Phase I CCI faculty bolded
Proton-Transfer Kinetics at Liquid-Liquid Interfaces
D’Antona, N.; Kelly, J.; Barnard, N.; Ardo, S.; Wang, Y.; Surendranath, Y.; Markland, T.; Kempler, P.; Boettcher, S. (Under re-review after positive initial review, J. Amer. Chem Soc.), ChemRxiv, 2024.
https://doi.org/10.26434/chemrxiv-2024-sxzbn.
Ion-Exchange-Mediated Pre-Association Gates Interfacial PCET
Lewis, N. B.; Kelly, J.; Gardner, J. G.; Razdan, N. K.; Ardo, S.; Markland, T. E.; Surendranath, Y. (Under review, J. Amer. Chem Soc.), ChemRxiv, 2024
https://doi.org/10.26434/chemrxiv-2024-8vb2n-v3
– The observed effect is consistent with a mechanism where concentrated NaClO4 solutions inhibit pre-association between hydronium and the active site, with MD simulations corroborating this interpretation. These results demonstrate the relevance of a previously overlooked elementary step in I-PCET and highlight the importance of supporting electrolyte in controlling IIT reactivity.
Homogeneous-heterogeneous bifunctionality in Pd-catalyzed vinyl acetate synthesis
Harraz, D. M.; Lodaya, K.; Tang, B. Y.; Surendranath, Y. Science, 2025, 388, eads7913. https://doi.org/10.1126/science.ads7913
– Pd catalyzed vinyl acetate synthesis is a large-scale industrial process for which the mechanism is not fully understood. Under reaction conditions, both Pd metal and Pd(II) acetate species can exist.
– Electrochemical tools elucidate the roles of Pd metal and Pd(II) during vinyl acetate synthesis.
– Interconversion between homogeneous and heterogeneous Pd species is required for catalysis, with corrosion of Pd metal to Pd(II) being kinetically relevant.
“Common catalyst works by cycling between two different forms, upending a long-held supposition”
Synthesis of 4,5-Disubstituted o-Phenylenediamines: An Enabling Platform for Electrochemical Evaluation of Intramolecular Concerted Proton–Electron Transfer Reactions
Tang, D.; Keyes, N; Rose, J.; Gonzalez, J.; Giles, M.; Surendranath, Y.; Ardo, S.; M. Minus (Under review, J. Org. Chem.) ChemRxiv, 2024. https://doi.org/10.26434/chemrxiv-2024-8772n
– We developed three distinct and modular synthetic strategies to symmetric and asymmetric 4,5-o-phenylenediamines in as little as 2 steps from commercial starting materials
– We have shown that graphitic electrodes modified by 4,5-o-phenylenediamines host interfacial proton-coupled-electron-transfer reactivity and provide rich platforms for mechanistic studies
– Prior to our work, synthetic access to 4,5-o-phenylenediamines remained limited and designs capable of hosting intramolecular interfacial proton-coupled-electron-transfer reactivity remained elusive
Teaching the Concepts of Donnan Potential and Liquid-Junction Potential by Evaluating Homemade pH and Ion-Sensitive Probes Constructed Using Commercial Ion-Exchange Membranes and Reference Electrodes.
Gaieck, W.; Zhang, A.; Sabatose, A.; Ngo, M.; Schwartz, E.; White, W.; Luo, S.; Schulte, L.; Wang,
Y.; Ardo, S. (Under review, J. Chem. Educ.) ChemRxiv, 2024. https://doi.org/10.26434/chemrxiv-2024-hxgnv-v2
– We designed, implemented, and evaluated a new hands-on laboratory activity intended for students in electroanalytical chemistry courses to teach the concepts of electric potential differences formed due to ions at interfaces
– A simple two-compartment electrochemical cell was constructed from inexpensive and readily available disposable plastic cuvettes and was used to measured open-circuit potentials across commercially available ion-exchange membranes to report on the magnitude of both Donnan and liquid-junction electric potential differences
– Depending on the ion-exchange membrane used and constituents in the aqueous solutions that wetted it, the cell responded like a pH, pK, pCl, or pOH probe
Interfacial Proton-Transfer Kinetics Using Model Tungsten Oxide Thin Films
Roychowdhury, D.; D’Antona, N.R.; Zhao, Y.; Surendranath, Y.; Augustyn, V.; Kempler, P.A.; & Boettcher, S.W. (under review ACS Electrochemistry) 2025 https://chemrxiv.org/engage/chemrxiv/article-details/67f34eed6dde43c908c0b423
– Dense tungsten oxide films were prepared to measure IIT in the absence of confounding ion and electron transport present in typical (nano)porous electrodes.
-We develop a new current-response model to decouple overlapping contributions of double-layer charging and interfacial proton-transfer kinetics
A Multiscale Investigation of a Cation Solvent Exchange Mechanism for Reversible K+ Insertion into Prussian Blue Analogs
Cora, S.; Briselli, V.; Cannan, C.; Gardner, J.; Toh, W.; Kempler, P.; Augustyn, V.; Boettcher, S.W.; Surendranath, Y.; Sa, N.* (submitted to ChemRxiv, 2025)
– This work utilized an in-situ multi-harmonics electrochemical quartz crystal microbalance with dissipation monitoring (EQCM-D) to uncover the dynamic, reversible K+ insertion into NiHCF material.
– Findings reveal a complicated and dynamic cation-water exchange mechanism that is accompanied by a microstructural evolution within the NiHCF film for K+ insertion/de-insertion.
Ion Dynamics and Polarizations in Simulated Nanopore under Alternating Current Controls
Yang, Z.; D’Antona, N.R.; Boettcher, S.W.; Sa, N.* (submitted to ChemRxiv, 2025)
– Built a time-dependent continuum modeling to investigate the competition between a surface-charge dominated electromigration process under an altering-current field induced dynamic ion distribution
– Findings highlight the interplay of the ion selectivity and distribution by exploiting the dynamic competition between electromigration and diffusion.
A Nanoporous Capacitive Electrochemical Ratchet for Continuous Ion Separations
Kautz, R. J.; Herman, A.; Heffernan, E. J.; Alshochat, K.S.; Grossman, E.; Saxena, R.; Muñetón, C.; Larson, D.; Ager, J. W.; Toma, F. M.; Ardo, S.; Segev, G. A. (Under review, Nat. Mater.) arXiv, 2023. https://doi.org/10.48550/ARXIV.2309.00951.
– First demonstration of an ion pump that drives aqueous ions against a force using a capacitive ratchet mechanism that does not require redox reactions.
– Modulation of an electric potential between thin metallic layers on either face of a nanoporous alumina wafer immersed in solution resulted in persistent voltages and ionic currents indicative of directional ion pumping.
– The non-linear capacitive nature of electric double layers sustains a continuous ion flux due to its repeated charging and discharging.
Watt’s the Risk?: Public Understanding of Battery Usage and Storage in the United States
Segrè Cohen, A.; Bunquin, J. B. PhysArXiv, 2024. https://doi.org/10.31234/osf.io/8ybeu — under review at Energy Research and Social Science
-An experimental survey was conducted on a representative US sample.
-Positive affect and trust in science are key predictors of battery acceptance.
-Batteries combating climate change and ones for personal use are accepted equally.
Charged communications: Understanding the dynamics of information exposure and risk perceptions in battery technology adoption
Bunquin, J. B., Segrè Cohen, A. – under review at Environmental Communication
– An experimental survey was conducted on a US sample of over 1,200 participants
-Social Amplification of Risk Framework was used to ascertain where people get their information about batteries and how these sources impact risk perception
-Battery information seems to be a special interest topic rather than one of general public interest.