Authors: Jon Ustarroz
Source:  (article, 2023-12-18)
Field: Chemistry — Electrochemistry

New insights on electrochemical nucleation, growth and dissolution by combining high-throughput local electrochemistry and (in-situ) electron microscopy New insights on electrochemical nucleation, growth and dissolution by combining high-throughput local electrochemistry and (in-situ) electron microscopyJon Ustarroz a, ba Université libre de Bruxelles, av. F. D. Roosevelt 50, Bruxelles, 1050, Belgiumb Vrije Universiteit Brussel , BelgiumMaterials for Sustainable Development Conference (MATSUS)Proceedings of MATSUS Spring 2024 Conference (MATSUS24)#InOpCat - In situ and operando characterization of electrocatalytic interfacesBarcelona, Spain, 2024 March 4th - 8thOrganizers: Esther Alarcon-Llado, Jesus Barrio Hermida and Paula Sebastian PascualInvited Speaker, Jon Ustarroz, presentation 078DOI: https://doi.org/10.29363/nanoge.matsus.2024.078Publication date: 18th December 2023Electrochemical nucleation and growth (EN&G) are the cornerstone for many (nano)material growth routes and the main factor limiting battery durability [1]. The in-depth experimental assessment of the process is very challenging due to the random nature of initiation events (nucleation), the heterogeneity of surfaces and the (very) fast kinetics across several length scales. For all that, our understanding of the mechanisms involved is inaccurate and incomplete [2]. On the other hand, electrochemical dissolution (ED) of nanostructured interfaces is the main cause of material degradation in exposed environments (corrosion) or energy conversion and storage devices. Dissolution is also affected by random initiation events, fast kinetics and surface heterogeneity. Hence, a complete picture of the (combination of) dissolution pathways taking place is also elusive. To address these challenges, we combine Scanning Electrochemical Cell Microscopy (SECCM) and in-situ Electrochemical Transmission Electron Microscopy (EC-TEM). On the one hand, we performed thousands of high-throughput local electrochemical measurements for the nucleation of Au and Cu on different surfaces such as glassy carbon (GC), ITO, and Pt [3-4], which we analyzed with a data-centric approach. In addition, the spatially resolved electrochemical characterization enables a one-to-one correlation between the electrochemical data and the local surface properties, which are evaluated by SEM in identical locations to where the local electrochemical measurements have been performed. On the other hand, we use SECCM as a high throughput tool to collect ED activity from randomly probed locations where metal nanoparticles (NPs) are pre-deposited by different methods (electrodeposition, sputtering, drop casting, etc.). Taking gold NPs as a case study, we show that, in the presence of chloride and at certain potentials, NP dissolution events are separated in time and can be therefore monitored by SECCM as single NP dissolution events [3, 5]. Data science methods, previously applied in the group for the study of pitting corrosion in stainless steel [6, 7] have been here deployed to explore the very large datasets containing information of the dissolution of several thousands of NPs. The analysis of the SECCM EN&G and ED datasets is leveraged to discuss mechanistic aspects of noble metal nucleation, growth and dissolution processes. In addition, we show how EC-TEM allows the study of the early-stage growth/dissolution dynamics of the metallic phase. Interestingly, these measurements corroborate that the nature of the events resolved by SECCM corresponds to the dissolution of individual NPs. The combination of high-throughput SECCM, EC-TEM and data-centric analysis opens new opportunities for the rational design (electrodeposition) of functional nanostructured materials and the evaluation of their durability under electrochemical polarization (resistance to electrodissolution). References:[1] Bernal, M.; Ustarroz J. Electrodeposition of nanostructured catalysts for electrochemical energy conversion: current trends and innovative strategies. Current Opinion in Electrochemistry 2021, 100688[2] Ustarroz J. Current atomic-level understanding of electrochemical nucleation and growth on low-energy surfaces. Current Opinion in Electrochemistry 2020, 19, 144-152.[3] Bernal, M.; Torres, D.; Parapari, S.S.; Čeh, M.; Rožman, K.Ž.; Šturm, S.; Ustarroz, J. A microscopic view on the electrochemical deposition and dissolution of Au with scanning electrochemical cell microscopy–Part I. Electrochimica Acta 2023, 445, 142023[4] Torres, D.; Bernal, M. ; Demaude, A. ; Hussain, S. ; Bar, L. ; Losada-Pérez, P. ; Reniers, F. ; Ustarroz, J. Distribution of Copper Electrochemical Nucleation Activities on Glassy Carbon: A New Perspective Based on Local Electrochemistry. Journal of The Electrochemical Society 2022, 169 (10), 102513[5] Bernal, M.; Torres, D.; Semsari Parapari, S.; Coelho, L.B.; Delfosse, S.; .; Čeh, M.; Rožman, K.Ž.; Šturm, S.; Ustarroz, J. A Microscopic View on the Electrochemical Deposition and Dissolution of AU with Scanning Electrochemical Cell Microscopy – Part II: Potentiostatic Dissolution and Correlation with In-Situ EC-TEM. Electrochimica Acta 2023, In Revision.[6] Coelho, L.B.; Torres, D.; Bernal, M.; Paldino, G.M.; Bontempi, G.; Ustarroz, J. Probing the randomness of the local current distributions of 316 L stainless steel corrosion in NaCl solution. Corrosion Science 2023, 11110[7] Coelho, L.B.; Torres, D.; Vangrunderbeek, V.; Bernal, M.; Paldino, G.M.; Bontempi, G.; Ustarroz, J. Estimating pitting descriptors of 316 L stainless steel by machine learning and statistical analysis. npj Materials Degradation 2023, 7(1), 82Acknowledgements:J.U. acknowledges financial support to the Fonds de la Recherche Scientifique de Belgique (F.R.S.-FNRS) under Grant No. F.4531.19 ; the Fonds Wetenschappelijk Onderzoek in Vlaanderen (FWO) under contract G0C3121N ; the Federation Wallonie Bruxelles for the ARC-Consolidator grant (RENEGADE) ; and Innovoris for the Research Project NDIAMO. © FUNDACIO DE LA COMUNITAT VALENCIANA SCITOnanoGe is a prestigious brand of successful science conferences that are developed along the year in different areas of the world since 2009. Our worldwide conferences cover cutting-edge materials topics like perovskite solar cells, photovoltaics, optoelectronics, solar fuel conversion, surface science, catalysis and two-dimensional materials, among many others.nanoGe Fall MeetingnanoGe Fall Meeting (NFM) is a multiple symposia conference celebrated yearly and focused on a broad set of topics of advanced materials preparation, their fundamental properties, and their applications, in fields such as renewable energy, photovoltaics, lighting, semiconductor quantum dots, 2-D materials synthesis, charge carriers dynamics, microscopy and spectroscopy semiconductors fundamentals, etc.nanoGe Spring MeetingThis conference is a unique series of symposia focused on advanced materials preparation and fundamental properties and their applications, in fields such as renewable energy (photovoltaics, batteries), lighting, semiconductor quantum dots, 2-D materials synthesis and semiconductors fundamentals, bioimaging, etc.International Conference on Hybrid and Organic PhotovoltaicsInternational Conference on Hybrid and Organic Photovoltaics (HOPV) is celebrated yearly in May. The main topics are the development, function and modeling of materials and devices for hybrid and organic solar cells. The field is now dominated by perovskite solar cells but also other hybrid technologies, as organic solar cells, quantum dot solar cells, and dye-sensitized solar cells and their integration into devices for photoelectrochemical solar fuel production.Asia-Pacific International Conference on Perovskite, Organic Photovoltaics and OptoelectronicsThe main topics of the Asia-Pacific International Conference on Perovskite, Organic Photovoltaics and Optoelectronics (IPEROP) are discussed every year in Asia-Pacific for gathering the recent advances in the fields of material preparation, modeling and fabrication of perovskite and hybrid and organic materials. Photovoltaic devices are analyzed from fundamental physics and materials properties to a broad set of applications. The conference also covers the developments of perovskite optoelectronics, including light-emitting diodes, lasers, optical devices, nanophotonics, nonlinear optical properties, colloidal nanostructures, photophysics and light-matter coupling.International Conference on Perovskite Thin Film Photovoltaics Perovskite Photonics and OptoelectronicsThe International Conference on Perovskite Thin Film Photovoltaics Perovskite Photonics and Optoelectronics (NIPHO) is the best place to hear the latest developments in perovskite solar cells as well as on recent advances in the fields of perovskite light-emitting diodes, lasers, optical devices, nanophotonics, nonlinear optical properties, colloidal nanostructures, photophysics and light-matter coupling. Electrochemistry ; Nucleation ; Dissolution ; In situ ; Materials science ; Electron microscope ; Throughput ; Electrode ; Microscopy ; Nanotechnology ; Chemical engineering ; Chemistry ; Computer science ; Optics ; Physics ; Physical chemistry Electrochemical Analysis and Applications ; Corrosion Behavior and Inhibition ; Hydrogen embrittlement and corrosion behaviors in metals