Heterometallic Electrocatalysts Derived from High-Nuclearity Metal Clusters for Efficient Overall Water Splitting

ACS Nano, Journal Year: 2024, Volume and Issue: 18(8), P. 6202 - 6214

Published: Feb. 12, 2024

The development of cost-effective electrocatalysts with an optimal surface affinity for intermediates is essential sustainable hydrogen fuel production, but this remains insufficient. Here we synthesize Ni2P/MoS2-CoMo2S4@C heterometallic based on the high-nuclearity cluster {Co24(TC4A)6(MoO4)8Cl6}, in which Ni2P nanoparticles were anchored to MoS2-CoMo2S4@C nanosheets via strong interfacial interactions. Theoretical calculations revealed that introduction phases induces significant disturbances electronic configuration Ni2P/MoS2-CoMo2S4@C, resulting more relaxed d–d orbital electron transfers between metal atoms. Moreover, continuous transport was established by formation multiple heterojunction interfaces. optimized electrocatalyst exhibited ultralow overpotentials 198 and 73 mV oxygen evolution reactions, respectively, alkaline media, at 10 mA cm–2. alkali electrolyzer constructed using required a cell voltage only 1.45 V (10 cm–2) drive overall water splitting excellent long-term stability.

Language: Английский

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Electrochemical oxidation of glucose in alkaline environment—A comparative study of Ni and Au electrodes

Electrochimica Acta, Journal Year: 2024, Volume and Issue: 487, P. 144159 - 144159

Published: March 25, 2024

The glucose oxidation reaction (GOR) was studied on Au and Ni electrodes by cyclic voltammetry (CV), rotating disk electrode (RDE) measurements coupled with Koutecky-Levich analysis, Differential Electrochemical Mass Spectrometry (DEMS), In situ Fourier Transform Infrared spectroscopy (FTIRS) High Performance Liquid Chromatography (HPLC) analysis of the products after electrolysis in potentiostatic mode under continuous flow conditions. This study allowed to identify propose tentative mechanisms. On gold, is adsorbed metallic sites through its anomeric function (C1) resulting formation gluconate as main GOR product at potentials close 0.6 V vs. RHE, a selectivity towards 100% projected faradaic efficiency ca. 70%. conversion rate rather low, 20%, due poisoning surface, leading strong deactivation. At above 0.8 decreases non-selective proceeds CC bond cleavage. nickel, occurs high (close 1.2 RHE) Ni(OH)2 NiOOH sites, C1C2 breaking, arabinose formate. higher potentials, decreases, formate being product.

Language: Английский

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Deciphering the Role of Nickel in Electrochemical Organic Oxidation Reactions

Advanced Energy Materials, Journal Year: 2024, Volume and Issue: 14(22)

Published: April 8, 2024

Abstract Organic oxidation reactions (OORs) powered by renewable energy sources are gaining importance as a favorable alternative to oxygen evolution reaction, with the promise of reducing cell potential and enhancing overall viability water electrolysis. This comprehensive review delves into electrochemical diverse organic compounds, including alcohols, aldehydes, amines, urea, well biomass‐derived feedstocks such hydroxymethylfurfural glycerol. The key focus centers on role nickel (Ni)‐based catalysts for these OORs. unique redox activity chemical nature Ni have been proven instrumental sustainable cost‐effective various molecules more efficiently selectively. article discusses how strategic choices, selection foreign metals, intercalating species, vacancies, defects, secondary element (e.g. chalcogens non‐metals), contribute tuning performances Ni‐based (pre)catalyst Moreover, this provides insights active species in reaction environments further explores mechanisms, apparent phase changes catalyst most relevant examples. Finally, not only elucidates limitations current approaches but also outlines avenues future advancements OOR.

Language: Английский

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Evaluating the impact of anodic oxidation reactions on water splitting using Prussian blue analog-derived metal-(oxy)hydroxides

Journal of Materials Chemistry A, Journal Year: 2024, Volume and Issue: 12(30), P. 19321 - 19330

Published: Jan. 1, 2024

Prussian blue analog (PBA)-derived Fe–Co(O)OH showed improved anodic oxidation of a series organic and inorganic compounds without the interference from oxygen evolution reaction.

Language: Английский

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Recent advances in Ni-based catalysts for the electrochemical oxidation of ethanol

Journal of Energy Chemistry, Journal Year: 2024, Volume and Issue: 98, P. 588 - 614

Published: July 3, 2024

Language: Английский

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Visible-Light-Induced Acylative Pyridylation of Styrenes

Organic Letters, Journal Year: 2024, Volume and Issue: 26(22), P. 4727 - 4732

Published: May 29, 2024

A visible-light-induced photocatalyst-free acylative pyridylation of styrenes with 4-acyl-1,4-dihydropyridines (DHPs) and 4-cyanopyridines has been described, featuring mild reaction conditions, a broad substrate scope, good functional group tolerance. The could also be performed under sunlight irradiation albeit slightly lower conversion. 4-Acyl-1,4-DHPs serve dual role, acting as both photoreductant to reduce the cyanopyridine its radical anion intermediate precursor produce acyl radical. mechanism was especially elucidated through Hammett analysis, quadratic linear regression analysis by using parameters, σmb σjj·. findings from further demonstrate that rate-limiting step process is single electron transfer between 4-acyl-1,4-DHPs 4-cyanopyridines.

Language: Английский

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Direct Synthesis of Gem-β,β′-Bis(alkyl) Alcohols Using Nickel Catalysis via Sequential DCR Approach

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(6), P. 4018 - 4029

Published: Feb. 28, 2024

Chemoselective synthesis of functionalized gem-β,β′-bis(alkyl)alcohols by coupling a β-alkylated secondary alcohol with primary is reported using nickel via sequential DCR (dehydrogenation–condensation–rehydrogenation) approach. Using our method, 1-arylethanol and benzyl alcohols undergo one-pot successive double alkylation reaction to form alcohols. Methanol, C2–C12 alcohols, citronellol, fatty acid-derived oleic are tolerated, including late-stage functionalization steroid hormones (cholesterol testosterone) 5-pregnen-3β-ol-20-one. The catalytic transformations enabled the donepezil drug (used for Alzheimer's disease), N-heteroarenes (quinoline acridine), chromane intermediate flavan derivatives. Hammett kinetic plot analysis differently p-substituted 1-phenyl propanol indicated that oxidation might be rate-determining step expected strong influence substitution on kinetics. A negative ρ value (−0.60) strongly signify formation positive charge alcohol. Preliminary mechanistic investigation revealed dehydrogenation aldehyde as it involves C–H/D bond breaking alcohol, PH/PD 6.0 was calculated. Reaction profile studies, EPR experiments, Hammett-plot cyclic voltammetry, UV–visible XPS analysis, structural electronic changes at Ni-center well behavior catalysts during progress reactions.

Language: Английский

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The Influence of Metal Impurities on NiOOH Electrocatalytic Activity in the Oxygen Evolution Reaction

ChemElectroChem, Journal Year: 2024, Volume and Issue: 11(13)

Published: June 17, 2024

Abstract The energy transition and the implementation of new electrochemical technologies will result in an increased reliance on critical raw materials for electrodes. Their large‐scale application ultimately mean working with lower grade materials. Here we study influence metal impurities nickel foam electrocatalysts. We do this by electrodepositing known amounts first‐row metals (Cu, Cr, Mn, Fe, Co Ni) studying their performance oxygen evolution reaction (OER) as a model reaction. electrodes’ is studied using cyclic voltammetry (CV), linear sweep (LSV), Tafel analysis, stepwise chronoamperometry (CA) impedance spectroscopy (EIS). Combining these results microscopy show that even small transition‐metal have profound effects catalytic changes affect OER onset potential (the system requires to convert OH – O 2 ) slope each electrode electrode's initial activity region). Our highlight implications such design future application.

Language: Английский

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Rapid Reconstruction of Nickel Iron Hydrogen Cyanamide with in-situ Produced Proton Acceptor for Efficient Oxygen Evolution

Applied Catalysis B Environment and Energy, Journal Year: 2024, Volume and Issue: 361, P. 124561 - 124561

Published: Sept. 6, 2024

Language: Английский

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Electrochemical ammonia oxidation on terephthalic acid framework (BDC-NH2) derived core-shell nickel oxide/nickel-enriched 2D carbon nanoflakes (NiO/Ni/CNF)

Applied Catalysis B Environment and Energy, Journal Year: 2024, Volume and Issue: 357, P. 124244 - 124244

Published: June 1, 2024

Language: Английский

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