Efficient Electrocatalytic Oxidation of Glycerol via Promoted OH* Generation over Single-Atom-Bismuth-Doped Spinel Co₃O₄

ACS Catalysis, Год журнала: 2022, Номер 12(19), С. 12432 - 12443

Опубликована: Сен. 28, 2022

The renewable electricity-driven electrocatalytic oxidation of biomass represents a pathway to produce value-added chemicals from waste such as glycerol (a byproduct industrial biodiesel production). However, it remains difficult design an efficient electrocatalyst with explicit structure–property relationships. Herein, we report single-atom bismuth (Bi)-doping strategy endow Co3O4 enhanced activity and selectivity toward reaction (GOR). Experimental characterizations theoretical calculations reveal that Bi substitutes cobalt at octahedral sites (CoOh3+) in Co3O4, facilitating the generation reactive hydroxyl species (OH*) adjacent tetrahedral Co (CoTd2+). Mechanism studies demonstrate OH* accelerates groups carbon–carbon (C–C) bond cleavage, achieving GOR (400 mA cm–2 1.446 V vs reversible hydrogen electrode, RHE) high faradaic efficiency formate (97.05 ± 2.55%). Our study shows promising way promote electro-oxidation spinel oxides for valorization by doping strategy.

Язык: Английский

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A review on photo-, electro- and photoelectro- catalytic strategies for selective oxidation of alcohols

Journal of Energy Chemistry, Год журнала: 2022, Номер 77, С. 80 - 118

Опубликована: Ноя. 1, 2022

Язык: Английский

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Recent Advancements in Electrochemical Hydrogen Production via Hybrid Water Splitting

Advanced Materials, Год журнала: 2023, Номер 36(4)

Опубликована: Окт. 10, 2023

Abstract As one of the most promising approaches to producing high‐purity hydrogen (H 2 ), electrochemical water splitting powered by renewable energy sources such as solar, wind, and hydroelectric power has attracted considerable interest over past decade. However, electrolysis process is seriously hampered sluggish electrode reaction kinetics, especially four‐electron oxygen evolution at anode side, which induces a high overpotential. Currently, emerging hybrid strategy proposed integrating thermodynamically favorable electro–oxidation reactions with cathode, providing new opportunity for energy–efficient H2 production. To achieve highly efficient cost–effective toward large–scale practical H production, much work been continuously done exploit alternative anodic oxidation cutting–edge electrocatalysts. This review will focus on recent developments production coupled reactions, including choice substrates, investigation electrocatalytic materials, deep understanding underlying mechanisms. Finally, some insights into scientific challenges now standing in way future advancement technique are shared, hope inspiring further innovative efforts this rapidly growing field.

Язык: Английский

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Highly Efficient Biomass Upgrading by a Ni−Cu Electrocatalyst Featuring Passivation of Water Oxidation Activity

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(37)

Опубликована: Июль 24, 2023

Abstract Electricity‐driven organo‐oxidations have shown an increasing potential recently. However, oxygen evolution reaction (OER) is the primary competitive reaction, especially under high current densities, which leads to low Faradaic efficiency (FE) of product and catalyst detachment from electrode. Here, we report a bimetallic Ni−Cu electrocatalyst supported on Ni foam (Ni−Cu/NF) passivate OER process while oxidation 5‐hydroxymethylfurfural (HMF) significantly enhanced. A density 1000 mA cm −2 can be achieved at 1.50 V vs . reversible hydrogen electrode, both FE yield keep close 100 % over wide range potentials. Both experimental results theoretical calculations reveal that Cu doping impedes OH* deprotonation O* hereby greatly passivated. Those instructive provide new approach realizing highly efficient biomass upgrading by regulating activity.

Язык: Английский

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Dual-site activation of H2 over Cu/ZnAl2O4 boosting CO2 hydrogenation to methanol

Applied Catalysis B Environment and Energy, Год журнала: 2022, Номер 322, С. 122137 - 122137

Опубликована: Ноя. 1, 2022

Язык: Английский

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Advances in Selective Electrochemical Oxidation of 5‐Hydroxymethylfurfural to Produce High‐Value Chemicals

Advanced Science, Год журнала: 2022, Номер 10(4)

Опубликована: Дек. 8, 2022

The conversion of biomass is a favorable alternative to the fossil energy route solve crisis and environmental pollution. As one most versatile platform compounds, 5-hydroxymethylfural (HMF) can be transformed various value-added chemicals via electrolysis combining with renewable energy. Here, recent advances in electrochemical oxidation HMF, from reaction mechanism reactor design are reviewed. First, pathway summarized systematically. Second, parameters easy ignored emphasized discussed. Then, electrocatalysts reviewed comprehensively for different products reactors introduced. Finally, future efforts on exploring mechanism, electrocatalysts, prospected. This review provides deeper understanding electrocatalyst reactor, which expected promote economical efficient industrial applications.

Язык: Английский

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Electrochemical Oxidation of 5‐Hydroxymethylfurfural on CeO₂‐Modified Co₃O₄ with Regulated Intermediate Adsorption and Promoted Charge Transfer

Advanced Functional Materials, Год журнала: 2023, Номер 33(14)

Опубликована: Янв. 17, 2023

Abstract Electrocatalytic 5‐hydroxymethylfurfural oxidation reaction (HMFOR) can replace the kinetically slow oxygen evolution to yield high value‐added chemicals. In this study, interface engineering is constructed by modifying CeO 2 nanoparticles on Co 3 O 4 nanowires supported nickel foam (NF). The construction of heterointerface facilitate structural catalysts and charge transfer, as a result, successfully synthesized NF@Co /CeO exhibits higher conversion (98.0%), 2,5‐furandicarboxylic acid (FDCA) (94.5%), Faradaic efficiency (97.5%) at low electrolysis potential 1.40 V RHE compared NF@CeO . Density‐functional theory calculations indicate that establishment effectively regulate intermediate adsorption promote electron which greatly reduces activation energy dehydrogenation step in 5‐formyl‐2‐furancarboxylic (FFCA), promotes further FFCA FDCA, thereby improving performance HMFOR. HMFOR behavior effect deeply explored, provides guidance for future design with efficient performance.

Язык: Английский

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Electrocatalytic Refinery of Biomass-Based 5-Hydroxymethylfurfural to Fine Chemicals

ACS Catalysis, Год журнала: 2023, Номер 13(17), С. 11204 - 11231

Опубликована: Авг. 10, 2023

Because of depleting fossil-fuel reserves, together with the impacts climate change, alternative eco-friendly production high-value chemicals and renewables is needed. Biomass feedstock particular research interest. 5-Hydroxymethylfural (HMF) a versatile precursor that can be converted to via electrolysis. Reduction generates precursors for ethers, ketones, polyurethanes, polyesters, polyethers, e.g., 2,5-dihydroxymethylfuran (DHMF) 2,5-dimethyletrahydrofuran (DHMTHF), high-energy-density premium biofuels, 2,5-dimethylfuran (DMF), 2,5-hexanedione (HD) 5,5′-bis(hydroxymethyl) hydrofuroin (BHH). Oxidation HMF yields valuable chemical products, including 2,5-diformyl furan (DFF), 5-hydroxymethyl-2-furan carboxylic acid (HMFCA), 2,5-furan dicarboxylic (FDCA), maleic (MA) are precursors/intermediates polymer industry chemical/pharmaceutical production(s). In this review, we 1) report comparative summary electrocatalytic refinery HMF, both electro-oxidation electroreduction pathways, 2) appraise advances in reaction (HRR) (HOR), 3) assess pathways mechanisms, 4) establish design electrocatalysts selection metal materials, geometric structure, electronic structural modifications boost HRR HOR activity selectivity, 5) evaluate impact parameters pH, electrolyte composition, applied potential, initial substrate concentration on HOR, 6) provide prospect future electrochemical refinement HMF. We conclude an improved understanding conditions needed practically selectivity Findings will benefit electrochemistry chemistry generating fine and, therefore, interest researchers manufacturers.

Язык: Английский

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S‐Species‐Evoked High‐Valence Ni^2+δ of the Evolved β‐Ni(OH)₂ Electrode for Selective Oxidation of 5‐Hydroxymethylfurfural

Advanced Materials, Год журнала: 2023, Номер 35(12)

Опубликована: Янв. 6, 2023

An efficient NiSx -modified β-Ni(OH)2 electrode is reported for the selective oxidation reaction of 5-hydroxymethylfurfural (HMFOR) with excellent electrocatalytic (HMF) selectivity (99.4%), conversion (97.7%), and Faradaic efficiency (98.3%). The decoration will evoke high-valence Ni2+δ species in reconstructed electrode, which are real active HMFOR. generated /Ni(OH)O modulates proton-coupled electron-transfer (PCET) process HMFOR, where electrocatalytically Ni(OH)O can effectively trap protons from CHO end HMF to realize electron transfer. oxygen evolution (OER) competes HMFOR when continues accumulate, generate /NiOx (OH)y intermediate. Density functional theory (DFT) calculations experimental results verify that adsorption energy be optimized through increased composition more capture electrons

Язык: 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, Год журнала: 2023, Номер 330, С. 122590 - 122590

Опубликована: Март 6, 2023

Язык: Английский

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