Dynamic Redox Induced Localized Charge Accumulation Accelerating Proton Exchange Membrane Electrolysis

Advanced Materials, Год журнала: 2025, Номер unknown

Опубликована: Янв. 2, 2025

The sluggish anodic oxygen evolution reaction (OER) in proton exchange membrane (PEM) electrolysis necessitates applied bias to facilitate electron transfer as well bond cleavage and formation. Traditional electrocatalysis focuses on analyzing the effects of transfer, while role charge accumulation induced by overpotential has not been thoroughly investigated. To explore influence mechanism bias-driven accumulation, capacitive Mn is incorporated into IrO

Язык: Английский

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Transient pulsed discharge preparation of graphene aerogel supports asymmetric Cu cluster catalysts promote CO2 electroreduction

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Янв. 31, 2025

Designing asymmetrical structures is an effective strategy to optimize metallic catalysts for electrochemical carbon dioxide reduction reactions. Herein, we demonstrate a transient pulsed discharge method instantaneously constructing graphene-aerogel supports asymmetric copper nanocluster catalysts. This process induces the convergence of atoms decomposed by chloride onto graphene originating from intense current pulse and high temperature. The exhibit atomic electronic due lattice distortion oxygen doping clusters. In reaction, selectivity activity ethanol production are enhanced structure abundance active sites on catalysts, achieving Faradaic efficiency 75.3% 90.5% multicarbon products at −1.1 V vs. reversible hydrogen electrode. Moreover, strong interactions between nanoclusters support confer notable long-term stability. We elucidate key reaction intermediates mechanisms Cu4O-Cu/C2O1 moieties through in situ testing density functional theory calculations. study provides innovative approach balancing stability asymmetric-structure energy conversion. Asymmetric show promise CO2 catalytic reduction. Here, authors develop prepare graphene-aerogel-supported Cu that enhance conversion into products.

Язык: Английский

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Location‐Specific Microenvironment Modulation Around Single‐Atom Metal Sites in Metal‐Organic Frameworks for Boosting Catalysis

Angewandte Chemie, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 7, 2024

Abstract Despite coordination environment of catalytic metal sites has been recognized to be great importance in single‐atom catalysts (SACs), a significant challenge remains the understanding how location‐specific microenvironment higher sphere influences their catalysis. Herein, series Cu‐based SACs, namely Cu 1 /UiO‐66‐X (X=‐NO 2 , ‐H, and ‐NH ), are successfully constructed by anchoring single atoms onto Zr‐oxo clusters metal–organic frameworks (MOFs), i.e., UiO‐66‐X. The ‐X functional groups dangling on MOF linkers could regarded as remote regulate electronic properties atoms. Remarkably, they exhibit differences catalysis toward hydroboration alkynes. activity follows order /UiO‐66‐NO > /UiO‐66 /UiO‐66‐NH under identical reaction conditions, where showcases phenylacetylene conversion 92 %, ~3.5 times efficiency than that . Experimental calculation results jointly support structure is modulated microenvironment, thereby regulating product desorption promoting

Язык: Английский

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Oxophilic Low‐Coordination Gd‐N₃ Single Atom Sites With P‐Enhanced Second Coordination for High‐Performance Al‐Air Batteries

Advanced Functional Materials, Год журнала: 2024, Номер unknown

Опубликована: Сен. 29, 2024

Abstract The development of efficient rare earth single‐atom (SA) catalysts for the oxygen reduction reaction (ORR) is essential yet challenging high‐performance aluminum‐air batteries (AABs). This study introduces a concept‐to‐proof strategy synthesizing hollow carbon‐supported gadolinium (Gd) SA catalyst using low‐coordination and second‐coordination sphere engineering. In this design, Gd atoms are coordinated to three nitrogen (N) in N‐doped carbon surrounded by six phosphorus (P) atoms, forming Gd‐N 3 ‐P 6 sites. These demonstrated exceptional ORR performance, achieving half‐wave potential 0.895 V superior durability compared commercial Pt/C benchmark. When integrated into AABs, they delivered impressive with peak power density 257 mW/cm 2 an energy 2916 Wh/kg, alongside enhanced cycling stability. situ characterization theoretical calculations revealed that strategic placement P second coordination significantly valence state site. enhancement improved adsorption capacity O H while facilitating rapid desorption * OH intermediates during ORR. offers valuable insights cost‐effective catalysts, emphasizing significance modulating local environment metal

Язык: Английский

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Location‐Specific Microenvironment Modulation Around Single‐Atom Metal Sites in Metal‐Organic Frameworks for Boosting Catalysis

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

Опубликована: Ноя. 7, 2024

Abstract Despite coordination environment of catalytic metal sites has been recognized to be great importance in single‐atom catalysts (SACs), a significant challenge remains the understanding how location‐specific microenvironment higher sphere influences their catalysis. Herein, series Cu‐based SACs, namely Cu 1 /UiO‐66‐X (X=‐NO 2 , ‐H, and ‐NH ), are successfully constructed by anchoring single atoms onto Zr‐oxo clusters metal–organic frameworks (MOFs), i.e., UiO‐66‐X. The ‐X functional groups dangling on MOF linkers could regarded as remote regulate electronic properties atoms. Remarkably, they exhibit differences catalysis toward hydroboration alkynes. activity follows order /UiO‐66‐NO > /UiO‐66 /UiO‐66‐NH under identical reaction conditions, where showcases phenylacetylene conversion 92 %, ~3.5 times efficiency than that . Experimental calculation results jointly support structure is modulated microenvironment, thereby regulating product desorption promoting

Язык: Английский

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Upcycling of mixed polyolefin wastes to 3D structured carbon Joule heaters for decarbonized hydrogen production

Materials Horizons, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

This work presents an integrated approach to industrial decarbonization by converting mixed polyolefin waste into structured carbon with exceptional Joule heating properties, enabling efficient electrified hydrogen production via NH 3 decomposition.

Язык: Английский

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In-situ reconstruction of electrocatalysts for efficient energy and environmental electrocatalytic reactions

Materials Science and Engineering R Reports, Год журнала: 2025, Номер 164, С. 100978 - 100978

Опубликована: Март 23, 2025

Язык: Английский

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Photocatalytic H₂O₂ Production with >30% Quantum Efficiency via Monovalent Copper Dynamics

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Май 8, 2025

Photocatalytic O2 reduction to H2O2 is a green and promising technology with advantages in cost-effectiveness, sustainability, environmental friendliness, but its efficiency constrained by limited selectivity for the two-electron oxygen reaction (ORR) pathway. Here, we anchored isolated Cu atoms tunable oxidation states onto WO3 as effective active centers enhance photocatalytic production. Due charge compensation between single support, state of species exhibited loading-dependent transition +2 +1 valence. Experimental theoretical analyses indicate that Cu(I) sites exhibit outstanding adsorption activation capabilities, transforming thermodynamically unfavorable hydrogenation *OOH intermediate (the rate-determining step ORR pathway) into an exothermic process, thereby significantly improving efficiency. The Cu(I)-SA/WO3 photocatalyst production rate 102 μmol h-1 under visible light irradiation, much higher than other reported photocatalysts. More importantly, it achieves impressive apparent quantum 30% at 420 nm, making significant breakthrough this field. This work provides novel perspectives designing single-atom catalysts efficient synthesis via electronic modulation.

Язык: Английский

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Regulating the spin state of triple-atom catalysts for improved oxygen electrocatalysis in zinc-air batteries at subzero temperature

The Innovation Materials, Год журнала: 2025, Номер unknown, С. 100131 - 100131

Опубликована: Янв. 1, 2025

<p>Triple-atom catalysts (TACs), building upon dual-atom catalysts, have demonstrated exceptional catalytic activity toward oxygen reduction reaction (ORR). Nevertheless, advancing the of TACs for application in low-temperature (Low-T) energy conversion devices remains a formidable challenge, primarily limited by slow capture efficiency reactants at sites. In this work, utilizing Fe-Fe double atomic pairs as foundational research model, we plant CoN₄ site adjacent to activate them construct efficient ORR electrocatalysts (named Fe₂/Co-NHCS) featuring Fe₂N₅+CoN₄ tri-atomic structure. The can optimize spin state from low medium with <inline-formula><tex-math id="M1">${ {t}_{{2g}^{4}}} $</tex-math></inline-formula> id="M2">${ {e}_{{g}^{1}} }$</tex-math></inline-formula>3d-electron configuration, which makes bind more readily complete process. As anticipated, Fe₂/Co-NHCS achieved high half-wave potential 0.92 V. Moreover, flexible Zn-air batteries powered deliver large peak power density 57.3 mW cm^-2 and brilliant charge-discharge stability over 150 stable cycles -40°C. This advances modulating electron states diatomic Fe sites, paving viable route expanding range ZABs environment.</p>

Язык: Английский

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Atomically Mixed High‐Entropy‐Alloy Nanoframes with 3D Subnanometer‐Thick Electrocatalytic Surfaces

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Май 20, 2025

Abstract High‐entropy‐alloy (HEA) nanocrystals, characterized by multicomponent solid solutions and synergistic effects, hold great potential in catalysis. However, synthesizing HEA hollow nanocrystals with 3D architectures controlled surface atomic arrangements to enhance catalytic activity durability remains challenging. Highly active durable electrocatalysts are presented, derived from Pd@HEA core‐shell featuring a few layers containing five platinum‐group metals, synthesized via Fe(III)‐based wet etching strategy. The process transformed nanocubes enclosed {100} facets into porous nanocubes, cubic nanocages, eventually, nanoframes composed of subnanometer‐thick ridges dominated {110} facets, vacancies, step atoms. Electron microscopy synchrotron X‐ray absorption spectroscopy revealed the randomly mixed coordination environments constituent elements, underscoring excellent mixing within nanoframes. These demonstrated 9.72‐fold higher acidic hydrogen evolution reaction (HER) specific at an overpotential −0.1 V than commercial Pt/C catalysts, remarkable after 15 000 cycles, competitive performance as cathode catalysts for practical applications proton exchange membrane water electrolyzers. Density functional theory calculations attributed superior HER {110}‐enclosed atomically surfaces low‐coordination sites, optimizing adsorption free energy (ΔG H* ) near ideal value 0.

Язык: Английский

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