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While traditional linear spectroscopies can be used to probe bulk chemical changes, the interfacial response is buried within, limiting insight into solvation environments that modulate homogeneous electrochemical transformations. Here, we address these challenges by studying the protic catalytic mechanism of a Cr-based bipyridine catalyst capable of the selective reduction of carbon dioxide (CO2) to carbon monoxide (CO), at an applied potential using sum frequency generation (SFG) vibrational spectroscopy. Measurements on a series of increasingly complex samples allowed for the characterization of species and solvent environments in an electrochemical solution at a gold working electrode surface. SFG spectra show how applied potential affects the packing of molecules and their conformations at interfaces to allow catalytic species to approach and transfer electrons\u2500emphasizing the divide between species in the bulk versus at the surface and underscoringthe need for further research in this area.<\/jats:p>","DOI":"10.1021\/acs.jpclett.6c02610","type":"journal-article","created":{"date-parts":[[2026,10,1]],"date-time":"2026-10-01T03:01:26Z","timestamp":1790823686000},"page":"11940-11946","source":"Crossref","is-referenced-by-count":0,"title":["Solvation Mediates\nthe Mechanisms of Homogeneous Co-Electrocatalysis\nat Interfaces"],"prefix":"10.1021","volume":"17","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-2083-9877","authenticated-orcid":true,"given":"Megan E.","family":"Moberg","sequence":"first","affiliation":[{"name":"University of Virginia , , PO Box 400319, , ,","place":["Charlottesville, Virginia, United States, 22904-4319"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0073-5221","authenticated-orcid":true,"given":"Robert","family":"Sacci","sequence":"additional","affiliation":[{"name":"Oak Ridge National Laboratory , , , ,","place":["Oak Ridge, Tennessee, United States, 37831"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6429-9329","authenticated-orcid":true,"given":"Benjamin","family":"Doughty","sequence":"additional","affiliation":[{"name":"Oak Ridge National Laboratory , , , ,","place":["Oak Ridge, Tennessee, United States, 37831"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5182-1138","authenticated-orcid":true,"given":"Charles W.","family":"Machan","sequence":"additional","affiliation":[{"name":"University of Virginia , , PO Box 400319, , ,","place":["Charlottesville, Virginia, United States, 22904-4319"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,9,30]]},"reference":[{"key":"2026101508213140600_cit1","unstructured":"Carbon dioxide now more than 50% higher than pre-industrial levels. U.S. Department of Commerce, 2022; https:\/\/www.noaa.gov\/news-release\/carbon-dioxide-now-more-than-50-higher-than-pre-industrial-levels, accessed 7\/29\/2026."},{"issue":"1","key":"2026101508213140600_cit2","doi-asserted-by":"publisher","first-page":"2","DOI":"10.1186\/s42480-019-0026-4","article-title":"Process intensification technologies\nfor CO2 capture and conversion \u2013 a review","volume":"2","author":"Adamu","year":"2020","journal-title":"BMC Chem. Eng."},{"issue":"14","key":"2026101508213140600_cit3","doi-asserted-by":"publisher","first-page":"3345","DOI":"10.1021\/om060228g","article-title":"Electrochemical\nReduction of CO2 to CO Catalyzed\nby a Bimetallic Palladium Complex","volume":"25","author":"Raebiger","year":"2006","journal-title":"Organometallics"},{"issue":"47","key":"2026101508213140600_cit4","doi-asserted-by":"publisher","first-page":"12607","DOI":"10.1039\/c1cc15071e","article-title":"Electrocatalytic\nreduction of CO2 to CO by polypyridyl ruthenium complexes","volume":"47","author":"Chen","year":"2011","journal-title":"Chem. comm."},{"issue":"1","key":"2026101508213140600_cit5","doi-asserted-by":"publisher","first-page":"161","DOI":"10.1016\/S0022-0728(98)00116-8","article-title":"The effect\nof weak Bro\u0308nsted\nacids on the electrocatalytic reduction of carbon dioxide by a rhenium\ntricarbonyl bipyridyl complex","volume":"453","author":"Wong","year":"1998","journal-title":"J. Electroanal.\nChem."},{"issue":"14","key":"2026101508213140600_cit6","doi-asserted-by":"publisher","first-page":"5460","DOI":"10.1021\/ja501252f","article-title":"Manganese Catalysts with Bulky Bipyridine\nLigands for\nthe Electrocatalytic Reduction of Carbon Dioxide: Eliminating Dimerization\nand Altering Catalysis","volume":"136","author":"Sampson","year":"2014","journal-title":"J. Am. Chem. Soc."},{"issue":"5","key":"2026101508213140600_cit7","doi-asserted-by":"publisher","first-page":"2484","DOI":"10.1021\/ic302391u","article-title":"Manganese as a Substitute\nfor Rhenium in CO2 Reduction\nCatalysts: The Importance of Acids","volume":"52","author":"Smieja","year":"2013","journal-title":"Inorg. Chem."},{"issue":"51","key":"2026101508213140600_cit8","doi-asserted-by":"publisher","first-page":"28951","DOI":"10.1021\/acs.jpcc.6b09947","article-title":"Dissection\nof Electronic Substituent Effects in Multielectron\u2013Multistep\nMolecular Catalysis. Electrochemical CO2-to-CO Conversion\nCatalyzed by Iron Porphyrins","volume":"120","author":"Azcarate","year":"2016","journal-title":"J. Phys. Chem.\nC"},{"issue":"51","key":"2026101508213140600_cit9","doi-asserted-by":"publisher","first-page":"16639","DOI":"10.1021\/jacs.6b07014","article-title":"Through-Space\nCharge Interaction Substituent Effects in Molecular Catalysis Leading\nto the Design of the Most Efficient Catalyst of CO2-to-CO\nElectrochemical Conversion","volume":"138","author":"Azcarate","year":"2016","journal-title":"J. Am. Chem. Soc."},{"issue":"4","key":"2026101508213140600_cit10","doi-asserted-by":"publisher","first-page":"3411","DOI":"10.1021\/acscatal.7b04412","article-title":"Highly Selective Molecular Catalysts for the CO2-to-CO\nElectrochemical Conversion at Very Low Overpotential. Contrasting\nFe vs Co Quaterpyridine Complexes upon Mechanistic Studies","volume":"8","author":"Cometto","year":"2018","journal-title":"ACS Catal."},{"issue":"7","key":"2026101508213140600_cit11","doi-asserted-by":"publisher","first-page":"3932","DOI":"10.1021\/ic3001619","article-title":"Homogeneous CO2 Reduction by Ni(cyclam)\nat a Glassy Carbon Electrode","volume":"51","author":"Froehlich","year":"2012","journal-title":"Inorg. 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Catal."},{"key":"2026101508213140600_cit29","doi-asserted-by":"publisher","first-page":"141","DOI":"10.1016\/j.jelechem.2015.12.029","article-title":"Experimentation\nand numerical modeling\nof cyclic voltammetry for electrochemical micro-sized sensors under\nthe influence of electrolyte flow","volume":"763","author":"Adesokan","year":"2016","journal-title":"J. Electroanal.\nChem."},{"issue":"39","key":"2026101508213140600_cit30","doi-asserted-by":"publisher","first-page":"13791","DOI":"10.1021\/jacs.7b06898","article-title":"The Role of Electrode\u2013Catalyst\nInteractions in Enabling Efficient CO2 Reduction with Mo(bpy)(CO)4 As Revealed by Vibrational Sum-Frequency Generation Spectroscopy","volume":"139","author":"Neri","year":"2017","journal-title":"J. Am. Chem. 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