In Situ Quantification of Surface Intermediates and Correlation to Discharge Products on Hematite Photoanodes using a Combined Scanning Electrochemical Microscopy Approach

Hematite is a promising photoanode for solar driven water splitting. Elucidating its surface chemical pathways is key to improving its performance. Here, we use redox titrations in the Surface Interrogation mode of Scanning Electrochemical Microscopy (SI-SECM) to quantitatively probe in situ the reactivity and time evolution of surface species formed on hematite during photo assisted water oxidation. Using SI-SECM, two distinct populations of oxidizing surface species were resolved with measured k_(si) of 316 m^3/(mol·s) and 2 m^3/(mol·s) for the more and less reactive species, respectively. While the surface coverage of both species was found to increase as a function of applied bias, the rate constants did not change appreciably, suggesting that the mechanism of water oxidation is independent of bias potential. In the absence of applied potential, both populations exhibit decay that is well described by second order kinetics, with k_d values of 1.2 × 10^5 ± 0.2 × 10^5 and 6.3 × 10^3 ± 0.9 × 10^3 m^2/(mol·s) for the fast and slow reacting adsorbates, respectively. Using transient substrate generation/tip collection mode, we detected the evolution of as much as 1.0 μmol/m^2 of H_2O_2 during this decay process, which correlates with the coverage observed by one of the titrated species. By deconvoluting the reactivity of multiple adsorbed reactants, these experiments demonstrate how SI-SECM enables direct observation of multiple adsorbates and reaction pathways on operating photoelectrodes

Operando Investigation of Solid Electrolyte Interphase Formation, Dynamic Evolution, and Degradation During Lithium Plating/Stripping

The solid electrolyte interphase (SEI) dictates the stability and cycling performance of highly reactive battery electrodes. Characterization of the thin, dynamic, and environmentally sensitive nature of the SEI presents a formidable challenge, which calls for the use of microscopic, time-resolved operando methods. Herein, we employ scanning electrochemical microscopy (SECM) to directly probe the heterogeneous surface electronic conductivity during SEI formation and degradation. Complementary operando electrochemical quartz crystal microbalance (EQCM) and ex situ X-ray photoelectron spectroscopy (XPS) provide comprehensive analysis of the dynamic size and compositional evolution of the complex interfacial microstructure. We have found that stable anode passivation occurs at potentials of 0.5 V vs Li/Li+, even in cases where anion decomposition and interphase formation occur above 1.0 V. We investigated the bidirectional relationship between the SEI and lithium plating-stripping, finding that plating-stripping ruptures the SEI. The current efficiency of this reaction is correlated to the anodic stability of the SEI, highlighting the interdependent relationship between the two. We anticipate this work will provide critical insights on the rational design of stable and effective SEI layers for safe, fast-charging, and long-lifetime lithium metal batteries

In Situ Quantification of Surface Intermediates and Correlation to Discharge Products on Hematite Photoanodes Using a Combined Scanning Electrochemical Microscopy Approach

Hematite is a promising photoanode for solar driven water splitting. Elucidating its surface chemical pathways is key to improving its performance. Here, we use redox titrations in the Surface Interrogation mode of Scanning Electrochemical Microscopy (SI-SECM) to quantitatively probe in situ the reactivity and time evolution of surface species formed on hematite during photo assisted water oxidation. Using SI-SECM, two distinct populations of oxidizing surface species were resolved with measured <i>k</i>_si of 316 m³/(mol·s) and 2 m³/(mol·s) for the more and less reactive species, respectively. While the surface coverage of both species was found to increase as a function of applied bias, the rate constants did not change appreciably, suggesting that the mechanism of water oxidation is independent of bias potential. In the absence of applied potential, both populations exhibit decay that is well described by second order kinetics, with <i>k</i>_d values of 1.2 × 10⁵ ± 0.2 × 10⁵ and 6.3 × 10³ ± 0.9 × 10³ m²/(mol·s) for the fast and slow reacting adsorbates, respectively. Using transient substrate generation/tip collection mode, we detected the evolution of as much as 1.0 μmol/m² of H₂O₂ during this decay process, which correlates with the coverage observed by one of the titrated species. By deconvoluting the reactivity of multiple adsorbed reactants, these experiments demonstrate how SI-SECM enables direct observation of multiple adsorbates and reaction pathways on operating photoelectrodes

Operando methods: A new era of electrochemistry

One of the grand challenges facing electrochemistry is to directly resolve the complex nature of (electro)catalyst active sites and capture real-time “movies” of reaction dynamics, i.e. “watching chemistry in action”. The need for such fundamental understanding has stimulated the development of operando/in situ methods, which have greatly enhanced our ability to identify activity descriptors of electrocatalysts and establish structure–property relationships of energy materials. This review summarizes the frontiers of operando electrochemical liquid-cell scanning transmission electron microscopy and correlative synchrotron X-ray methods, which are complementary tools to comprehensively investigate reaction dynamics across multiple spatiotemporal scales. In an effort to encourage greater adoption of advanced operando methods by the general electrochemistry community, this review points out the need to benchmark electrochemistry in confined and heterogenous liquid environment with minimal beam-induced damage. We anticipate that multimodal operando methods will become indispensable for understanding interfacial reaction mechanisms for the broad chemistry and energy materials communities

Electrocatalysis in Alkaline Media and Alkaline Membrane-Based Energy Technologies

Hydrogen energy-based electrochemical energy conversion technologies offer the promise of enabling a transition of the global energy landscape from fossil fuels to renewable energy. Here, we present a comprehensive review of the fundamentals of electrocatalysis in alkaline media and applications in alkaline-based energy technologies, particularly alkaline fuel cells and water electrolyzers. Anion exchange (alkaline) membrane fuel cells (AEMFCs) enable the use of nonprecious electrocatalysts for the sluggish oxygen reduction reaction (ORR), relative to proton exchange membrane fuel cells (PEMFCs), which require Pt-based electrocatalysts. However, the hydrogen oxidation reaction (HOR) kinetics is significantly slower in alkaline media than in acidic media. Understanding these phenomena requires applying theoretical and experimental methods to unravel molecular-level thermodynamics and kinetics of hydrogen and oxygen electrocatalysis and, particularly, the proton-coupled electron transfer (PCET) process that takes place in a proton-deficient alkaline media. Extensive electrochemical and spectroscopic studies, on single-crystal Pt and metal oxides, have contributed to the development of activity descriptors, as well as the identification of the nature of active sites, and the rate-determining steps of the HOR and ORR. Among these, the structure and reactivity of interfacial water serve as key potential and pH-dependent kinetic factors that are helping elucidate the origins of the HOR and ORR activity differences in acids and bases. Additionally, deliberately modulating and controlling catalyst–support interactions have provided valuable insights for enhancing catalyst accessibility and durability during operation. The design and synthesis of highly conductive and durable alkaline membranes/ionomers have enabled AEMFCs to reach initial performance metrics equal to or higher than those of PEMFCs. We emphasize the importance of using membrane electrode assemblies (MEAs) to integrate the often separately pursued/optimized electrocatalyst/support and membranes/ionomer components. Operando/in situ methods, at multiscales, and ab initio simulations provide a mechanistic understanding of electron, ion, and mass transport at catalyst/ionomer/membrane interfaces and the necessary guidance to achieve fuel cell operation in air over thousands of hours. We hope that this Review will serve as a roadmap for advancing the scientific understanding of the fundamental factors governing electrochemical energy conversion in alkaline media with the ultimate goal of achieving ultralow Pt or precious-metal-free high-performance and durable alkaline fuel cells and related technologies.This work was supported by the Center for Alkaline-Based Energy Solutions, an Energy Frontier Research Center program supported by the U.S. Department of Energy, under Grant DE-SC0019445. This work acknowledges the long-term support of TEM facilities at the Cornell Center for Materials Research (CCMR) which are supported through the National Science Foundation Materials Research Science and Engineering Center (NSF MRSEC) program (DMR1719875), and Cornell high-energy synchrotron sources (CHESS), which is supported by the National Science Foundation under Award DMR-1332208