Oxygen Evolution/Reduction Reaction Catalysts: From In Situ Monitoring and Reaction Mechanisms to Rational Design

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(9), P. 6257 - 6358

Published: March 21, 2023

The oxygen evolution reaction (OER) and reduction (ORR) are core steps of various energy conversion storage systems. However, their sluggish kinetics, i.e., the demanding multielectron transfer processes, still render OER/ORR catalysts less efficient for practical applications. Moreover, complexity catalyst–electrolyte interface makes a comprehensive understanding intrinsic mechanisms challenging. Fortunately, recent advances in situ/operando characterization techniques have facilitated kinetic monitoring under conditions. Here we provide selected highlights mechanistic studies with main emphasis placed on heterogeneous systems (primarily discussing first-row transition metals which operate basic conditions), followed by brief outlook molecular catalysts. Key sections this review focused determination true active species, identification sites, reactive intermediates. For in-depth insights into above factors, short overview metrics accurate characterizations is provided. A combination obtained time-resolved information reliable activity data will then guide rational design new Strategies such as optimizing restructuring process well overcoming adsorption-energy scaling relations be discussed. Finally, pending current challenges prospects toward development homogeneous presented.

Language: Английский

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Promoting Surface Reconstruction of NiFe Layered Double Hydroxide for Enhanced Oxygen Evolution

Advanced Energy Materials, Journal Year: 2022, Volume and Issue: 12(48)

Published: Oct. 30, 2022

A dynamic surface reconstruction of oxide electrocatalysts in alkaline media is widely observed especially for layered double hydroxide (LDH), but little known about how to promote the toward desired surfaces improved oxygen evolution reaction (OER). Here, NiFe LDH nanosheets successfully induced a higher degree via situ sulfur doping than that by natural electrochemical activation. Theoretical calculations, operando Raman, and various ex characterizations reveal S anion-induced effect can lower energy barrier facilitate phase transformation into highly active S-doped oxyhydroxides. The generated S-NixFeyOOH optimize intermediate adsorption OER kinetics. reconstructed S-oxyhydroxides catalyst presents superior activity long-term durability compared undoped ones. This work provides structure–composition–activity relationship during restructuring pre-catalysts.

Language: Английский

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Amorphous Mo‐doped NiS_0.5Se_0.5 Nanosheets@Crystalline NiS_0.5Se_0.5 Nanorods for High Current‐density Electrocatalytic Water Splitting in Neutral Media

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(6)

Published: Dec. 3, 2022

Abstract It is vitally important to develop highly active, robust and low‐cost transition metal‐based electrocatalysts for overall water splitting in neutral solution especially at large current density. In this work, amorphous Mo‐doped NiS 0.5 Se nanosheets@crystalline nanorods (Am−Mo−NiS ) was synthesized using a facil one‐step strategy. phosphate buffer saline solution, the Am−Mo−NiS shows tiny overpotentials of 48 209 mV hydrogen evolution reaction (HER), 238 514 oxygen (OER) 10 1000 mA cm −2 , respectively. Moreover, delivers excellent stability least 300 h without obvious degradation. Theoretical calculations revealed that Ni sites defect‐rich structure owns higher electron state density strengthened binding energy H 2 O, which will optimize adsorption/desorption barriers reduce adsorption OER determining step.

Language: Английский

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Effect of Surface‐Adsorbed and Intercalated (Oxy)anions on the Oxygen Evolution Reaction

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(38)

Published: June 28, 2022

Abstract As the kinetically demanding oxygen evolution reaction (OER) is crucial for decarbonization of our society, a wide range (pre)catalysts with various non‐active‐site elements (e.g., Mo, S, Se, N, P, C, Si…) have been investigated. Thermodynamics dictate that these oxidize during industrial operation. The formed oxyanions are water soluble and thus predominantly leach in reconstruction process. Nevertheless, recently, it was unveiled thermodynamically stable (oxy)anions can adsorb on surface or intercalate interlayer space active catalyst. There, they tune electronic properties sites interact intermediates, changing OER kinetics potentially breaking persisting *OH/*OOH scaling relations. Thus, addition to electrolyte opens new design dimension catalysis herein discussed observations deepen understanding role anions OER.

Language: Английский

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Manipulating electron redistribution induced by asymmetric coordination for electrocatalytic water oxidation at a high current density

Science Bulletin, Journal Year: 2023, Volume and Issue: 68(13), P. 1389 - 1398

Published: June 3, 2023

Language: Английский

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Synergistic Activation of Crystalline Ni₂P and Amorphous NiMoO_x for Efficient Water Splitting at High Current Densities

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(14), P. 9792 - 9805

Published: July 11, 2023

The overpotential of alkaline water electrolysis at high current density is significantly increased by the energy barriers intermediate (H* and OH*) slow mass/charge transfer. Modifying electronic structure morphology catalysts to decrease enhance transfer a promising approach, but it presents significant challenges. In this study, crystalline Ni2P clusters were coupled with an amorphous NiMoOx nanorod support on nickel foam substrate (Ni2P–NiMoOx/NF) create heterojunction that enhances transfer, tunes barriers, improves reaction kinetics through synergistic activation. Ni2P–NiMoOx/NF exhibits ultralow overpotentials 91, 188, 297 mV 10, 100, 500 mA cm–2, respectively, for hydrogen evolution reaction, along stability. It also shows superior performance in oxygen reaction. Remarkably, Ni2P–NiMoOx/NF-based electrolyzer achieves 100 400 cm–2 low cell voltages 1.66 2.08 V, while maintaining stable h under industrial testing (65 °C 30% KOH). Additional characterization functional theory calculations demonstrate interaction between facilitates downshifting d-band centers Fermi level, which results activation local structure, promoting H2O dissociation enhancing overall catalytic activity.

Language: Английский

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The pivot to achieve high current density for biomass electrooxidation: Accelerating the reduction of Ni3+ to Ni2+

Applied Catalysis B Environment and Energy, Journal Year: 2023, Volume and Issue: 330, P. 122590 - 122590

Published: March 6, 2023

Language: Английский

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Lewis Acid Driving Asymmetric Interfacial Electron Distribution to Stabilize Active Species for Efficient Neutral Water Oxidation

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(7)

Published: Oct. 26, 2023

Abstract Neutral oxygen evolution reaction (OER) with unique reactive environments exhibits extremely slow kinetics, posing significant challenges in the design of catalysts. Herein, a built‐in electric field between tungstate (Ni‐FeWO 4 ) adjustable work function and Lewis acid WO 3 is elaborately constructed to regulate asymmetric interfacial electron distribution, which promotes accumulation Fe sites tungstate. This decelerates rapid dissolution under OER potentials, thereby retaining active hydroxyl oxide optimized pathway. Meanwhile, enhances adsorption near electrode surface improve mass transfer. As expected, Ni‐FeWO @WO /NF self‐supporting achieves low overpotential 235 mV at 10 mA cm −2 neutral media maintains stable operation for 200 h. Furthermore, membrane assembly by such robust stability 250 h during seawater electrolysis. deepens understanding reconstruction catalysts paves way development energy conversion technologies.

Language: Английский

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In Situ Generation of Molybdate‐Modulated Nickel‐Iron Oxide Electrodes with High Corrosion Resistance for Efficient Seawater Electrolysis

Advanced Energy Materials, Journal Year: 2023, Volume and Issue: 14(4)

Published: Dec. 6, 2023

Abstract The realization of seawater electrolysis requires the development electrode materials that can meet requirements high activity, selectivity, and corrosion resistance. Herein, this work successfully prepares a molybdate (MoO 4 2− )‐modulated nickel‐iron oxide for via quick easy thermal shock method, with activity extraordinary durability in oxygen evolution reaction (OER) electrolysis. experimental analyses theoretical calculations reveal situ generated MoO on surface modulate stabilize catalytic active phase γ ‐(Ni, Fe)OOH, improving OER as well play critical role protecting from chloride ions (Cl − ) extended service life. This catalyst thus displays an evidently slow degradation rate 20 µV h −1 during long‐term operation (>1500 h) at 100 mA cm −2 . provides new viewpoint design oxyanion‐modified catalysts be widely used to address challenges

Language: Английский

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Surface reconstruction of Se-doped NiS2 enables high-efficiency oxygen evolution reaction

Journal of Energy Chemistry, Journal Year: 2023, Volume and Issue: 84, P. 173 - 180

Published: May 22, 2023

Language: Английский

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