(131f) Interfacial and Surface Engineering of (Photo)Electrochemical Materials and Reactions at the Nanoscale

The study of electrochemical reactions such as CO₂ reduction and photoelectrochemical conversion relies on precise synthetic control of surfaces and interfaces. During my PhD, I employed nanoscale synthesis by plasma-enhanced atomic layer deposition (PEALD) to study the electrochemical selectivity of the CO₂ reduction reaction. PEALD of Cu-based catalyst is pioneered as a synthetic tool to enable control over the particle size, infiltration of catalyst, and programmable control of the surface chemistry and bimetallic alloys.^1–3

In my postdoctoral research, strategies to achieve unbiased (photo)electrochemical reforming of plastics such as ethylene glycol (EG) oxidation from polyethylene terephthalate (PET) with coupled hydrogen generation are applied. In particular, this research employs III-V photoelectrodes with tunable semiconductor-electrolyte interfaces (e.g, surface dipoles for band edge engineering) and electrocatalysts (Pt-based vs. metal phosphide, carbide) to modify the oxidation potential and surface binding energy, respectively.

This talk will also address bipolar membranes as an enabling functional material for water electrolysis, photoelectrochemical water splitting, CO₂ electroreduction, where reliable and reproducible electrochemical impedance spectroscopy is critical for in situ monitoring of the interfacial water dissociation reaction under reverse bias. In summary, this presentation will encompass three electrochemical reactions (1) CO₂ reduction, (2) EG oxidation and (3) water dissociation—where the ability to develop techniques and synthesis strategies to study these interfacial reactions is important to control their electrochemical performance (i.e., product selectivity, kinetic overpotentials).

References:

(1) Lenef, J. D.; Jo, J.; Trejo, O.; Mandia, D. J.; Peterson, R. L.; Dasgupta, N. P. Plasma-Enhanced Atomic Layer Deposition of p-Type Copper Oxide Semiconductors with Tunable Phase, Oxidation State, and Morphology. J. Phys. Chem. C 2021, 125 (17), 9383–9390. https://doi.org/10.1021/acs.jpcc.1c00429.

(2) Lenef, J. D.; Lee, S. Y.; Fuelling, K. M.; Rivera Cruz, K. E.; Prajapati, A.; Delgado Cornejo, D. O.; Cho, T. H.; Sun, K.; Alvarado, E.; Arthur, T. S.; Roberts, C. A.; Hahn, C.; McCrory, C. C. L.; Dasgupta, N. P. Atomic Layer Deposition of Cu Electrocatalysts on Gas Diffusion Electrodes for CO2 Reduction. Nano Lett. 2023, 23 (23), 10779–10787. https://doi.org/10.1021/acs.nanolett.3c02917.

(3) Young Lee, S.; D. Lenef, J.; Cornejo, D. O. D.; M. Ortiz-Ortiz, A.; Ma, T.; S. Arthur, T.; A. Roberts, C.; P. Dasgupta, N. Tuning the Selectivity of Bimetallic Cu Electrocatalysts for CO 2 Reduction Using Atomic Layer Deposition. Chem. Commun. 2025, 61 (5), 965–968. https://doi.org/10.1039/D4CC04820B.