Spectro-Electrochemical Decoding of Metals, Alloys, and Buried Interfaces
6 affiliations
- 1Department of Chemistry, University of Louisville, 2320 S. Brook St, Louisville, KY, USA, 40292
- 2Department of Physics
- 3University of Louisville
- 4Department of Chemical and Biomolecular Engineering and Materials Science and Nanoengineering
- 5Rice University
- 6Department of Chemical Engineering
Abstract
Metal-electrolyte interfaces govern corrosion, catalysis, energy-conversion and storage technologies, yet resolving their chemical evolution under operating conditions remains challenging. Electrochemical measurements report an integrated response, while post-mortem characterization can lose the transient sequence and spatial distribution of dissolved species. Here, we introduce the In-Situ Corrosion Monitoring Technique (ICMT), an operando spectro-electrochemical platform that converts interfacial metal dissolution into spatially and temporally resolved optical concentration fields. Under an applied bias, dissolution products migrate through a transparent gel electrolyte that suppresses convection and restricts mixing, thereby retaining dissolved species for interrogation by UV-visible spectroscopy. Using Cu and Ni as model systems, ICMT establishes element-specific absorption fingerprints and distinguishes active Ni dissolution from passivation-influenced Cu corrosion while enabling estimation of recession rates and apparent transport coefficients. Applied to Cu-coated Ni, ICMT sequentially detects Cu and Ni-associated species, revealing degradation from the outer coating to the buried substrate and detecting dissolution from a Cu overlayer as thin as 100 nm. Applied to a Cu-Zn-Ni ternary alloy, the platform resolves constituent-specific dissolution signatures that remain convoluted within the total electrochemical current. Collectively, ICMT provides a simple and accessible benchtop approach for determining how material interface evolves, which constituent dissolves and from which layer it arises, while preserving the transient chemical history of electrochemical interfaces.
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BibTeX
@misc{khan2026spectroelectrochemical,
title = {{Spectro-Electrochemical Decoding of Metals, Alloys, and Buried Interfaces}},
author = {Waliul Islam Khan and Craig A Grapperhaus and Johann Hemmer and Andrew Wilson and Gamini Sumanasekera and Robert M. Buchanan and Aditya D. Mohite and Gautam Gupta},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15011164/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15011164/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Spectro-Electrochemical Decoding of Metals, Alloys, and Buried Interfaces
AU - Waliul Islam Khan
AU - Craig A Grapperhaus
AU - Johann Hemmer
AU - Andrew Wilson
AU - Gamini Sumanasekera
AU - Robert M. Buchanan
AU - Aditya D. Mohite
AU - Gautam Gupta
PY - 2026
DA - 2026/10/27
PB - ChemRxiv
DO - 10.26434/chemrxiv.15011164/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15011164/v1
AB - Metal-electrolyte interfaces govern corrosion, catalysis, energy-conversion and storage technologies, yet resolving their chemical evolution under operating conditions remains challenging. Electrochemical measurements report an integrated response, while post-mortem characterization can lose the transient sequence and spatial distribution of dissolved species. Here, we introduce the In-Situ Corrosion Monitoring Technique (ICMT), an operando spectro-electrochemical platform that converts interfacial metal dissolution into spatially and temporally resolved optical concentration fields. Under an applied bias, dissolution products migrate through a transparent gel electrolyte that suppresses convection and restricts mixing, thereby retaining dissolved species for interrogation by UV-visible spectroscopy. Using Cu and Ni as model systems, ICMT establishes element-specific absorption fingerprints and distinguishes active Ni dissolution from passivation-influenced Cu corrosion while enabling estimation of recession rates and apparent transport coefficients. Applied to Cu-coated Ni, ICMT sequentially detects Cu and Ni-associated species, revealing degradation from the outer coating to the buried substrate and detecting dissolution from a Cu overlayer as thin as 100 nm. Applied to a Cu-Zn-Ni ternary alloy, the platform resolves constituent-specific dissolution signatures that remain convoluted within the total electrochemical current. Collectively, ICMT provides a simple and accessible benchtop approach for determining how material interface evolves, which constituent dissolves and from which layer it arises, while preserving the transient chemical history of electrochemical interfaces.
ER -