Carbon Oxyanion Self‐Transformation on NiFe Oxalates Enables Long‐Term Ampere‐Level Current Density Seawater Oxidation

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(1)

Published: Nov. 23, 2023

Seawater electrolysis is an attractive way of making H2 in coastal areas, and NiFe-based materials are among the top options for alkaline seawater oxidation (ASO). However, ample Cl- can severely corrode catalytic sites lead to limited lifespans. Herein, we report that situ carbon oxyanion self-transformation (COST) from oxalate carbonate on a monolithic NiFe micropillar electrode allows safeguard high-valence metal reaction ASO. In situ/ex studies show spontaneous, timely, appropriate COST safeguards active against attack during ASO even at ampere-level current density (j). Our catalyst shows efficient stable performance, which requires overpotential as low 349 mV attain j 1 A cm-2 . Moreover, with protective surface CO32- exhibits slight activity degradation after 600 h under seawater. This work reports effective design concepts level self-transformation, acting momentous step toward defending seawater-to-H2 conversion systems.

Language: Английский

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In Situ Reconstruction to Surface Sulfide Adsorbed Metal Scaffold for Enhanced Electrocatalytic Hydrogen Evolution Activity

Advanced Energy Materials, Journal Year: 2024, Volume and Issue: 14(23)

Published: March 26, 2024

Abstract Transition‐metal‐based compounds have been intensively explored as efficient electrocatalysts for hydrogen evolution reaction (HER). Feasible reconstruction to the real active sites, which is yet be identified, endows promotion of HER activity. Here, it reported that incoming S coordinates and anion vacancies prompt structural S‐doped Co 3 O 4 on carbon cloth (S‐Co /CC) during HER. A list in situ studies reveals sites are “metallic surface‐adparticles” system embracing metallic scaffold dilute coverage coordinated δ+ . Reaction mechanism exploration illustrates interfacial perimeters between moieties considerably facilitate adsorption H*, improve kinetics water dissociation, consequently promote The exemplified sulfide‐mediated topotactic transformation strategy extended preparation S, Fe codoped Ni(OH) 2 (S‐NiFe/CC) a bifunctional electrocatalyst. assembled exchange membrane electrolyzer achieves current density 1.0 cm −2 at 1.72 V, showing excellent capability catalyzing overall splitting ampere level. This study, feasible enables facile identify would inspire development other electrochemical hydrogenation reaction.

Language: Английский

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Engineering active and robust alloy-based electrocatalyst by rapid Joule-heating toward ampere-level hydrogen evolution

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Aug. 29, 2024

Rational design of bimetallic alloy is an effective way to improve the electrocatalytic activity and stability Mo-based cathode for ampere-level hydrogen evolution. However, it still critical realise desirable syntheses due wide reduction potentials between different metal elements uncontrollable nucleation processes. Herein, we propose a rapid Joule heating method effectively load RuMo onto MoOx matrix. As-prepared catalyst exhibits excellent (2000 h @ 1000 mA cm

Language: Английский

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Rationally designed Ru catalysts supported on TiN for highly efficient and stable hydrogen evolution in alkaline conditions

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: July 29, 2024

Electrocatalysis holds the key to enhancing efficiency and cost-effectiveness of water splitting devices, thereby contributing advancement hydrogen as a clean, sustainable energy carrier. This study focuses on rational design Ru nanoparticle catalysts supported TiN (Ru NPs/TiN) for evolution reaction in alkaline conditions. The designed exhibit high mass activity 20 A mg−1Ru at an overpotential 63 mV long-term stability, surpassing present benchmarks commercial electrolyzers. Structural analysis highlights effective modification properties by substrate, while density functional theory calculations indicate strong adhesion particles substrates advantageous modulation adsorption energies via particle-support interactions. Finally, we assemble anion exchange membrane electrolyzer using NPs/TiN catalyst, which operates 5 cm−2 more than 1000 h with negligible degradation, exceeding performance requirements Our findings contribute efficient exploiting Designing stable electrocatalysts is great interest H2 fuel production. Here, authors catalyst TiN, achieving mg−1 conditions, operating over hours electrolyzer.

Language: Английский

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Manipulating the Microenvironment of Single Atoms by Switching Support Crystallinity for Industrial Hydrogen Evolution

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(7)

Published: Dec. 28, 2023

Abstract Modulating the microenvironment of single‐atom catalysts (SACs) is critical to optimizing catalytic activity. Herein, we innovatively propose a strategy improve local reaction environment Ru single atoms by precisely switching crystallinity support from high crystalline and low crystalline, which significantly improves hydrogen evolution (HER) The catalyst anchored on low‐crystalline nickel hydroxide (Ru−LC−Ni(OH) 2 ) reconstructs distribution balance interfacial ions due activation effect metal dangling bonds support. Single‐site with oxidation state induces aggregation hydronium (H 3 O + ), leading formation acidic in alkaline media, breaking pH‐dependent HER As comparison, high‐crystalline (Ru−HC−Ni(OH) exhibits sluggish Volmer step conventional environment. expected, Ru−LC−Ni(OH) requires overpotentials 9 136 mV at 10 1000 mA cm −2 conditions operates stably 500 for h an seawater anion exchange membrane (AEM) electrolyzer. This study provides new perspective constructing highly active electrocatalysts.

Language: Английский

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Carbon Oxyanion Self‐Transformation on NiFe Oxalates Enables Long‐Term Ampere‐Level Current Density Seawater Oxidation

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 136(1)

Published: Nov. 23, 2023

Abstract Seawater electrolysis is an attractive way of making H 2 in coastal areas, and NiFe‐based materials are among the top options for alkaline seawater oxidation (ASO). However, ample Cl − can severely corrode catalytic sites lead to limited lifespans. Herein, we report that situ carbon oxyanion self‐transformation (COST) from oxalate carbonate on a monolithic NiFe micropillar electrode allows safeguard high‐valence metal reaction ASO. In situ/ex studies show spontaneous, timely, appropriate COST safeguards active against attack during ASO even at ampere‐level current density ( j ). Our catalyst shows efficient stable performance, which requires overpotential as low 349 mV attain 1 A cm −2 . Moreover, with protective surface CO 3 2− exhibits slight activity degradation after 600 h under seawater. This work reports effective design concepts level self‐transformation, acting momentous step toward defending seawater‐to‐H conversion systems.

Language: Английский

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Manipulating the Microenvironment of Single Atoms by Switching Support Crystallinity for Industrial Hydrogen Evolution

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 136(7)

Published: Dec. 28, 2023

Abstract Modulating the microenvironment of single‐atom catalysts (SACs) is critical to optimizing catalytic activity. Herein, we innovatively propose a strategy improve local reaction environment Ru single atoms by precisely switching crystallinity support from high crystalline and low crystalline, which significantly improves hydrogen evolution (HER) The catalyst anchored on low‐crystalline nickel hydroxide (Ru−LC−Ni(OH) 2 ) reconstructs distribution balance interfacial ions due activation effect metal dangling bonds support. Single‐site with oxidation state induces aggregation hydronium (H 3 O + ), leading formation acidic in alkaline media, breaking pH‐dependent HER As comparison, high‐crystalline (Ru−HC−Ni(OH) exhibits sluggish Volmer step conventional environment. expected, Ru−LC−Ni(OH) requires overpotentials 9 136 mV at 10 1000 mA cm −2 conditions operates stably 500 for h an seawater anion exchange membrane (AEM) electrolyzer. This study provides new perspective constructing highly active electrocatalysts.

Language: Английский

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Stainless Steel Activation for Efficient Alkaline Oxygen Evolution in Advanced Electrolyzers

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(21)

Published: Feb. 20, 2024

Abstract Designing robust and cost‐effective electrocatalysts for efficient alkaline oxygen evolution reaction (OER) is of great significance in the field water electrolysis. In this study, an electrochemical strategy to activate stainless steel (SS) electrodes OER introduced. By cycling SS electrode within a potential window that encompasses Fe(II)↔Fe(III) process, its activity can be enhanced extent compared using excludes redox reaction, decreasing overpotential at current density 100 mA cm −2 by 40 mV. Electrochemical characterization, Inductively Coupled Plasma – Optical Emission Spectroscopy, operando Raman measurements demonstrate Fe leaching surface accelerated through → γ‐Fe 2 O 3 4 or FeO 2+ (aq.) conversion leading sustained exposure Cr Ni species. While occurs during oxidation species display higher resistance gradually accumulate on form OER‐active Fe‐incorporated NiOOH Furthermore, potential‐pulse also introduced regenerate OER‐activity 316‐type stable OER, both three‐electrode configuration (without performance decay after 300 h 350 ) electrolyzer (≈30 mV cell voltage increase stress test‐AST). The AST‐stabilized still reach 1000 4000 voltages 1.69 2.1 V, which makes it competitive with state‐of‐the‐art electrolyzers based ion‐exchange membrane Ir‐based anodes.

Language: Английский

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Atomic Au₃Cu Palisade Interlayer in Core@Shell Nanostructures for Efficient Kirkendall Effect Mediation

Nano Letters, Journal Year: 2024, Volume and Issue: 24(9), P. 2719 - 2726

Published: Feb. 20, 2024

Plasmonic Cu@semiconductor heteronanocrystals (HNCs) have many favorable properties, but the synthesis of solid structures is often hindered by nanoscale Kirkendall effect. Herein, we present use an atomically thin Au3Cu palisade interlayer to reduce lattice mismatch and mediate effect, enabling successive topological Cu@Au3Cu@Ag, Cu@Au3Cu@Ag2S, further transformed Cu@Au3Cu@CdS core–shell HNCs via cation exchange. The intact effectively modulates diffusion kinetics Cu atoms as demonstrated experimental theoretical investigations simultaneously alleviates between Ag well CdS. feature exceptional crystallinity organized heterointerfaces plasmonic metal semiconductor. This results in efficient plasmon-induced injection hot electrons from Cu@Au3Cu into CdS shell, achieve high activity selectivity for photocatalytic reduction CO2 CO.

Language: Английский

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Electron‐Donating Cu Atoms Induced High Proton Supply and Anti‐Poisoning Ruthenium Clusters for Superior Direct Seawater Hydrogen Production

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: 34(40)

Published: March 21, 2024

Abstract Direct seawater hydrogen production via electrolysis would be a transformative technology for large‐scale pathways future sustainable energy systems. However, prohibiting the formation of insoluble hydroxides and promoting proton supply at electrode‐seawater interface are extremely desirable but remain challenging. Herein, inspired by dual‐metal pair sites in natural enzyme, de novo design an efficient, robust, precise electron‐donating Cu‐modulated ruthenium clusters on porous carbon matrix (Cu@Ru nc ‐C) is reported as high anti‐poisoning cathode material superior direct production. Benefitting from unique Cu@Ru sites, exhibits particularly evolution activities with ultralow overpotentials to reach current density 300 mA cm −2 both alkaline (115 mV) (459 electrolytes, notably, can maintain long‐lasting stability electrolysis. The mechanism exploration demonstrates that low oxophilic fast proton‐transferring local reaction environments prohibit precipitates provide efficient within interface. It expected proposed bioinspired regulation strategy offers new pathway constructing selective materials scalable

Language: Английский

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