Unveiling the Adsorption Behavior and Redox Properties of PtNi Nanowire for Biomass-Derived Molecules Electrooxidation

ACS Nano, Journal Year: 2022, Volume and Issue: 16(12), P. 21518 - 21526

Published: Dec. 7, 2022

Ni-based materials are auspicious electrocatalysts for 5-hydroxymethylfurfural oxidation reaction (HMFOR), including the adsorption and conversion of HMF OHad on electrocatalyst surface. However, intrinsic HMFOR activity catalysts is far from satisfactory due to weak species. Herein, a set PtxNi100-x bundle nanowires (NWs) were prepared HMFOR, which enables low onset-potential large current density. Operando methods reveal that Pt modulates redox property Ni in PtNi NWs accelerates Ni2+-OH Ni3+-O species during HMFOR. Moreover, studies demonstrate synergetic roles enhancing by forming Pt-O-Ni bonds. In detail, atoms modulate d band alter behavior HMF. promote sites. This work provides design principles modulating behaviors organic molecules OHad.

Language: Английский

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Boosting the Electrochemical 5‐Hydroxymethylfurfural Oxidation by Balancing the Competitive Adsorption of Organic and OH⁻ over Controllable Reconstructed Ni₃S₂/NiO_x

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(45)

Published: July 20, 2023

The electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF) is a promising method for the efficient production biomass-derived high-value-added chemicals. However, its practical application limited by: 1) low activity and selectivity caused by competitive adsorption HMF OH- 2) operational stability uncontrollable reconstruction catalyst. To overcome these limitations, series Ni3 S2 /NiOx -n catalysts with controllable compositions well-defined structures are synthesized using novel in situ controlled surface strategy. behavior can be continuously adjusted varying ratio NiOx to on surface, as indicated characterizations, contact angle analysis, theoretical simulations. Owing balanced , optimized -15 catalyst exhibited remarkable performance, current density reaching 366 mA cm-2 at 1.5 VRHE Faradaic efficiency product, 2,5-furanedicarboxylic acid, 98%. Moreover, exhibits excellent durability, structure remaining stable over 100 h operation. This study provides new route design construction value-added biomass conversion offers insights into enhancing catalytic performance balancing adsorption.

Language: Английский

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Biphasic Transition Metal Nitride Electrode Promotes Nucleophile Oxidation Reaction for Practicable Hybrid Water Electrocatalysis

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 33(25)

Published: April 28, 2023

Abstract Glycerol electrooxidation (GOR), as a typical nucleophile oxidation reaction, is deemed promising alternative anodic route to assist cathodic hydrogen evolution reaction. However, the investigations of high‐performance catalysts and industrial‐scale application GOR remain grand challenge. Herein, biphasic Ni 3 N/Co N heterostructure nanowires (denoted N‐NWs) are proposed an efficient bifunctional catalyst, which realizes high Faradaic efficiency 94.6% toward formate production. Importantly, flow electrolyzer achieves industry‐level current density 1 A cm −2 at 2.01 V with impressive stability for steady running over 200 h, realizing lower electricity expense 4.82 kWh m −3 H2 energy saving 9.7%, well outstanding co‐production rates 11 21.4 mmol h −1 H 2 , respectively. Theoretical calculations reveal that electron transfer on heterointerfaces simultaneously optimizes reaction tendency glycerol dehydrogenation kinetics, thus contributing excellent performance.

Language: Английский

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Simultaneous Oxidative Cleavage of Lignin and Reduction of Furfural via Efficient Electrocatalysis by P‐Doped CoMoO₄

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(14)

Published: Jan. 23, 2023

Electrochemical oxidative lignin cleavage and coupled 2-furaldehyde reduction provide a promising approach for producing high-value added products. However, developing efficient bifunctional electrocatalysts with noble-metal-like activity still remains challenge. Here, an electrochemical strategy is reported the selective of Cα -Cβ bonds in into aromatic monomers by tailoring electronic structure through P-doped CoMoO4 spinels (99% conversion, highest monomer selectivity 56%). Additionally, conversion to 2-methyl furan reach 87% 73%, respectively. In situ Fourier transform infrared density functional theory analysis reveal that upward shift Ed upon P-doping leads increase antibonding level, which facilitates adsorption model compounds, thereby enhancing electrocatalytic active site. This work explores potential spinel as electrocatalyst cracking reductive small organic molecules chemicals via P-anion modulation.

Language: Английский

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Electrocatalytic oxidation of 5‐hydroxymethylfurfural for sustainable 2,5‐furandicarboxylic acid production—From mechanism to catalysts design

SusMat, Journal Year: 2023, Volume and Issue: 3(1), P. 21 - 43

Published: Jan. 16, 2023

Abstract Catalytic conversion of biomass‐based platform chemicals is one the significant approaches to utilize renewable biomass resources. 2,5‐Furandicarboxylic acid (FDCA), obtained by an electrocatalytic oxidation 5‐hydroxymethylfurfural (HMF), has attracted extensive attention due potential replacing terephthalic synthesize high‐performance polymeric materials for commercialization. In present work, pH‐dependent reaction pathways and factors influencing degree functional group are first discussed. Then mechanism HMF further elucidated using representative examples. addition, emerging catalyst design strategies (defects, interface engineering) used in generalized, structure–activity relationships between abovementioned catalysts performance analyzed. Furthermore, cathode pairing reactions, such as hydrogen evolution reaction, CO 2 reduction (CO RR), oxygen thermodynamically favorable organic reactions lower cell voltage electrolysis system, Finally, challenges prospects electrochemical FDCA presented, focusing on deeply investigated mechanism, coupling reactor design, downstream product separation/purification.

Language: Английский

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

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 34(3)

Published: Oct. 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.

Language: Английский

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Proton transfer mediator for boosting the current density of biomass electrooxidation to the ampere level

Energy & Environmental Science, Journal Year: 2024, Volume and Issue: 17(4), P. 1603 - 1611

Published: Jan. 1, 2024

Phosphate can be employed as a hydrogen transfer mediator to accelerate the PCET process of HMF dehydrogenation, and Ru, high valence metal, reduce band gap improve charge efficiency.

Language: Английский

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Defect‐Promoted Ni‐Based Layer Double Hydroxides with Enhanced Deprotonation Capability for Efficient Biomass Electrooxidation

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(48)

Published: Sept. 21, 2023

Ni-based hydroxides are promising electrocatalysts for biomass oxidation reactions, supplanting the oxygen evolution reaction (OER) due to lower overpotentials while producing value-added chemicals. The identification and subsequent engineering of their catalytically active sites essential facilitate these anodic reactions. Herein, proportional relationship between catalysts' deprotonation propensity Faradic efficiency 5-hydroxymethylfurfural (5-HMF)-to-2,5 furandicarboxylic acid (FDCA, FEFDCA ) is revealed by thorough density functional theory (DFT) simulations atomic-scale characterizations, including in situ synchrotron diffraction spectroscopy methods. capability ultrathin layer-double (UT-LDHs) regulated tuning covalency metal (M)-oxygen (O) motifs through defect site selection M3+ co-chemistry. NiMn UT-LDHs show an ultrahigh 99% at 1.37 V versus reversible hydrogen electrode (RHE) retain a high 92.7% OER-operating window 1.52 V, about 2× that NiFe (49.5%) V. Ni-O Mn-O function as dual HMF electrooxidation, where continuous Mn-OH plays dominant role achieving selectivity suppressing OER potentials. results showcase universal concept modulating competing reactions aqueous electrolysis electronically behavior hydroxides, anticipated be translatable across various substrates.

Language: Английский

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Polyhedral Coordination Determined Co‐O Activity for Electrochemical Oxidation of Biomass Alcohols

Advanced Energy Materials, Journal Year: 2023, Volume and Issue: 13(37)

Published: Aug. 11, 2023

Abstract Earth‐abundant transition metal oxides are promising electrocatalysts for oxidation of biomass alcohols. Here, CoO and Co 3 O 4 selected as representative cobalt oxide catalysts grown on carbon fiber paper (CFP) electrodes to reveal the interplay between electronic structure catalytic activity glycerol, diols, monohydric In situ electrochemical tests elucidate that CoO/CFP electrode has lower interfacial impedance, higher charge transfer, faster rate, thereby alcohol than /CFP electrode. Especially glycerol oxidation, only requires 1.32 V reach 10 mA cm −2 , potential is 120 mV The can also produce value‐added products such formate, acetate, glycolate with high selectivity efficiency at low energy consumptions from Theoretical calculations further confirm dominant role octahedrally coordinated Co‐O sites in adsorption, activation, C3‐C1 This work sheds light design highly efficient alcohols by populating octahedral crystal structure.

Language: Английский

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Unlocking Efficient Hydrogen Production: Nucleophilic Oxidation Reactions Coupled with Water Splitting

Advanced Materials, Journal Year: 2024, Volume and Issue: unknown

Published: June 10, 2024

Abstract Electrocatalytic water splitting driven by sustainable energy is a clean and promising water‐chemical fuel conversion technology for the production of high‐purity green hydrogen. However, sluggish kinetics anodic oxygen evolution reaction (OER) pose challenges large‐scale hydrogen production, limiting its efficiency safety. Recently, OER has been replaced nucleophilic oxidation (NOR) with biomass as substrate coupled (HER), which attracted great interest. Anode NOR offers faster kinetics, generates high‐value products, reduces consumption. By coupling reaction, can be enhanced while yielding products or degrading pollutants. Therefore, NOR‐coupled HER another new electrolytic strategy after significance realizing development global decarbonization. This review explores potential reactions an alternative to delves into mechanisms, guiding future research in production. It assesses different methods, analyzing pathways catalyst effects. Furthermore, it evaluates role electrolyzers industrialized discusses prospects challenges. comprehensive aims advance efficient economical

Language: Английский

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