Atomically Precise Copper Nanoclusters for Highly Efficient Electroreduction of CO₂ towards Hydrocarbons via Breaking the Coordination Symmetry of Cu Site

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(36)

Опубликована: Июль 20, 2023

Abstract We propose an effective highest occupied d‐orbital modulation strategy engendered by breaking the coordination symmetry of sites in atomically precise Cu nanocluster (NC) to switch product CO 2 electroreduction from HCOOH/CO higher‐valued hydrocarbons. An well‐defined 6 NC with symmetry‐broken Cu−S N 1 active (named (MBD) , MBD=2‐mercaptobenzimidazole) was designed and synthesized a judicious choice ligand containing both S atoms. Different previously reported high HCOOH selectivity NCs 3 sites, structure shows Faradaic efficiency toward hydrocarbons 65.5 % at −1.4 V versus reversible hydrogen electrode (including 42.5 CH 4 23 C H ), partial current density −183.4 mA cm −2 . Theoretical calculations reveal that can rearrange 3d orbitals as d‐orbital, thus favoring generation key intermediate *COOH instead *OCHO favor *CO formation, followed hydrogenation and/or C−C coupling produce This is first attempt regulate mode atom for generation, provides new inspiration designing efficient RR towards highly‐valued products.

Язык: Английский

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General Formation of Interfacial Assembled Hierarchical Micro‐Nano Arrays for Biomass Upgrading‐Coupled Hydrogen Production

Advanced Functional Materials, Год журнала: 2023, Номер 34(6)

Опубликована: Ноя. 7, 2023

Abstract Construction of efficient catalysts to couple biomass upgrading with hydrogen production is significant for improving energy efficiency, which remains a challenge. Herein, general method manufacturing 3D hierarchical micro‐nano arrays consisting template framework and nanoparticle‐decorated nanosheets reported. This strategy provides an opportunity controllably tailor the interfacial assembly on precursor materials. The obtained Co@NiMoO‐Ni/NF exhibits enhanced electrocatalytic performance oxidation production. It only needs 1.21 V achieve 10 mA cm −2 5‐hydroxymethylfurfural electrooxidation reaction (HMFOR) assisted H 2 evolution (HER). good catalytic ascribed intense interaction between (Co) (NiMoO‐Ni), tunes electron structure catalyst optimize adsorption behavior HMFOR/HER intermediates promote bonds breakage key in process. work thus designing ideal upgrading‐coupled

Язык: Английский

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Electrochemical hydrogenation and oxidation of organic species involving water

Nature Reviews Chemistry, Год журнала: 2024, Номер 8(4), С. 277 - 293

Опубликована: Март 25, 2024

Язык: Английский

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Controllable Electron Distribution Reconstruction of Spinel NiCo₂O₄ Boosting Glycerol Oxidation at Elevated Current Density

Advanced Functional Materials, Год журнала: 2023, Номер 34(3)

Опубликована: Окт. 5, 2023

Abstract Electrocatalytic glycerol oxidation reaction (GOR) is an effective way to convert biomass byproduct high value‐added chemicals, which; however, suffers from the low activity and conversion ratio of presently available catalysts. Herein, NiCo 2 O 4 /NF bimetallic oxide nanoarray controllably fabricated by Ni substituting for octahedral Co 3+ in 3 , which exhibits excellent GOR catalytic at elevated current densities ( E 300 = 1.42 V, 600 1.62 V) overall Faradaic efficiency 97.5% V (FE formic acid 89.9% FE glycolic 7.62%). The performance attributed structure evolution including rapid generation III ‐OOH active species, optimized intermediates adsorption, accelerated electron transfer owing introduction, are evidenced operando spectroscopy measurements density functional theory calculations, respectively. GOR/hydrogen coupled two‐electrode electrolytic cell voltage ≈299 mV lower than that water splitting 50 mA cm −2 . More importantly, compared conventional splitting, this electrolyzer stable over 200 h 1.75 reducing energy consumption 16.9% obtaining products anode concurrently.

Язык: Английский

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Recent advances in low-temperature NH3-SCR of NOx over Ce-based catalysts: Performance optimizations, reaction mechanisms and anti-poisoning countermeasures

Chemical Engineering Journal, Год журнала: 2023, Номер 476, С. 146889 - 146889

Опубликована: Окт. 24, 2023

Язык: Английский

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Enabling high-efficiency ethanol oxidation on NiFe-LDH via deprotonation promotion and absorption inhibition

Journal of Energy Chemistry, Год журнала: 2023, Номер 85, С. 76 - 82

Опубликована: Июнь 28, 2023

Язык: Английский

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High‐Surface Area Mesoporous Sc₂O₃ with Abundant Oxygen Vacancies as New and Advanced Electrocatalyst for Electrochemical Biomass Valorization

Advanced Materials, Год журнала: 2024, Номер 36(16)

Опубликована: Янв. 15, 2024

Abstract Scandium oxide (Sc 2 O 3 ) is considered as omnipotent “Industrial Ajinomoto” and holds promise in catalytic applications. However, rarely little attention paid to its electrochemistry. Here, the first nanocasting design of high‐surface area Sc with abundant oxygen vacancies (mesoporous V ‐Sc for efficient electrochemical biomass valorization reported. In case electro‐oxidation 5‐hydroxymethylfurfural (HMF) 2,5‐furandicarboxylic acid (FDCA), quantitative HMF conversion, high yield, faradic efficiency FDCA via hydroxymethylfurancarboxylic pathway are achieved by this advanced electrocatalyst. The beneficial effect on electrocatalytic performance mesoporous revealed enhanced adsorption reactants reduced energy barrier process. concerted design, situ ex experimental studies theoretical calculations shown work should shed light rational elaboration electrocatalysts, contribute establishment a circular carbon economy since bio‐plastic monomer green hydrogen efficiently synthesized.

Язык: Английский

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Recent advances in hydrogen production coupled with alternative oxidation reactions

Coordination Chemistry Reviews, Год журнала: 2024, Номер 509, С. 215777 - 215777

Опубликована: Март 26, 2024

Язык: Английский

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Advancements in transition bimetal catalysts for electrochemical 5-Hydroxymethylfurfural (HMF) oxidation

Journal of Energy Chemistry, Год журнала: 2024, Номер 98, С. 24 - 46

Опубликована: Июнь 24, 2024

Язык: Английский

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5-Hydroxymethylfurfural Oxidation in Scaled Anion Exchange Membrane Electrolyzer with NiCuO_x Catalyst

ACS Energy Letters, Год журнала: 2025, Номер 10(1), С. 571 - 578

Опубликована: Янв. 2, 2025

The utilization of anion exchange membrane (AEM) electrolyzers presents an opportunity for commercial production 2,5-furandicarboxylic acid (FDCA) through electrochemical oxidation 5-hydroxymethylfurfural (HMF). Consequently, developing facile synthesis techniques scaled-up electrocatalysts HMF reaction (HMFOR) is a crucial step. Herein, we developed one-step soaking method preparing 100 cm2 NiCu-based catalyst on Ni foam (NiCuOx/NF) in 10 s. In single-pass 25 AEM electrolyzer assembled by the obtained catalyst, high yield ≥95.0% and selectivity ≥99.9% were achieved to produce FDCA continuously with 200 mM electrolyte. After h stable operation at A, 207.28 g was attained purity over 99%. This work provides valuable insights into industrial-scale commercialization biomass upgrading electrolyzers.

Язык: Английский

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