2026-10-13T03:22:18Z https://api.figshare.com/v2/oai

oai:figshare.com:article/34037757 2026-10-01T02:05:21Z category_1 category_4 category_146 category_915 category_21 category_24 category_873 category_39 category_734 category_69 portal_63 item_type_6 month_year_10_2026

Solvation Mediates the Mechanisms of Homogeneous Co-Electrocatalysis at Interfaces Megan E. Moberg (25147548) Robert Sacci (10053375) Benjamin Doughty (1362744) Charles W. Machan (1417663) Biophysics Biochemistry Space Science Physical Sciences not elsewhere classified Biotechnology Evolutionary Biology Chemical Sciences not elsewhere classified Ecology Biological Sciences not elsewhere classified Inorganic Chemistry traditional linear spectroscopies protic catalytic mechanism applied potential affects mechanistic insight required sfg spectra show allow catalytic species limiting insight vibrational spectroscopy underscoringthe need solvent environments solvation mediates solvation environments selective reduction overall rates long obscured interfacial response interfacial environment improve selectivity electrochemical solution carbon monoxide carbon dioxide buried within bulk versus Electrochemical reactions occur near electrode surfacesthis interfacial environment has long obscured the mechanistic insight required to improve selectivity and overall rates. 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emphasizing the divide between species in the bulk versus at the surface and underscoringthe need for further research in this area. 2026-09-30T00:00:00Z Text Journal contribution 10.1021/acs.jpclett.6c02610.s001 https://figshare.com/articles/journal_contribution/Solvation_Mediates_the_Mechanisms_of_Homogeneous_Co-Electrocatalysis_at_Interfaces/34037757 CC BY-NC 4.0