Sight into a Rare-Earth-Based Catalyst with Spatial Confinement Effect from the Perspective of Electronic Structure

ACS Applied Materials & Interfaces, Год журнала: 2025, Номер unknown

Опубликована: Март 1, 2025

Rare-earth elements include 15 kinds of lanthanides as well Sc and Y elements. Interestingly, the special electronic configuration a lanthanide rare earth is [Xe]4fn5d0–16s2 (n = 0–14), which results in rare-earth materials' unique activity such areas thermal catalysis, electrocatalysis, photocatalysis, etc. It worth noting that class materials with spatial confinement effects are playing an increasingly important role catalytic performance; especially, construction hollow multishelled structures (HoMSs) can further enhance materials. In this review, we discuss depth roles 4f5d structure. Subsequently, review systematically summarizes synthesis methods HoMSs their research progress field catalysis specifically introduces advanced characterization analysis HoMSs. Finally, directions, application prospects, challenges need to be focused on future rare-earth-based discussed anticipated. We believe will not only inspire more creativity optimizing local structure design catalysts but also provide valuable insights for designing other types catalysts.

Язык: Английский

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Gd‐Induced Oxygen Vacancy Creation Activates Lattice Oxygen Oxidation for Water Electrolysis

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Фев. 26, 2025

Abstract As a key reaction in water electrolysis and fuel cells, the oxygen evolution (OER) involves sluggish four‐electron proton transfer process. Understanding OER pathways kinetics is critical for designing efficient electrocatalysts. In this study, through density functional theory (DFT) calculations, it demonstrated that incorporation of Gd into Fe‐doped NiO elevates O 2 p band center generates more unoccupied states. Furthermore, promotes formation vacancies, which, together, enhance lattice oxidation mechanism (LOM) pathway OER. The adsorption‐free energy diagrams confirm doping significantly lowers theoretical overpotentials at both Fe Ni sites NiO, thereby improving activity. Based on these findings, co‐doped ultrathin nanosheets are synthesized via spray combustion. an catalyst, material exhibited low overpotential 227 mV, which 40 mV lower than long‐term catalytic stability over 150 h. anion exchange membrane system, stable performance 120 h current 20 mA cm −2 .

Язык: Английский

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Ameliorating water splitting by entropy regulation and electronic structure engineering on pristine Prussian blue analog

Journal of Colloid and Interface Science, Год журнала: 2025, Номер 690, С. 137316 - 137316

Опубликована: Март 12, 2025

Язык: Английский

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Crystal phase-induced electronic structure modulation at Mn sites enhances singlet oxygen generation for selective catalytic ozonation of NH4+

Chemical Engineering Journal, Год журнала: 2025, Номер unknown, С. 161616 - 161616

Опубликована: Март 1, 2025

Язык: Английский

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Tungsten Defect‐Induced Surface Reconstruction of Ce₂W₂O₉ Arrays for Enhanced Oxygen Evolution Reaction Performance

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Апрель 7, 2025

Abstract Cerium oxide has emerged as a crucial promoter for regulating the electrocatalytic oxygen evolution reaction (OER) performance of other active components; however, mechanism underlying its intrinsic activity remains poorly understood. Herein, novel self‐supported coral‐like Ce 2 W O 9 array is synthesized on carbon cloth using simple ion‐exchange method. The in situ electrochemical surface reconstruction facilitated formation defects, which effectively altered local bonding environment atoms. Based advanced characterization techniques and theoretical calculations, it concluded that optimized centers served sites, substantially reducing energy barrier potential‐determining step ( * OOH formation), turn, facilitating generation boosting activity. Consequently, reconstructed electrode exhibited an exceptionally low overpotential 351 mV at 100 mA cm −2 1 m KOH, while maintaining remarkable stability over 000 h 20 . This study provides valuable insights into mechanistic understanding strategic design rare‐earth oxide‐based electrocatalysts.

Язык: Английский

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Rational Design of Rare Earth-Based Nanomaterials for Electrocatalytic Reactions

ACS Nano, Год журнала: 2025, Номер unknown

Опубликована: Май 1, 2025

Rare earth-based nanomaterials hold great promise for applications in the electrocatalysis field owing to their unique 4f electronic structure, adjustable coordination modes, and high oxophilicity. As a cocatalyst, location of rare earth elements can alter intrinsic properties support, including environments, structure evolution under applied potentials variable manner, potentially impact catalytic performance with respect activity, stability, selectivity. Therefore, comprehensive understanding effects elements' on local reaction mechanisms is prerequisite designing advanced nanomaterials. In this review, have been categorized into three main groups based upon namely lattice, surface, interface structure. We initially discuss recent advances representing breakthroughs realize controllable synthesis Next, we state-of-the-art modulation strategy employed enhance performance. Combined characterizations, role process also discussed. Finally, further highlight future research directions remaining challenges development practical applications.

Язык: Английский

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Bridged Mn─O─Ru Motifs in RuO₂ Catalyst Promoting Hydrogen Production at Ampere‐Level Current Density

Advanced Energy Materials, Год журнала: 2025, Номер unknown

Опубликована: Апрель 26, 2025

Abstract Accurately regulating the reactive sites of catalysts is vital for highly efficient catalytic processes but still faces considerable challenges. In view this, a local oxidation‐state asymmetric Mn‐O‐Ru bridged moiety developed by introducing Mn atoms into RuO 2 host. The synergistic effect respective active on microstructure ensures its excellent alkaline HER performance. Theoretical calculations profiled that induced moiety, water dissociation ability Ru significantly boosted, while bridging oxygen exhibits optimal hydrogen adsorption free energy. As predicted, Mn‐RuO catalyst achieved overpotentials as low 118 and 160 mV at industrial level current densities 1 A cm ‒2 in m KOH, respectively, superior to commercial Pt/C catalyst. Such electrocatalyst can operate stably with long lifetime 300 h 10 mA under conditions. Furthermore, it only requires 1.87 V reach density 1.0 when serving cathode an assembled flow cell. This work provides new insight environment design obtaining ideal electrocatalysts.

Язык: Английский

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Modulation of interface electric field over CoMoP-CoMoP2 heterostructure for high-efficiency oxygen evolution reaction

Chemical Engineering Journal, Год журнала: 2024, Номер 498, С. 155184 - 155184

Опубликована: Авг. 25, 2024

Язык: Английский

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

Angewandte Chemie, 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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Electrospun Co‐MoC Nanoparticles Embedded in Carbon Nanofibers for Highly Efficient pH‐Universal Hydrogen Evolution Reaction and Alkaline Overall Water Splitting

Small Methods, Год журнала: 2024, Номер unknown

Опубликована: Окт. 22, 2024

The construction of highly efficient and self-supported electrocatalysts with abundant active sites for pH-universal hydrogen evolution reaction (HER) alkaline water splitting is significantly challenging. Herein, Co MoC nanoparticles embedded in nitrogen-doped carbon nanofibers (Co-MoC/NCNFs) which display a bamboo-like morphology are prepared by electrospinning followed the carbonization method. electrospun possesses an ultrasmall size (≈5 nm) can provide more during electrocatalysis, while introduction greatly optimizes electronic structure MoC. Both endow Co-MoC/NCNFs superior HER performances over wide pH range, low overpotentials 86, 116, 145 mV to achieve current density 10 mA cm

Язык: Английский

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