Asymmetric charge distribution boosts hydrogen evolution performance in two‐dimensional MoO₂/MoS₂ step heterostructure

Carbon Energy, Год журнала: 2025, Номер unknown

Опубликована: Янв. 3, 2025

Abstract Step heterostructures are predicted to hold a profound catalytic performance because of the rearranged electronic structure at their interface. However, limitations in morphology prepared by hydrothermal reactions or molten salt‐assisted strategies make it challenging directly assess charge distribution and evaluate single interface's hydrogen evolution reaction (HER) performance. Here, we two‐dimensional MoO 2 /MoS step with large specific surface area chemical vapor deposition method. Surface Kelvin probe force microscopy electrical transport measurement verified asymmetric By fabricating series micro on‐chip electrocatalytic devices, investigate HER for interface confirm that is essential superior We experimentally confirmed enhancement heterostructure attributed This work lays foundation designing highly efficient systems based on heterostructures.

Язык: Английский

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Heterostructured Electrocatalysts: from Fundamental Microkinetic Model to Electron Configuration and Interfacial Reactive Microenvironment

Advanced Materials, Год журнала: 2025, Номер unknown

Опубликована: Март 4, 2025

Electrocatalysts can efficiently convert earth-abundant simple molecules into high-value-added products. In this context, heterostructures, which are largely determined by the interface, have emerged as a pivotal architecture for enhancing activity of electrocatalysts. review, atomistic understanding heterostructured electrocatalysts is considered, focusing on reaction kinetic rate and electron configuration, gained from both empirical studies theoretical models. We start fundamentals microkinetic model, adsorption energy theory, electric double layer model. The importance heterostructures to accelerate electrochemical processes via modulating configuration interfacial reactive microenvironment highlighted, considering rectification, space charge region, built-in field, synergistic interactions, lattice strain, geometric effect. conclude review summarizing challenges perspectives in field electrocatalysts, such determination transition state energy, their dynamic evolution, refinement approaches, use machine learning.

Язык: Английский

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Toward a molecular-scale picture of water electrolysis: mechanistic insights, fundamental kinetics and electrocatalyst dynamic evolution

Coordination Chemistry Reviews, Год журнала: 2025, Номер 536, С. 216651 - 216651

Опубликована: Апрель 6, 2025

Язык: Английский

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Unveiling the Aggregation of M−N−C Single Atoms into Highly Efficient MOOH Nanoclusters during Alkaline Water Oxidation

Angewandte Chemie International Edition, Год журнала: 2024, Номер 64(1)

Опубликована: Авг. 28, 2024

M-N-C-type single-atom catalysts (SACs) are highly efficient for the electrocatalytic oxygen evolution reaction (OER). And isolated metal atoms usually considered real active sites. However, oxidative structural of coordinated N during OER will probably damage structure M-N-C, hence resulting in a completely different mechanism. Here, we reveal aggregation M-N-C materials alkaline OER. Taking Ni-N-C as an example, multiple characterizations show that on surface is almost dissolved form NO

Язык: Английский

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Atomic Cluster Outperforms Single Atom in Hydrogen Evolution and Hydrazine Oxidation for Energy‐Efficient Water Splitting

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Янв. 2, 2025

Abstract The hydrazine‐assisted water splitting (HzAWS) is promising for energy‐saving hydrogen production. However, developing efficient bifunctional catalysts that exert evolution reaction (HER) and hydrazine oxidation (HzOR) at industrial‐grade current densities remains challenging. Here, Ru C ‐NiCoP catalyst, ruthenium clusters (Ru ) immobilized onto NiCoP, developed to elucidate the superior performance of in enhancing electrocatalytic activity over single atoms SA ). achieves 10 100 mA cm −2 HER HzOR with working potentials −10 −89 mV, respectively, outperforming (−16 −65 mV). During HzAWS, a cell voltage reduction 1.77 V 300 observed compared overall splitting. Density functional theory calculations reveal improves adsorption energy H 2 O N 4 , optimizes H* intermediate desorption, reduces dehydrogenation barrier from *N 3 . Additionally, direct fuel anode delivers an impressive power density 226 mW enables self‐powered production system, achieving unprecedented rate 4.9 mmol h −1 This work offers new perspective on sub‐nanoscale electrocatalysts advancing practical techniques.

Язык: Английский

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Enhancing Built‐In Electric Field via Defect‐Mediated Interfacial Chemical Bond Construction in Chalcogenide Heterojunction for Alcohol Photooxidation Coupled with H₂ Production

Advanced Functional Materials, Год журнала: 2024, Номер unknown

Опубликована: Сен. 14, 2024

Abstract Rationally designing nanostructures based on an adequate understanding of structure‐performance relationships is key for directional charge transfer regulation in heterojunction photocatalysts. A general strategy developed synthesizing bifunctional Sv‐chalcogenide/Ti 3 C 2 Schottky junctions (Sv = sulfur vacancies, chalcogenides containing CdS, CdIn S 4 , ZnIn ZnS, CuInS ) featuring a giant built‐in electric field (BIEF) via defect‐mediated heterocomponent anchorage, which consists vacancy modulation and Ti nanoparticle anchoring at defects interfacial Metal─Oxygen (M─O) bonds. These heterojunctions have the distinctive interface structure semicoherent phase boundaries directionally aligned BIEF pointing from to . The enhanced creates asymmetrical distribution, not only governs migration behavior by enabling carrier localization delocalized electron transport continuity but also regulates molecular catalytic optimizing pivotal intermediate adsorption/activation ( * Ar‐CH(R )‐OH dehydrogenation H evolution) selective alcohol photooxidation coupled with generation. Encouragingly, exhibits unprecedented performance (up 13.34‐fold higher efficiency than unmodulated chalcogenides) good substrate compatibility various alcohols. This work demonstrates synergistic effects surface density control interaction regulating BIEFs, elucidating substantial impact reinforced properties behavior.

Язык: Английский

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Reactive Oxygen Species-Mediated Photooxidation in a Full-Space Electric Field Catalyst: Selectivity and Activity Control of Intramolecular Alcohol Hydroxyl and Aldehyde Groups

ACS Catalysis, Год журнала: 2024, Номер unknown, С. 17716 - 17726

Опубликована: Ноя. 15, 2024

The rational design of nanocatalysts with high activity and selectivity is crucial for photocatalytic selective oxidation, where reactive oxygen species (ROS) serve as the key oxidants inducing molecular catalytic behavior. We developed a defective ZnIn2S4/Ti3C2 Schottky junction featuring full-space electric field by chemically anchoring Ti3C2 nanoparticles onto defects ZnIn2S4 nanosheet via defect-mediated heterocomponent anchorage approach, photocatalyst platform manipulating efficient alternative ROS generation (•OH or •O2–) to controllably oxidate intramolecular alcohol hydroxyl aldehyde group toward tunable oxygenates. directionally aligned creates asymmetrical charge distributions, facilitating carrier localization delocalized electron transportation, ultimately leading an order magnitude increase in concentration superhigh activity. Meanwhile, due their thermodynamic kinetic advantages under different atmospheres, radicals preferentially activate alcohols induce two consecutive dehydrogenation reactions, whereas superoxide aldehydes insertion processes, thereby achieving control products. Encouragingly, several compounds groups are compatible using current protocol. This work provides paradigm programmable construction composite photocatalysts elucidating substantial impact (concentrations types) on oxidation specific functional groups.

Язык: Английский

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Self-supported Ru-doped NiMoO₄ for efficient hydrogen evolution with 1000 mA cm⁻² at a low overpotential

Chemical Communications, Год журнала: 2024, Номер 60(50), С. 6423 - 6426

Опубликована: Янв. 1, 2024

This work reports the growth of self-supported Ru-doped NiMoO 4 on commercial NiMo foam, which acts as a highly active and robust electrocatalyst for ampere-level current density hydrogen evolution.

Язык: Английский

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Crystalline/amorphous nickel sulfide interface for high current density in alkaline HER: surface and volume confinement matters!

Chemical Communications, Год журнала: 2024, Номер 60(53), С. 6817 - 6820

Опубликована: Янв. 1, 2024

In this report, we have developed a novel CA interface between crystalline and amorphous nickel sulfide which required low overpotential of 15 mV for 10 mA cm −2 with the intrinsic activation alkaline hydrogen evolution reaction.

Язык: Английский

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Unveiling the Aggregation of M−N−C Single Atoms into Highly Efficient MOOH Nanoclusters during Alkaline Water Oxidation

Angewandte Chemie, Год журнала: 2024, Номер 137(1)

Опубликована: Авг. 28, 2024

Abstract M−N−C‐type single‐atom catalysts (SACs) are highly efficient for the electrocatalytic oxygen evolution reaction (OER). And isolated metal atoms usually considered real active sites. However, oxidative structural of coordinated N during OER will probably damage structure M−N−C, hence resulting in a completely different mechanism. Here, we reveal aggregation M−N−C materials alkaline OER. Taking Ni−N−C as an example, multiple characterizations show that on surface is almost dissolved form NO 3 − , accompanied by generation abundant O functional groups carbon support. Accordingly, Ni−N bonds broken. Through dissolution‐redeposition mechanism and further oxidation, Ni finally converted to NiOOH nanoclusters supported sites enhanced Fe−N−C Co−N−C also have similar Our findings provide unique insight into activity origin M−N−C‐based under electrooxidative conditions.

Язык: Английский

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