Stacked High‐Entropy Hydroxides Promote Charge Transfer Kinetics for Photoelectrochemical Water Splitting

Advanced Functional Materials, Год журнала: 2024, Номер 34(40)

Опубликована: Май 2, 2024

Abstract Although various kinds of cocatalyst are developed and decorated on the bismuth vanadate (BiVO 4 ) photoanode, its photoelectrochemical (PEC) water splitting performance is limited owing to severe charge recombination sluggish oxygen evolution reaction (OER). Herein, a high‐entropy hydroxide electrocatalyst (FeCoNiMoCrOOH) constructed as co‐catalyst deposited BiVO with good PEC activity stability in potassium borate buffer, addressing substantial poor surface material. FeCoNiMoCrOOH synthesized by simple electrodeposition stacking strategy, delivers an overpotential 172 mV at 10 mA cm −2 600 h under alkaline conditions, representing one best performances high‐entropy‐based catalysts. The FeCoNiMoCrOOH/BiVO photoanode shows photocurrent density 5.23 1.23 V RHE 100 durability buffer. Experimental investigations theoretical calculations demonstrate that synergistic effect Mo Cr FeCoNi catalyst effectively decreases dissolution Fe, Co, Ni after long‐term operation, increases transfer kinetics, promotes OER performances, therefore enhancing photocorrosion resistance . This work provides new avenue design high entropy‐based electrocatalysts boosting solar stability.

Язык: Английский

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Optimizing photocatalysis via electron spin control

Chemical Society Reviews, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

This review systematically summarizes recent advanced strategies for manipulating electron spin to optimize photocatalysis. It provides valuable insights guide future research on control enhancing photocatalytic applications.

Язык: Английский

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Pumping Electrons from Oxygen-Bridged Cobalt for Low-Charging-Voltage Zn-Air Batteries

Nano Letters, Год журнала: 2024, Номер 24(43), С. 13653 - 13661

Опубликована: Окт. 21, 2024

Reducing the charging voltage is a prerequisite for improving chargeability and energy efficiency of Zn-air batteries (ZABs). Herein, Fe

Язык: Английский

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Fe-Doped CoS₂ Nanocages as Bifunctional Electrocatalysts for Water Splitting

ACS Applied Nano Materials, Год журнала: 2024, Номер 7(8), С. 9685 - 9695

Опубликована: Апрель 18, 2024

Currently, electrochemical water-splitting activity is limited by the slow intrinsic reaction kinetics and energy conversion efficiency, so designing highly efficient electrocatalysts that can facilitate reactions remains necessary. Herein, catalyst architecture consisting of Fe-doped CoS2 nanocages with nitrogen-doped carbon wrapping (CN/Fe-CoS2) was explored as an outstanding bifunctional electrocatalyst. Through density functional theory calculations, introduction Fe into would modulate states, making reduced band gap enhanced charge transfer efficiency CoS2. Simultaneously, adsorption intermediates during hydrogen evolution (HER) oxygen (OER) processes regulated, leading to improvement in catalytic activity. The experimental results demonstrate doping significantly enhances electron transfer, specific surface area, active area CoS2, which facilitates utilization exposes additional sites for reactions. In addition, nanocage CN/Fe-CoS2 act a protective layer prevent aggregation, thereby exposing enhancing interface electrolyte. By optimizing amount Fe, demonstrates remarkably superior electrocatalytic performance stability, evidenced low overpotential (η10) 186 304 mV at current 10 mA cm–2 1.0 M KOH media HER OER, respectively. Overall, combining heteroatom structure represents promising approach develop high-performance water splitting.

Язык: Английский

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Structural Reconstruction of a Cobalt- and Ferrocene-Based Metal–Organic Framework during the Electrochemical Oxygen Evolution Reaction

ACS Applied Materials & Interfaces, Год журнала: 2024, Номер 16(31), С. 40814 - 40824

Опубликована: Июль 23, 2024

Metal–organic frameworks (MOFs) are increasingly being investigated as electrocatalysts for the oxygen evolution reaction (OER) due to their unique modular structures that present a hybrid between molecular and heterogeneous catalysts, featuring well-defined active sites. However, many fundamental questions remain open regarding electrochemical stability of MOFs, structural reconstruction coordination sites, role in situ-formed species. Here, we report transformation surface-grown MOF containing cobalt nodes 1,1′-ferrocenedicarboxylic acid linkers (denoted CoFc-MOF) during OER alkaline electrolyte. Ex situ investigations CoFc-MOF film suggest acts precatalyst undergoes two-step restructuring process under operating conditions generate metal oxyhydroxide phase. The MOF-derived catalyst, supported on nickel foam electrodes, displays high activity toward with an overpotential 190 mV at current density 10 mA cm–2. While this study demonstrates necessity investigating MOFs electrocatalysis, it also shows potential using precursors catalyst design.

Язык: Английский

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Unveiling active sites in FeOOH nanorods@NiOOH nanosheets heterojunction for superior OER and HER electrocatalysis in water splitting

Journal of Colloid and Interface Science, Год журнала: 2024, Номер 679, С. 487 - 495

Опубликована: Окт. 3, 2024

Язык: Английский

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Spiral‐concave Prussian Blue Crystals with Rich Steps: Growth Mechanism and Coordination Regulation

Angewandte Chemie International Edition, Год журнала: 2024, Номер 64(2)

Опубликована: Авг. 29, 2024

Abstract Investigating the formation and transformation mechanisms of spiral‐concave crystals holds significant potential for advancing innovative material design comprehension. We examined kinetics‐controlled nucleation growth Prussian Blue with spiral concave structures, constructed a detailed crystal phase diagram. The hexacyanoferrate (SC‐HCF) crystals, characterized by high‐density surface steps low stress‐strain architecture, exhibit enhanced activity due to their facile interaction reactants. Notably, coordination environment SC‐HCF can be precisely modulated introduction diverse metals. Utilizing X‐ray absorption fine structure spectroscopy in situ ultraviolet‐visible spectroscopy, we elucidated mechanism Co‐HCF facilitated oriented adsorption‐ion exchange (OA‐IE) process. Both experimental data, density functional theory confirm that possesses an optimized energy band structure, capable adjusting local electronic enhancing performance oxygen evolution reaction. This work not only elucidates regulation rich HCF, but also offers novel perspective constructing nanocrystals intricate structures.

Язык: Английский

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Improved Ammonia Synthesis and Energy Output from Zinc-Nitrate Batteries by Spin-State Regulation in Perovskite Oxides

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

Опубликована: Янв. 16, 2025

Electrocatalytic nitrate reduction to ammonia (eNRA) is a promising route toward environmental sustainability and clean energy. However, its efficiency often limited by the slow conversion of intermediates due spin-forbidden processes. Here, we introduce novel A-site high-entropy strategy develop new perovskite oxide (La0.2Pr0.2Nd0.2Ba0.2Sr0.2)CoO3-δ (LPNBSC) for eNRA. The LPNBSC possesses higher concentration high-spin (HS) cobalt-active centers, resulting from an increased [CoO5] structural motifs compared conventional LaCoO3. Consequently, this material exhibits significantly improved electrocatalytic performance (NH3) production, in 3-fold increase yield rate (129 μmol h–1 mgcat.–1) 2-fold Faradaic (FE, 76%) LaCoO3 at optimal potential. Furthermore, LPNBSC-based Zn-nitrate battery reaches maximum FE 82% NH3 57 cm–2. Density functional theory calculations reveal that management perovskites facilitates activation potentially optimizes thermodynamic rate-determining step eNRA process, namely, *HNO3 + H+ e– → *NO2 H2O. This work presents efficient concept modulating spin state B-site metal offers valuable insights design high-performance catalysts.

Язык: Английский

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Confined Atomically Mo‐Regulating Co³⁺ Sites Enhanced Electrocatalytic Seawater Oxidation

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Фев. 19, 2025

Abstract Design and construction of stable single‐atom modified catalysts with suppressed deep reconstruction for long‐term durability highly active targeted catalysis in emains a great challenge. Herein, nitrogen/oxygen co‐doped carbon (NOC) encapsulated Mo atomically dispersed at Co 3+ sites 3 O 4 , are constructed through directed corrosion strategy. Meanwhile, the NOC confinement maintains stability single atoms promotes adsorbate evolution into lattice oxygen‐mediated mechanism. The reconstructed CoOOH is confined by layer, thus inhibiting its reconstruction, electrostatically repelling chloride ions to achieve electrolysis seawater. In real seawater flow cell, electrode requires 1.94 V reach 1.0 A cm −2 energy consumption 4.64 kWh Nm −3 ‐H 2 lower than that industrial alkaline electrolysis. continuous 300 h shows almost no decay, Faraday efficiency close 100%, indicating long‐lasting stability.

Язык: Английский

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Reconstruction of Ferromagnetic/non‐magnetic Cobalt‐based Electrocatalysts under Gradient Magnetic Fields for Enhanced Oxygen Evolution

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(46)

Опубликована: Авг. 6, 2024

Abstract The rational manipulation of the surface reconstruction catalysts is a key factor in achieving highly efficient water oxidation, but it challenge due to complex reaction conditions. Herein, we introduce novel situ strategy under gradient magnetic field form catalytically active species on ferromagnetic/paramagnetic CoFe 2 O 4 @CoBDC core–shell structure for electrochemical oxygen evolution (OER). We demonstrate that Kelvin force from cores’ local modulates shells’ reconstruction, leading higher proportion Co 2+ as sites. These sites with optimized electronic configuration exhibit more favorable adsorption energy oxygen‐containing intermediates and lower activation overall catalytic reaction. As result, significant enhancement OER performance achieved large current density increment about 128 % at 1.63 V an overpotential reduction by 28 mV 10 mA cm −2 after reconstruction. Interestingly, removing external field, activity could persist over 100 h. This work showcases directional enhanced oxidation.

Язык: Английский

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