -converting Ag-based gas diffusion electrode (GDE) with product analysis using gas chromatography. A Pt nanosensor is positioned in the vicinity of the working GDE using shear-force-based scanning electrochemical microscopy (SECM) approach curves, which allows monitoring changes invoked by reactions proceeding within an otherwise inaccessible porous GDE by potentiodynamic measurements at the Pt-tip nanosensor. We show that high turnover HER/CO RR at a GDE lead to modulations of the alkalinity of the local electrolyte, that resemble a 16 m KOH solution, variations that are in turn linked to the reaction selectivity.

Citing Articles

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References

Sheng W, Zhuang Z, Gao M, Zheng J, Chen J, Yan Y . Correlating hydrogen oxidation and evolution activity on platinum at different pH with measured hydrogen binding energy. Nat Commun. 2015; 6:5848. DOI: 10.1038/ncomms6848. View

Hall A, Yoon Y, Wuttig A, Surendranath Y . Mesostructure-Induced Selectivity in CO2 Reduction Catalysis. J Am Chem Soc. 2015; 137(47):14834-7. DOI: 10.1021/jacs.5b08259. View

Michalak M, Kurel M, Jedraszko J, Toczydlowska D, Wittstock G, Opallo M . Voltammetric pH Nanosensor. Anal Chem. 2015; 87(23):11641-5. DOI: 10.1021/acs.analchem.5b03482. View

Zhang F, Co A . Direct Evidence of Local pH Change and the Role of Alkali Cation during CO Electroreduction in Aqueous Media. Angew Chem Int Ed Engl. 2019; 59(4):1674-1681. DOI: 10.1002/anie.201912637. View

Monteiro M, Jacobse L, Touzalin T, Koper M . Mediator-Free SECM for Probing the Diffusion Layer pH with Functionalized Gold Ultramicroelectrodes. Anal Chem. 2019; 92(2):2237-2243. PMC: 6977089. DOI: 10.1021/acs.analchem.9b04952. View

Monteiro M, Jacobse L, Koper M . Understanding the Voltammetry of Bulk CO Electrooxidation in Neutral Media through Combined SECM Measurements. J Phys Chem Lett. 2020; 11(22):9708-9713. PMC: 7681782. DOI: 10.1021/acs.jpclett.0c02779. View

Dieckhofer S, Ohl D, Junqueira J, Quast T, Turek T, Schuhmann W . Probing the Local Reaction Environment During High Turnover Carbon Dioxide Reduction with Ag-Based Gas Diffusion Electrodes. Chemistry. 2021; 27(19):5906-5912. PMC: 8048634. DOI: 10.1002/chem.202100387. View

Rohe M, Kubannek F, Krewer U . Processes and Their Limitations in Oxygen Depolarized Cathodes: A Dynamic Model-Based Analysis. ChemSusChem. 2019; 12(11):2373-2384. DOI: 10.1002/cssc.201900312. View

Dinh C, Burdyny T, Kibria M, Seifitokaldani A, Gabardo C, Garcia de Arquer F . CO electroreduction to ethylene via hydroxide-mediated copper catalysis at an abrupt interface. Science. 2018; 360(6390):783-787. DOI: 10.1126/science.aas9100. View

10.

Wittstock G, Burchardt M, Pust S, Shen Y, Zhao C . Scanning electrochemical microscopy for direct imaging of reaction rates. Angew Chem Int Ed Engl. 2007; 46(10):1584-617. DOI: 10.1002/anie.200602750. View

11.

Moura de Salles Pupo M, Kortlever R . Electrolyte Effects on the Electrochemical Reduction of CO. Chemphyschem. 2019; 20(22):2926-2935. PMC: 6899813. DOI: 10.1002/cphc.201900680. View

12.

Wuttig A, Yaguchi M, Motobayashi K, Osawa M, Surendranath Y . Inhibited proton transfer enhances Au-catalyzed CO2-to-fuels selectivity. Proc Natl Acad Sci U S A. 2016; 113(32):E4585-93. PMC: 4987813. DOI: 10.1073/pnas.1602984113. View

13.

Ryu J, Wuttig A, Surendranath Y . Quantification of Interfacial pH Variation at Molecular Length Scales Using a Concurrent Non-Faradaic Reaction. Angew Chem Int Ed Engl. 2018; 57(30):9300-9304. DOI: 10.1002/anie.201802756. View

14.

Wuttig A, Yoon Y, Ryu J, Surendranath Y . Bicarbonate Is Not a General Acid in Au-Catalyzed CO Electroreduction. J Am Chem Soc. 2017; 139(47):17109-17113. DOI: 10.1021/jacs.7b08345. View

15.

Hengstenberg A, Kranz C, Schuhmann W . Facilitated tip-positioning and applications of non-electrode tips in scanning electrochemical microscopy using a shear force based constant-distance mode. Chemistry. 2000; 6(9):1547-54. DOI: 10.1002/(sici)1521-3765(20000502)6:9<1547::aid-chem1547>3.3.co;2-3. View

16.

Yang K, Kas R, Smith W . In Situ Infrared Spectroscopy Reveals Persistent Alkalinity near Electrode Surfaces during CO Electroreduction. J Am Chem Soc. 2019; 141(40):15891-15900. PMC: 6788196. DOI: 10.1021/jacs.9b07000. View

17.

Hatsukade T, Kuhl K, Cave E, Abram D, Jaramillo T . Insights into the electrocatalytic reduction of CO₂ on metallic silver surfaces. Phys Chem Chem Phys. 2014; 16(27):13814-9. DOI: 10.1039/c4cp00692e. View

18.

Nebel M, Erichsen T, Schuhmann W . Constant-distance mode SECM as a tool to visualize local electrocatalytic activity of oxygen reduction catalysts. Beilstein J Nanotechnol. 2014; 5:141-51. PMC: 3943292. DOI: 10.3762/bjnano.5.14. View

19.

Nebel M, Grutzke S, Diab N, Schulte A, Schuhmann W . Microelectrochemical visualization of oxygen consumption of single living cells. Faraday Discuss. 2014; 164:19-32. DOI: 10.1039/c3fd00011g. View

20.

Yang X, Nash J, Oliveira N, Yan Y, Xu B . Understanding the pH Dependence of Underpotential Deposited Hydrogen on Platinum. Angew Chem Int Ed Engl. 2019; 58(49):17718-17723. DOI: 10.1002/anie.201909697. View