Operando studies reveal active Cu nanograins for CO_2 electroreduction

ACCESS Metrics & More Article Recommendations ■ CONTENTS High-Throughput Nanopores 320 Nanopore Working Principle 320 Arrayed Nanopore Configurations 321 Machine-Learning Assisted Nanopore Readout 321 Integration Modalities for Nanopores 321 Nanopore-Confined Electrochemistry 322 High-Throughput Scanning Ion Conductance Microscopy 324 From Nanopore to Nanoprobe 324 High-Throughput SICM 324 High-Throughput Imaging 325 High-Throughput Single-Cell Manipulation and Measurements 326 SICM as an Electrochemical Probe 326 Applications in Material Sciences 327 Applications in Life Sciences 328 High-Throughput Scanning Electrochemical Cell Microscopy 329 Technical and Theoretical Developments 329 Electrochemical Measurements and Characterization 331 Popular Redox Reactions and Electrode Materials 331 Corrosion 332 Phase Formation 332 Two-Dimensional Materials 333 Photoelectrochemistry 335 Electrocatalysis: Single Particles and PseudoSingle-Crystal Screening of Structure−Activity 336 Battery Electrode Materials 339 Optical Microscopies in Electrochemistry 339 Overview of Operational Principles 339 Operational Principles 339 Methodologies for Quantitative Image Analysis 340 Converting Local Optical Information into an Electrochemically Relevant Signal 340 Computing and Automatized Image Analysis 340 Imaging Single Events 340 A Complement to Single Nanoobject Electrochemistry 340 Electron Transfer 341 Probing Concentration Profiles 341 Conversion 341 Growth and Dissolution 342 Catalysis and Motion 342 Competing Processes 343 Electrochemistry versus Physical Transformation 343 Competing Electrochemical Reactions 344 One versus Many 344 Seeing Collective Behaviors 344 How to Access Missing Pieces of Information 344 Hyphenation with Local Complementary Information 345 Other Electrochemical and Electronic HighThroughput Imaging Techniques 345 Conclusion 346 Author Information 347 Corresponding Authors 347 Authors 347 Author Contributions 347 Notes 347 Biographies 347 Acknowledgments 348 List of Abbreviations Used 348 References 349

https://pubs.acs.org/doi/pdf/10.1021/acs.analchem.2c05105

The New Era of High-Throughput Nanoelectrochemistry

The activity of Ni (hydr)oxides for the electrochemical evolution of oxygen (OER), a key component of the overall water splitting reaction, is known to be greatly enhanced by the incorporation of Fe. However, a complete understanding of the role of cationic Fe species and the nature of the catalyst surface under reaction conditions remains unclear. Here, using a combination of electrochemical cell and conventional transmission electron microscopy, we show how the surface of NiO electrocatalysts, with initially well-defined surface facets, restructures under applied potential and forms an active NiFe layered double (oxy)hydroxide (NiFe-LDH) when Fe3+ ions are present in the electrolyte. Continued OER under these conditions, however, leads to the creation of additional FeOx aggregates. Electrochemically, the NiFe-LDH formation correlates with a lower onset potential toward the OER, whereas the formation of the FeOx aggregates is accompanied by a gradual decrease in the OER activity. Complementary insight into the catalyst near-surface composition, structure, and chemical state is further extracted using X-ray photoelectron spectroscopy, operando Raman spectroscopy, and operando X-ray absorption spectroscopy together with measurements of Fe uptake by the electrocatalysts using time-resolved inductively coupled plasma mass spectrometry. Notably, we identified that the catalytic deactivation under stationary conditions is linked to the degradation of in situ-created NiFe-LDH. These insights exemplify the complexity of the active state formation and show how its structural and morphological evolution under different applied potentials can be directly linked to the catalyst activation and degradation.

Spatially and Chemically Resolved Visualization of Fe Incorporation into NiO Octahedra during the Oxygen Evolution Reaction.

Heterogeneous catalysis in thermal gas-phase and electrochemical liquid-phase chemical conversion plays an important role in our modern energy landscape. However, many of the structural features that drive efficient chemical energy conversion are still unknown. These features are, in general, highly distinct on the local scale and lack translational symmetry, and thus, they are difficult to capture without the required spatial and temporal resolution. Correlating these structures to their function will, conversely, allow us to disentangle irrelevant and relevant features, explore the entanglement of different local structures, and provide us with the necessary understanding to tailor novel catalyst systems with improved productivity. This critical review provides a summary of the still immature field of operando electron microscopy for thermal gas-phase and electrochemical liquid-phase reactions. It focuses on the complexity of investigating catalytic reactions and catalysts, progress in the field, and analysis. The forthcoming advances are discussed in view of correlative techniques, artificial intelligence in analysis, and novel reactor designs.

Operando Electron Microscopy of Catalysts: The Missing Cornerstone in Heterogeneous Catalysis Research?

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. 

Operando Methods: A New Era of Electrochemistry

Cathodic corrosion represents an enigmatic electrochemical process in which metallic electrodes corrode under sufficiently reducing potentials. Although discovered by Fritz Haber in the 19th century, only recently has progress been made in beginning to understand the atomistic mechanisms of corroding bulk electrodes. The creation of nanoparticles as the end-product of the corrosion process suggests an additional length scale of complexity. Here, we studied the dynamic evolution of morphology, composition, and crystallographic structural information of nanocrystal corrosion products by analytical and four-dimensional electrochemical liquid-cell scanning transmission electron microscopy (EC-STEM). Our operando/in situ electron microscopy revealed, in real-time, at the nanometer scale, that cathodic corrosion yields significantly higher levels of structural degradation for heterogeneous nanocrystals than bulk electrodes. In particular, the cathodic corrosion of Au nanocubes on bulk Pt electrodes led to the unexpected formation of thermodynamically immiscible Au-Pt alloy nanoparticles. The highly kinetically driven corrosion process is evidenced by the successive anisotropic transition from stable Pt(111) bulk single-crystal surfaces evolving to energetically less-stable (100) and (110) steps. The motifs identified in this microscopy study of cathodic corrosion of nanocrystals are likely to underlie the structural evolution of nanoscale electrocatalysts during many electrochemical reactions under highly reducing potentials, such as CO2 and N2 reduction.

Elucidating Cathodic Corrosion Mechanisms with Operando Electrochemical Transmission Electron Microscopy.

Flue gas produced by biomass fuel combustion contains various chlorine-containing substances and is an important factor causing biomass boiler corrosion. The corrosion processes of chlorine, hydrogen chloride and water on iron covered with an intact/damaged oxide film were investigated under the high temperature of 1300 K through reactive molecular dynamics simulation. The results show that the diffusion processes of oxygen and chlorine are similar and can be divided into three stages: rapid diffusion, continuous diffusion, and no oxide film (stable). Oxygen diffusion in Fe2O3 into a pure iron layer is the main cause of gas corrosion in iron/iron oxide systems. A complete oxide film can hinder iron corrosion by chlorine and hydrogen chloride. Damage in an oxide film significantly affects oxygen and chlorine diffusion and iron corrosion. However, such influence is gradually reduced. The integrity of a protective film is the key to alleviating corrosion. Water facilitates the dissociation of chlorine and hydrogen chloride, and it reacts with iron at high temperatures to enhance corrosion. This study improves the understanding of the iron oxide/iron corrosion from chlorine-containing gases from a microscopic perspective and is of great significance to metal corrosion protection and biomass combustion technologies.

/pdf/corrosion-of-iron-covered-with-iron-oxide-film-by-chlorine-2l3bpp72.pdf

Corrosion of Iron Covered with Iron Oxide Film by Chlorine and Hydrogen Chloride Gases: A Molecular Dynamics Simulation Study Using the ReaxFF

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Elucidating Cathodic Corrosion Mechanisms with Operando Electrochemical Transmission Electron Microscopy.

Corrosion of Iron Covered with Iron Oxide Film by Chlorine and Hydrogen Chloride Gases: A Molecular Dynamics Simulation Study Using the ReaxFF