Regulating the Spin‐State of Rare‐Earth Ce Single Atom Catalyst for Boosted Oxygen Reduction in Neutral Medium

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 33(47)

Published: July 16, 2023

Abstract The development of neutral zinc–air batteries (ZABs) is long been impeded by the sluggish oxygen reduction reaction (ORR) derived from insufficient O 2 activation and OH* blocking effect. Herein, synthesis a series rare‐earth Ce single‐atom catalysts (CeNCs) reported with enhanced spin‐state for boosting ORR. Experimental analysis theoretical calculations indicate that unique local coordination/geometric structure reshapes electronic configuration sites to achieve transition 4d 10 4f 1 8 3 . high‐spin active accelerate unpaired f electrons occupy anti‐π orbitals generate suitable binding strength intermediates. In conditions, CeNC‐40 exhibits excellent ORR performance half‐wave potentials 0.78 V negligible decay after 000 cycles. Additionally, self‐breathing ZABs based on demonstrates peak power density 81 mW cm −2 impressive long‐cycle stability (>1 600 cycles) at mA This work presents an effective strategy developing address challenges ZABs.

Language: Английский

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The surface states of transition metal X-ides under electrocatalytic conditions

The Journal of Chemical Physics, Journal Year: 2023, Volume and Issue: 158(12)

Published: March 7, 2023

Due to conversion equilibrium between solvent and H- O-containing adsorbates, the true surface state of a catalyst under particular electrochemical condition is often overlooked in electrocatalysis research. Herein, by using Pourbaix analysis, we show that many electrocatalytically active transition metal X-ides (e.g., oxides, nitrides, carbides, hydroxides) tend possess states different from their pristine stoichiometric forms pH potential interest due water dissociation or generation. Summarizing density functional theory calculated diagrams 14 conditionally stable X-ide materials, found some these surfaces be covered adsorbates at moderate high potential, while vacancies H-covered may form low potential. These results suggest possibility poisoning creation sites beyond surface, implying reaction conditions (pH potentials) needs considered before identification analysis catalyst. In addition, provide an explanation observed experiment discrepancy are "more than theory." Based on our findings, conclude analyzing electrocatalysts theoretical calculations diagram analysis), situ/operando post-reaction experiments indispensable accurately understand underlying catalytic mechanisms.

Language: Английский

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Rare Earth Single‐Atom Catalysis for High‐Performance Li−S Full Battery with Ultrahigh Capacity

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(31)

Published: May 18, 2024

Lithium-sulfur (Li-S) batteries have many advantages but still face problems such as retarded polysulfides redox kinetics and Li dendrite growth. Most reported single atom catalysts (SACs) for Li-S are based on d-band transition metals whose d orbital constitutes active valence band, which is inclined to occur catalyst passivation. SACs 4f inner of rare earth challenging their great difficulty be activated. In this work, we design synthesize the first metal Sm has electron-rich promote catalytic conversion uniform deposition Li. enhance catalysis by activated through an f-d-p hybridization. Using Sm-N

Language: Английский

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Ethanol‐Induced Hydrogen Insertion in Ultrafine IrPdH Boosts pH‐Universal Hydrogen Evolution

Small, Journal Year: 2022, Volume and Issue: 18(35)

Published: Aug. 7, 2022

Engineering Pt-free catalysts for hydrogen evolution reaction (HER) with high activity and stability is of great significance in electrochemical production. Herein, situ chemical H intercalation into ultrafine Pd to activate this otherwise HER-inferior material form the IrPdH hydride as an efficient stable HER electrocatalyst proposed. The formation PdIrH depends on a new hydrogenation strategy via using ethanol resource. It demonstrated that atoms originate from OH CH2  ethanol, which fills gap source preparation hydride. Thanks incorporation H/Ir structure, exhibits superior whole pH range. delivers very low overpotentials 14, 25 60 mV at current density 10 mA cm-2 respectively 0.5 m H2 SO4 , 1 KOH, PBS electrolytes, are much better than those commercial Pt/C most reported noble metal electrocatalysts. Theoretical calculations confirm interstitial availably refines electronic Ir sites, optimizes adsorption *H leads significant enhancement performance.

Language: Английский

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N-doped LaPO4: An effective Pt-free catalyst for electrocatalytic oxygen reduction

Chem Catalysis, Journal Year: 2022, Volume and Issue: 2(12), P. 3590 - 3606

Published: Dec. 1, 2022

Language: Английский

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Single‐atom catalyst application in distributed renewable energy conversion and storage

SusMat, Journal Year: 2023, Volume and Issue: 3(2), P. 160 - 179

Published: March 2, 2023

Abstract In recent years, owing to the depletion of fossil energy and aggravation environmental pollution, conversion storage distributed renewable (such as solar energy, wind tidal energy) based on electrochemical technology have attracted extensive attention. Electrocatalytic processes with high efficiency selectivity play a key role in clean storage. With nearly 100% atomic utilization rate unique catalytic activity, single‐atom catalysts (SACs) been rapidly developed widely used field this review, we first introduce characteristics SACs. Then, focus application SACs conversion, including water electrolysis reaction, nitrogen reduction nitrate oxygen carbon dioxide reaction. terms storage, supercapacitors Li–S batteries. Further, enumerate some methods for synthesis metal loading or large scale. Finally, main challenges opportunities emerging future are discussed prospected.

Language: Английский

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Recent Advances on Single‐Atom Catalysts for Photocatalytic CO₂ Reduction

Small, Journal Year: 2023, Volume and Issue: 19(48)

Published: Aug. 1, 2023

Abstract The present energy crisis and environmental challenges may be efficiently resolved by converting carbon dioxide (CO 2 ) into various useful products. development of more effective catalysts has been the main focus current research on photocatalytic CO reduction. Due to their high atomic efficiency superior catalytic activity, single‐atom (SACs) have attracted considerable interest in conversion. This review discusses developments, obstacles, potential SACs for And further, principle work compared analyzed effects support materials active site types reduction performance. believes that sharing these some inspiration rational design stable based can provided.

Language: Английский

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Efficient Benzylic C–H Bond Activation over Single-Atom Yttrium Supported on TiO₂ via Facilitated Molecular Oxygen and Surface Lattice Oxygen Activation

ACS Catalysis, Journal Year: 2023, Volume and Issue: 14(1), P. 249 - 261

Published: Dec. 14, 2023

Selective activation of C(sp3)–H bonds is important for value-added chemical production, but it remains challenging to proceed under moderate conditions. Herein, we report single-atom yttrium supported on TiO2 (Y1/TiO2) as a catalyst photocatalytic benzylic C–H bond at room temperature. In toluene oxidation, exhibits conversion rate 850 μmol g–1 h–1 with high benzaldehyde selectivity 94.1%. Experimental data show that abundant Y1δ+–O–Ti3+ (δ > 3) sites are formed the interface strong electronic metal–support interactions, inducing highly spin-polarized electrons facilitate charge separation. Furthermore, Y species promote formation oxygen vacancies and lead lattice distortion TiO2, which facilitates molecular surface activation. These reactive can directly react benzyl radical light irradiation produce hence increase performance. This work shows great potential rare-earth catalysts in mild conditions driven by renewable solar energy.

Language: Английский

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Spin‐Selective Coupling in Mott–Schottky Er₂O₃‐Co Boosts Electrocatalytic Oxygen Reduction

Small Methods, Journal Year: 2023, Volume and Issue: 7(7)

Published: April 8, 2023

Abstract Alkaline oxygen reduction reaction (ORR) is critical to electrochemical energy conversion technology, yet the rational breaking of thermodynamic inhibition for ORR through spin regulation remains a challenge. Herein, Mott–Schottky catalyst consisting Er 2 O 3 ‐Co particles uniformly implanted into carbon nanofibers (Er ‐Co/CNF) designed enhancing via spin‐selective coupling. The optimized ‐Co/CNF affords high half‐wave potential (0.835 V vs reversible hydrogen electrode, RHE) and onset (0.989 RHE ) surpassing individual Co/CNF /CNF. Theoretical calculations reveal introduction optimizes electronic structure Co Er(4f)‐O(2p)‐Co(3d) gradient orbital coupling, resulting in significantly enhanced performance. Through induced spin‐up hole 3d states endows Er‐O‐Co unit active site with coupling channel electron transition. This favors decrease gap potential‐limiting step, thus achieving theoretical limiting 0.77 ‐Co. Moreover, practicability as an air‐cathode also demonstrated Zn‐air batteries. work believed provide, new perspectives design efficient electrocatalysts by engineering rare‐earth oxides.

Language: Английский

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Rare‐Earth–Modified Metal–Organic Frameworks and Derivatives for Photo/Electrocatalysis

Small, Journal Year: 2023, Volume and Issue: 19(41)

Published: June 8, 2023

Metal-organic frameworks (MOFs) and their derivatives have attracted much attention in the field of photo/electrocatalysis owing to ultrahigh porosity, tunable properties, superior coordination ability. Regulating valence electronic structure environment MOFs is an effective way enhance intrinsic catalytic performance. Rare earth (RE) elements with 4f orbital occupancy provide opportunity evoke electron rearrangement, accelerate charged carrier transport, synergize surface adsorption catalysts. Therefore, integration RE makes it possible optimize environment, resulting enhanced In this review, progress current research on use RE-modified for summarized discussed. First, theoretical advantages MOF modification are introduced, a focus roles ion organic ligands. Then, application systematically Finally, challenges, future opportunities, prospects RE-MOFs also

Language: Английский

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