Oxygen Evolution/Reduction Reaction Catalysts: From In Situ Monitoring and Reaction Mechanisms to Rational Design

Chemical Reviews, Год журнала: 2023, Номер 123(9), С. 6257 - 6358

Опубликована: Март 21, 2023

The oxygen evolution reaction (OER) and reduction (ORR) are core steps of various energy conversion storage systems. However, their sluggish kinetics, i.e., the demanding multielectron transfer processes, still render OER/ORR catalysts less efficient for practical applications. Moreover, complexity catalyst–electrolyte interface makes a comprehensive understanding intrinsic mechanisms challenging. Fortunately, recent advances in situ/operando characterization techniques have facilitated kinetic monitoring under conditions. Here we provide selected highlights mechanistic studies with main emphasis placed on heterogeneous systems (primarily discussing first-row transition metals which operate basic conditions), followed by brief outlook molecular catalysts. Key sections this review focused determination true active species, identification sites, reactive intermediates. For in-depth insights into above factors, short overview metrics accurate characterizations is provided. A combination obtained time-resolved information reliable activity data will then guide rational design new Strategies such as optimizing restructuring process well overcoming adsorption-energy scaling relations be discussed. Finally, pending current challenges prospects toward development homogeneous presented.

Язык: Английский

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Ensemble effect for single-atom, small cluster and nanoparticle catalysts

Nature Catalysis, Год журнала: 2022, Номер 5(9), С. 766 - 776

Опубликована: Сен. 20, 2022

Язык: Английский

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The reformation of catalyst: From a trial-and-error synthesis to rational design

Nano Research, Год журнала: 2023, Номер 17(4), С. 3261 - 3301

Опубликована: Сен. 27, 2023

Язык: Английский

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Engineering the Electronic Structure of Single‐Atom Iron Sites with Boosted Oxygen Bifunctional Activity for Zinc–Air Batteries

Advanced Materials, Год журнала: 2022, Номер 35(9)

Опубликована: Дек. 19, 2022

Abstract Rechargeable zinc–air batteries typically require efficient, durable, and inexpensive bifunctional electrocatalysts to support oxygen reduction/evolution reactions (ORR/OER). However, sluggish kinetics mass transportation challenges must be addressed if the performance of these catalysts is enhanced. Herein, a strategy fabricate catalyst comprising atomically dispersed iron atoms supported on mesoporous nitrogen‐doped carbon (Fe SAs/NC) with accessible metal sites optimized electronic metal–support interactions developed. Both experimental results theoretical calculations reveal that engineered structures active can regulate charge distribution Fe centers optimize adsorption/desorption oxygenated intermediates. The SAs/NC containing 1 N 4 O achieves remarkable ORR activity over entire pH range, half‐wave potentials 0.93, 0.83, 0.75 V (vs reversible hydrogen electrode) in alkaline, acidic, neutral electrolytes, respectively. In addition, it demonstrates promising low overpotential 320 mV at 10 mA cm −2 for OER alkaline conditions. battery assembled exhibits superior than Pt/C+RuO 2 counterpart terms peak power density, specific capacity, cycling stability. These findings demonstrate importance structure engineering directing catalytic activity.

Язык: Английский

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Size of cerium dioxide support nanocrystals dictates reactivity of highly dispersed palladium catalysts

Science, Год журнала: 2023, Номер 380(6650), С. 1174 - 1179

Опубликована: Июнь 15, 2023

The catalytic performance of heterogeneous catalysts can be tuned by modulation the size and structure supported transition metals, which are typically regarded as active sites. In single-atom metal catalysts, support itself strongly affect properties. Here, we demonstrate that cerium dioxide (CeO2) governs reactivity atomically dispersed palladium (Pd) in carbon monoxide (CO) oxidation. Catalysts with small CeO2 nanocrystals (~4 nanometers) exhibit unusually high activity a CO-rich reaction feed, whereas medium-size (~8 preferred for lean conditions. Detailed spectroscopic investigations reveal size-dependent redox properties Pd-CeO2 interface.

Язык: Английский

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Geometric and Electronic Engineering of Atomically Dispersed Copper‐Cobalt Diatomic Sites for Synergistic Promotion of Bifunctional Oxygen Electrocatalysis in Zinc–Air Batteries

Advanced Materials, Год журнала: 2023, Номер 35(25)

Опубликована: Апрель 11, 2023

The development of rechargeable zinc-air batteries is heavily dependent on bifunctional oxygen electrocatalysts to offer exceptional reduction/evolution reaction (ORR/OER) activities. However, the design such with high activity and durability challenging. Herein, a strategy proposed create an electrocatalyst comprised copper-cobalt diatomic sites highly porous nitrogen-doped carbon matrix (Cu-Co/NC) abundantly accessible metal optimal geometric electronic structures. Experimental findings theoretical calculations demonstrate that synergistic effect Cu-Co dual-metal metal-N4 coordination induce asymmetric charge distributions moderate adsorption/desorption behavior intermediates. This exhibits extraordinary electrocatalytic activities in alkaline media, half-wave potential 0.92 V for ORR low overpotential 335 mV at 10 mA cm-2 OER. In addition, it demonstrates acidic (0.85 V) neutral (0.74 media. When applied battery, achieves operational performance outstanding (510 h), ranking as one most efficient reported date. work importance engineering isolated boosting electrochemical energy devices.

Язык: Английский

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Best practices for experiments and reporting in photocatalytic CO2 reduction

Nature Catalysis, Год журнала: 2023, Номер 6(8), С. 657 - 665

Опубликована: Авг. 10, 2023

Язык: Английский

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Bridging the complexity gap in computational heterogeneous catalysis with machine learning

Nature Catalysis, Год журнала: 2023, Номер 6(2), С. 122 - 136

Опубликована: Фев. 23, 2023

Язык: Английский

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Restructuring of titanium oxide overlayers over nickel nanoparticles during catalysis

Science, Год журнала: 2023, Номер 380(6645), С. 644 - 651

Опубликована: Май 11, 2023

Reducible supports can affect the performance of metal catalysts by formation suboxide overlayers upon reduction, a process referred to as strong metal-support interaction (SMSI). A combination operando electron microscopy and vibrational spectroscopy revealed that thin TiOx formed on nickel/titanium dioxide during 400°C reduction were completely removed under carbon hydrogenation conditions. Conversely, after 600°C exposure reaction conditions led only partial reexposure nickel, forming interfacial sites in contact with favoring carbon-carbon coupling providing species reservoir. Our findings challenge conventional understanding SMSIs call for more-detailed investigations nanocatalysts at single-particle level revisit static models structure-activity relationships.

Язык: Английский

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An Atomically Dispersed Mn-Photocatalyst for Generating Hydrogen Peroxide from Seawater via the Water Oxidation Reaction (WOR)

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(30), С. 16584 - 16596

Опубликована: Июль 24, 2023

In this work, we have fabricated an aryl amino-substituted graphitic carbon nitride (g-C3N4) catalyst with atomically dispersed Mn capable of generating hydrogen peroxide (H2O2) directly from seawater. This new exhibited excellent reactivity, obtaining up to 2230 μM H2O2 in 7 h alkaline water and 1800 seawater under identical conditions. More importantly, the was quickly recovered for subsequent reuse without appreciable loss performance. Interestingly, unlike usual two-electron oxygen reduction reaction pathway, generation through a less common oxidation (WOR) process which both direct indirect WOR processes occurred; namely, photoinduced h+ oxidized H2O via one-step 2e- WOR, first hydroxide (OH-) ion generate hydroxy radical (•OH), formed indirectly by combination two •OH. We characterized material, at catalytic sites, atomic level using electron paramagnetic resonance, X-ray absorption near edge structure, extended fine high-resolution transmission microscopy, photoelectron spectroscopy, magic-angle spinning solid-state NMR multiscale molecular modeling, combining classical reactive dynamics simulations quantum chemistry calculations.

Язык: Английский

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