Importing Atomic Rare‐Earth Sites to Activate Lattice Oxygen of Spinel Oxides for Electrocatalytic Oxygen Evolution

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Окт. 9, 2024

Abstract Spinel oxides have emerged as highly active catalysts for the oxygen evolution reaction (OER). Owing to covalency competition, OER process on spinel often follows an arduous adsorbate mechanism (AEM) pathway. Herein, we propose a novel rare‐earth sites substitution strategy tune lattice redox of and bypass AEM scaling relationship limitation. Taking NiCo 2 O 4 model, incorporation Ce into octahedral site induces formation Ce−O−M (M=Ni, Co) bridge, which triggers charge redistribution within . The developed Ce−NiCo exhibits remarkable activity with low overpotential, satisfactory electrochemical stability, good practicability in anion‐exchange membrane water electrolyzer. Theoretical analyses reveal that surface more favorable (LOM) pathway non‐concerted proton‐electron transfers compared pure , also verified by pH‐dependent behavior situ Raman analysis. 18 O‐labeled mass spectrometry provides direct evidence released during originates from We discover electron delocalization f states through favoring antibonding state occupation Ni−O bonding [Ce−O−Ni] unit site, thereby activating OER. This work new perspective designing offers significant insights rare‐earth‐enhanced LOM mechanism.

Язык: Английский

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Non‐Noble‐Metal‐Based Electrocatalysts for Acidic Oxygen Evolution Reaction: Recent Progress, Challenges, and Perspectives

Small, Год журнала: 2024, Номер 20(48)

Опубликована: Авг. 25, 2024

Abstract The oxygen evolution reaction (OER) plays a pivotal role in diverse renewable energy storage and conversion technologies, including water electrolysis, electrochemical CO 2 reduction, nitrogen fixation, metal‐air batteries. Among various electrolysis techniques, proton exchange membrane (PEM)‐based devices offer numerous advantages, high current densities, exceptional chemical stability, excellent conductivity, high‐purity H . Nevertheless, the prohibitive cost associated with Ir/Ru‐based OER electrocatalysts poses significant barrier to broad‐scale application of PEM‐based splitting. Consequently, it is crucial advance development non‐noble metal catalysis substance acid‐activity thereby fostering their widespread integration into PEM electrolyzers (PEMWEs). In this review, comprehensive analysis acidic mechanism, encompassing adsorbate mechanism (AEM), lattice (LOM) oxide path (OPM) offered. Subsequently, systematic summary recently reported noble‐metal‐free catalysts transition metal‐based, carbon‐based other types provided. Additionally, compilation situ/operando characterization techniques provided, serving as invaluable tools for furnishing experimental evidence comprehend catalytic mechanism. Finally, present challenges future research directions concerning precious‐metal‐free are comprehensively summarized discussed review.

Язык: Английский

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Triggered factors and structure-activity relationship in the dynamic reconstruction processing of MOF for the alkaline oxygen evolution reaction

Coordination Chemistry Reviews, Год журнала: 2024, Номер 522, С. 216235 - 216235

Опубликована: Окт. 1, 2024

Язык: Английский

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High-Entropy Ultrathin Amorphous Metal–Organic Framework-Stabilized Ru(Mo) Dual-Atom Sites for Water Oxidation

ACS Energy Letters, Год журнала: 2024, Номер unknown, С. 5763 - 5770

Опубликована: Ноя. 6, 2024

High-entropy metal–organic frameworks (HE-MOFs) offer immense potential in electrocatalysis due to their diverse metallic compositions and high densities of active sites. Integrating bimetallic single-atom catalysts (SACs) with HE-MOFs for enhanced oxygen evolution reaction (OER) performance remains challenging. Here, we stabilize atomically dispersed Ru Mo amorphous HE-MOF nanosheets (HE(Ru,Mo)-MOFs) via situ-formed high-entropy oxides, elucidating the deprotonation mechanism. Evidence supports presence high-density O-bridged dual-atom The multimetallic composition induces electronic redistribution balances oxidation state metal sites, enhancing intrinsic OER activity. HE(Ru,Mo)-MOFs exhibit low overpotentials 267 mV@10 mA cm–2 266 alkaline freshwater industrial wastewater, respectively, exceptional durability surpassing that commercial RuO2 catalysts. Mechanistic insights reveal atomic dispersion facilitates rapid charge transfer intermediate transformation, promising advanced energy conversion.

Язык: Английский

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High entropy catalysts in electrolytic water splitting: A review from properties to applications

Chemical Engineering Journal, Год журнала: 2024, Номер 498, С. 155736 - 155736

Опубликована: Сен. 12, 2024

Язык: Английский

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Spiral‐concave Prussian Blue Crystals with Rich Steps: Growth Mechanism and Coordination Regulation

Angewandte Chemie International Edition, Год журнала: 2024, Номер 64(2)

Опубликована: Авг. 29, 2024

Abstract Investigating the formation and transformation mechanisms of spiral‐concave crystals holds significant potential for advancing innovative material design comprehension. We examined kinetics‐controlled nucleation growth Prussian Blue with spiral concave structures, constructed a detailed crystal phase diagram. The hexacyanoferrate (SC‐HCF) crystals, characterized by high‐density surface steps low stress‐strain architecture, exhibit enhanced activity due to their facile interaction reactants. Notably, coordination environment SC‐HCF can be precisely modulated introduction diverse metals. Utilizing X‐ray absorption fine structure spectroscopy in situ ultraviolet‐visible spectroscopy, we elucidated mechanism Co‐HCF facilitated oriented adsorption‐ion exchange (OA‐IE) process. Both experimental data, density functional theory confirm that possesses an optimized energy band structure, capable adjusting local electronic enhancing performance oxygen evolution reaction. This work not only elucidates regulation rich HCF, but also offers novel perspective constructing nanocrystals intricate structures.

Язык: Английский

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Acidic oxygen evolution reaction via lattice oxygen oxidation mechanism: progress and challenges

Energy Materials, Год журнала: 2025, Номер 5(3)

Опубликована: Янв. 15, 2025

The lattice oxygen mechanism (LOM) plays a critical role in the acidic evolution reaction (OER) as it provides more efficient catalytic pathway compared to conventional adsorption (AEM). LOM effectively lowers energy threshold of and accelerates rate by exciting atoms catalyst directly participate OER process. In recent years, with increase in-depth understanding LOM, researchers have developed variety iridium (Ir) ruthenium (Ru)-based catalysts, well non-precious metal oxide optimized their performance through different strategies. However, still faces many challenges practical applications, including long-term stability precise modulation active sites, application efficiency real electrolysis systems. Here, we review OER, analyze its difference traditional AEM new (OPM) mechanism, discuss experimental theoretical validation methods pathway, prospect future development electrocatalyst design conversion, aiming provide fresh perspectives strategies for solving current challenges.

Язык: Английский

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Spin effects in electrocatalysis: Mechanisms, catalyst engineering, modulation, and applications

Materials Science and Engineering R Reports, Год журнала: 2025, Номер 164, С. 100967 - 100967

Опубликована: Март 5, 2025

Язык: Английский

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DFT-Driven Approaches to Optimizing Small Bandgap Doping Structures: A Brief Review

Journal of Inorganic and Organometallic Polymers and Materials, Год журнала: 2025, Номер unknown

Опубликована: Март 20, 2025

Язык: Английский

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Electrochemical hydrogen production through anion exchange membrane water electrolysis (AEMWE): Recent progress and associated challenges in hydrogen production

International Journal of Hydrogen Energy, Год журнала: 2024, Номер 94, С. 1174 - 1211

Опубликована: Ноя. 16, 2024

Язык: Английский

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