Spin-Polarized Photocatalytic CO₂ Reduction of Mn-Doped Perovskite Nanoplates

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(34), P. 15718 - 15726

Published: Aug. 17, 2022

"Spin" has been recently reported as an important degree of electronic freedom to improve the performance electrocatalysts and photocatalysts. This work demonstrates manipulations spin-polarized electrons in CsPbBr3 halide perovskite nanoplates (NPLs) boost photocatalytic CO2 reduction reaction (CO2RR) efficiencies by doping manganese cations (Mn2+) applying external magnetic field. Mn-doped (Mn-CsPbBr3) NPLs exhibit outstanding CO2RR compared pristine due creating after Mn doping. Notably, Mn-CsPbBr3 is significantly enhanced 5.7 times improved under a field 300 mT with permanent magnet NPLs. The corresponding mechanism systematically investigated circular dichroism spectroscopy, ultrafast transient absorption density functional theory simulation. origin increased number photoexcited carriers synergistic elements field, resulting prolonged carrier lifetime suppressed charge recombination. Our result shows that manipulating semiconductors provides effective strategy efficiencies.

Language: Английский

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The Open Catalyst 2022 (OC22) Dataset and Challenges for Oxide Electrocatalysts

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(5), P. 3066 - 3084

Published: Feb. 16, 2023

The development of machine learning models for electrocatalysts requires a broad set training data to enable their use across wide variety materials. One class materials that currently lacks sufficient is oxides, which are critical the Oxygen Evolution Reaction (OER) catalysts. To address this, we developed Open Catalyst 2022 (OC22) dataset, consisting 62,331 Density Functional Theory (DFT) relaxations (∼9,854,504 single point calculations) range oxide materials, coverages, and adsorbates. We define generalized total energy tasks property prediction beyond adsorption energies; test baseline performance several graph neural networks; provide predefined dataset splits establish clear benchmarks future efforts. In most general task, GemNet-OC sees ∼36% improvement in predictions when combining chemically dissimilar 2020 Data (OC20) OC22 datasets via fine-tuning. Similarly, achieved ∼19% on OC20 ∼9% force using joint training. demonstrate practical utility top performing model by capturing literature energies important OER scaling relationships. expect an benchmark seeking incorporate intricate long-range electrostatic magnetic interactions surfaces. open sourced, public leaderboard available encourage continued community developments data.

Language: Английский

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Spin-related symmetry breaking induced by half-disordered hybridization in BixEr2-xRu2O7 pyrochlores for acidic oxygen evolution

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: July 15, 2022

While acidic oxygen evolution reaction plays a critical role in electrochemical energy conversion devices, the sluggish kinetics and poor stability electrolyte challenges materials development. Unlike traditional nano-structuring approaches, this work focuses on structural symmetry breaking to rearrange spin electron occupation optimize spin-dependent orbital interaction alter charge transfer between catalysts reactants. Herein, we propose an atomic half-disordering strategy multistage-hybridized BixEr2-xRu2O7 pyrochlores reconfigure degeneracy spin-related occupation. This involves controlling bonding of Bi-6s lone pair electrons, which partial atom rearrangement makes active sites transform into asymmetric high-spin states from symmetric low-spin states. As result, half-disordered demonstrate overpotential ~0.18 V at 10 mA cm-2 accompanied with excellent 100 h electrolyte. Our findings not only provide for designing atom-disorder-related catalysts, but also provides deeper understanding kinetics.

Language: Английский

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Chiral Induced Spin Selectivity

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(4), P. 1950 - 1991

Published: Feb. 16, 2024

Since the initial landmark study on chiral induced spin selectivity (CISS) effect in 1999, considerable experimental and theoretical efforts have been made to understand physical underpinnings mechanistic features of this interesting phenomenon. As first formulated, CISS refers innate ability materials act as filters for electron transport; however, more recent experiments demonstrate that displacement currents arising from charge polarization molecules lead without need net flow. With its identification a fundamental connection between symmetry materials, promises profound ubiquitous implications existing technologies new approaches answering age old questions, such homochiral nature life. This review begins with discussion different methods measuring then provides comprehensive overview known exhibit CISS-based phenomena before proceeding identify structure-property relations delineate leading models effect. Next, it identifies some physics, chemistry, biology. The ends critical assessment field comments future outlook.

Language: Английский

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Spin‐Polarization Strategy for Enhanced Acidic Oxygen Evolution Activity

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(35)

Published: July 12, 2023

Spin-polarization is known as a promising way to promote the anodic oxygen evolution reaction (OER), since intermediates and products endow spin-dependent behaviors, yet it rarely reported for ferromagnetic catalysts toward acidic OER practically used in industry. Herein, first spin-polarization-mediated strategy create net moment antiferromagnetic RuO2 via dilute manganese (Mn2+ ) (S = 5/2) doping enhancing activity electrolyte. Element-selective X-ray magnetic circular dichroism reveals coupling between Mn Ru ions, fulfilling Goodenough-Kanamori rule. The ferromagnetism behavior at room temperature can be well interpreted by principles calculations interaction Mn2+ impurity ions. Indeed, Mn-RuO2 nanoflakes exhibit strongly field enhanced activity, with lowest overpotential of 143 mV 10 mA cmgeo-2 negligible decay 480 h stability (vs 200 mV/195 without field) effects literature. intrinsic turnover frequency also improved reach 5.5 s-1 1.45 VRHE . This work highlights an important avenue spin-engineering designing efficient catalysts.

Language: Английский

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The origin of magnetization-caused increment in water oxidation

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: April 29, 2023

Magnetization promoted activity of magnetic catalysts towards the oxygen evolution reaction (OER) has attracted great attention, but remains a puzzle where increment comes from. ferromagnetic material only changes its domain structure. It does not directly change spin orientation unpaired electrons in material. The confusion is that each small magnet and theoretically spin-polarization OER already occurs on these domains, thus enhancement should have been achieved without magnetization. Here, we demonstrate from disappeared wall upon leads to structure, multi-domain one single one, which disappears. surface occupied by reformatted into domain, follows spin-facilitated pathways overall electrode occurs. This study fills missing gap for understanding spin-polarized it further explains type can give

Language: Английский

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Dynamic orbital hybridization triggered spin-disorder renormalization via super-exchange interaction for oxygen evolution reaction

Proceedings of the National Academy of Sciences, Journal Year: 2023, Volume and Issue: 120(21)

Published: May 15, 2023

The oxygen evolution reaction (OER) underpins many aspects of energy storage and conversion in modern industry technology, but which still be suffering from the dilemma sluggish kinetics poor electrochemical performance. Different viewpoint nanostructuring, this work focuses on an intriguing dynamic orbital hybridization approach to renormalize disordering spin configuration porous noble-metal-free metal-organic frameworks (MOFs) accelerate spin-dependent OER. Herein, we propose extraordinary super-exchange interaction reconfigure domain direction nets at MOFs through temporarily bonding with magnetic ions electrolytes under alternating electromagnetic field stimulation, renormalization low-spin state high-spin facilitates rapid water dissociation optimal carrier migration, leading a pathway. Therefore, spin-renormalized demonstrate mass activity 2,095.1 A gmetal-1 overpotential 0.33 V, is about 5.9 time pristine ones. Our findings provide insight into reconfiguring spin-related catalysts ordering directions kinetics.

Language: Английский

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Inducing spin polarization via Co doping in the BiVO4 cell to enhance the built-in electric field for promotion of photocatalytic CO2 reduction

Journal of Colloid and Interface Science, Journal Year: 2024, Volume and Issue: 664, P. 500 - 510

Published: March 11, 2024

Language: Английский

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Tracking the correlation between spintronic structure and oxygen evolution reaction mechanism of cobalt-ruthenium-based electrocatalyst

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Jan. 2, 2025

Regulating the spintronic structure of electrocatalysts can improve oxygen evolution reaction performance efficiently. Nonetheless, effects tuning for mechanisms have rarely been discussed. Here, we show a ruthenium-cobalt-tin oxide with optimized due to quantum spin interaction Ru and Co. The specific promotes charge transfer kinetics intermediates behavior under applied potential, generating long-lived active species higher density sites after reconstruction process. Moreover, possesses decoupled proton-electron procedure during process, demonstrating that electron O-O bond formation between *O intermediate lattice in Co-O-Ru is rate-determining step This work provides rational perspectives on correlation mechanism. Tuning reactions underexplored, despite its potential enhance catalytic performance. authors report an structure, highlighting improved mechanisms.

Language: Английский

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Evolution and Reconstruction of Air‐Electrode Surface Composition in Reversible Protonic Ceramic Cells: Mechanisms, Impacts on Catalytic Performance, and Optimization Strategies – A Review

Advanced Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 5, 2025

Abstract Reversible protonic ceramic cells (R‐PCCs) are at the forefront of electrochemical conversion devices, capable reversibly and efficiently converting chemical energy into electricity intermediate temperatures (350–700 °C) with zero carbon emissions. However, slow surface catalytic reactions air‐electrode often hinder their performance durability. The electrode is not merely an extension bulk structure, equilibrium reconstruction can lead to significantly different crystal‐plane terminations morphologies, which influenced by material's intrinsic properties external reaction conditions. Understanding evolution elevated in water‐containing, oxidative atmospheres presents significant importance. In this review, a comprehensive summary recent processes applying advanced characterization techniques for high‐temperature surfaces provided, exploring correlations between fluctuations examining structural various associated degradation activation phenomena, offering insights impact on performance. Furthermore, reported strategies advances enhancing R‐PCCs through engineering discussed. This review offers valuable expected guide future developments catalysis, solid‐state ionics, materials.

Language: Английский

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