Electrocatalysis in Alkaline Media and Alkaline Membrane-Based Energy Technologies

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(6), P. 6117 - 6321

Published: Feb. 8, 2022

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

Language: Английский

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Single-Atom Engineering to Ignite 2D Transition Metal Dichalcogenide Based Catalysis: Fundamentals, Progress, and Beyond

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(1), P. 1273 - 1348

Published: Nov. 17, 2021

Single-atom catalysis has been recognized as a pivotal milestone in the development history of heterogeneous by virtue its superior catalytic performance, ultrahigh atomic utilization, and well-defined structure. Beyond single-atom protrusions, two more motifs substitutions vacancies along with synergistic motif assemblies have progressively developed to enrich family. On other hand, besides traditional carbon material based substrates, wide variety 2D transitional metal dichalcogenides (TMDs) emerging promising platform for owing their diverse elemental compositions, variable crystal structures, flexible electronic intrinsic activities toward many reactions. Such substantial expansion both substrates provides an enriched toolbox further optimize geometric structures pushing performance limit. Concomitantly, higher requirements put forward synthetic characterization techniques related technical bottlenecks being continuously conquered. Furthermore, this burgeoning catalyst (SAC) system triggered serial scientific issues about changeable single atom-2D substrate interaction, ambiguous effects various assemblies, well dynamic structure-performance correlations, all which necessitate clarification comprehensive summary. In context, Review aims summarize critically discuss engineering whole field TMD covering evolution history, methodologies, techniques, applications, correlations. situ are highlighted regarding critical roles real-time detection SAC reconstruction reaction pathway evolution, thus shedding light on lifetime correlations lay solid theoretical foundation field, especially SACs.

Language: Английский

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Recent advances in rare-earth-based materials for electrocatalysis

Chem Catalysis, Journal Year: 2022, Volume and Issue: 2(5), P. 967 - 1008

Published: March 3, 2022

Language: Английский

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Bridging the complexity gap in computational heterogeneous catalysis with machine learning

Nature Catalysis, Journal Year: 2023, Volume and Issue: 6(2), P. 122 - 136

Published: Feb. 23, 2023

Language: Английский

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The Open Catalyst 2022 (OC22) Dataset and Challenges for Oxide Electrocatalysts

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(5), P. 3066 - 3084

Published: Feb. 16, 2023

The development of machine learning models for electrocatalysts requires a broad set training data to enable their use across wide variety materials. One class materials that currently lacks sufficient is oxides, which are critical the Oxygen Evolution Reaction (OER) catalysts. To address this, we developed Open Catalyst 2022 (OC22) dataset, consisting 62,331 Density Functional Theory (DFT) relaxations (∼9,854,504 single point calculations) range oxide materials, coverages, and adsorbates. We define generalized total energy tasks property prediction beyond adsorption energies; test baseline performance several graph neural networks; provide predefined dataset splits establish clear benchmarks future efforts. In most general task, GemNet-OC sees ∼36% improvement in predictions when combining chemically dissimilar 2020 Data (OC20) OC22 datasets via fine-tuning. Similarly, achieved ∼19% on OC20 ∼9% force using joint training. demonstrate practical utility top performing model by capturing literature energies important OER scaling relationships. expect an benchmark seeking incorporate intricate long-range electrostatic magnetic interactions surfaces. open sourced, public leaderboard available encourage continued community developments data.

Language: Английский

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Formation of active sites on transition metals through reaction-driven migration of surface atoms

Science, Journal Year: 2023, Volume and Issue: 380(6640), P. 70 - 76

Published: April 6, 2023

Adopting low-index single-crystal surfaces as models for metal nanoparticle catalysts has been questioned by the experimental findings of adsorbate-induced formation subnanometer clusters on several surfaces. We used density functional theory calculations to elucidate conditions that lead cluster and show how adatom energies enable efficient screening required formation. studied a combination eight face-centered cubic transition metals 18 common surface intermediates identified systems relevant catalytic reactions, such carbon monoxide (CO) oxidation ammonia (NH3) oxidation. kinetic Monte Carlo simulations CO-induced process copper surface. Scanning tunneling microscopy CO nickel (111) contains steps dislocations points structure sensitivity this phenomenon. Metal-metal bond breaking leads evolution catalyst structures under realistic reaction occurs much more broadly than previously thought.

Language: Английский

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Rare‐Earth Single‐Atom Catalysts: A New Frontier in Photo/Electrocatalysis

Small Methods, Journal Year: 2022, Volume and Issue: 6(8)

Published: June 25, 2022

Abstract Single‐atom catalysts (SACs) provide well‐defined active sites with 100% atom utilization, and can be prepared using a wide range of support materials. Therefore, they are attracting global attention, especially in the fields energy conversion storage. To date, research has focused on transition‐metal precious‐metal‐based SACs. More recently, rare‐earth (RE)‐based SACs have emerged as new frontier photo/electrocatalysis owing to their unique electronic structure arising from spin‐orbit coupling 4f valence orbitals, unsaturated coordination environment, behavior charge‐transport bridges. However, systematic review role RE sites, catalytic mechanisms, synthetic methods for is lacking. this review, latest developments having applications summarized discussed. First, theoretical advantages briefly introduced, focusing roles orbitals coupled levels. In addition, most recent progress several important photo/electrocatalytic reactions corresponding mechanisms Further, strategies production reported. Finally, challenges development highlighted, along future directions perspectives.

Language: Английский

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Intermetallic Nanocrystals for Fuel-Cells-Based Electrocatalysis

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(22), P. 12507 - 12593

Published: Nov. 1, 2023

Electrocatalysis underpins the renewable electrochemical conversions for sustainability, which further replies on metallic nanocrystals as vital electrocatalysts. Intermetallic have been known to show distinct properties compared their disordered counterparts, and long explored functional improvements. Tremendous progresses made in past few years, with notable trend of more precise engineering down an atomic level investigation transferring into practical membrane electrode assembly (MEA), motivates this timely review. After addressing basic thermodynamic kinetic fundamentals, we discuss classic latest synthetic strategies that enable not only formation intermetallic phase but also rational control other catalysis-determinant structural parameters, such size morphology. We demonstrate emerging nanomaterials potentially advancement energy electrocatalysis. Then, state-of-the-art characterizations representative electrocatalysts emphasis oxygen reduction reaction evaluated a MEA setup. summarize review by laying out existing challenges offering perspective future research directions toward practicing conversions.

Language: Английский

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Catalytic active centers beyond transition metals: atomically dispersed alkaline-earth metals for the electroreduction of nitrate to ammonia

Journal of Materials Chemistry A, Journal Year: 2022, Volume and Issue: 11(4), P. 1817 - 1828

Published: Dec. 19, 2022

Taking an alkaline-earth (AE) metal single-atom catalyst supported on graphene as the representative, feasibility of AE metals active centers for electrocatalytic nitrate reduction reaction to produce NH 3 has been theoretically explored.

Language: Английский

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Computational chemistry for water-splitting electrocatalysis

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(6), P. 2771 - 2807

Published: Jan. 1, 2024

This review presents the basics of electrochemical water electrolysis, discusses progress in computational methods, models, and descriptors, evaluates remaining challenges this field.

Language: Английский

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