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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Boosting Hydrogen Peroxide Electrosynthesis via Modulating the Interfacial Hydrogen‐Bond Environment

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(27)

Опубликована: Май 10, 2023

Abstract Designing highly efficient and stable electrode‐electrolyte interface for hydrogen peroxide (H 2 O ) electrosynthesis remains challenging. Inhibiting the competitive side reaction, 4 e − oxygen reduction to H O, is essential selective electrosynthesis. Instead of hindering excessive hydrogenation via catalyst modification, we discover that adding a hydrogen‐bond acceptor, dimethyl sulfoxide (DMSO), KOH electrolyte enables simultaneous improvement selectivity activity Spectral characterization molecular simulation confirm formation bonds between DMSO water molecules at can reduce dissociation into active H* species. The suitable supply environment hinders reaction (ORR), thus improving ORR achieving over 90 % . This work highlights importance regulating interfacial by organic as means boosting electrochemical performance in aqueous beyond.

Язык: Английский

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Designed Nanomaterials for Electrocatalytic Organic Hydrogenation Using Water as the Hydrogen Source

Accounts of Chemical Research, Год журнала: 2023, Номер 56(13), С. 1872 - 1883

Опубликована: Июнь 14, 2023

ConspectusThe hydrogenation reaction is one of the most frequently used transformations in organic synthesis. Electrocatalytic by using water (H2O) as hydrogen source offers an efficient and sustainable approach to synthesize hydrogenated products under ambient conditions. Such a technique can avoid use high-pressure flammable gas or other toxic/expensive donors, which usually cause environmental, safety, cost concerns. Interestingly, utilizing easily available heavy (D2O) for deuterated syntheses also attractive due widespread applications molecules synthesis pharmaceutical industry. Despite impressive achievements, electrode selection mainly relies on trial-and-error modes, how electrodes dictate outcomes remains elusive. Therefore, rational design nanostructured driving electrocatalytic series organics via H2O electrolysis developed.In this Account, we review recent advances different types functional groups, including C≡C, C≡N, C═C, C═O, C-Br/I bonds, -NO2, N-heterocycles, with over cathodes. First, general steps (reactant/intermediate adsorption, active atomic (H*) formation, surface reaction, product desorption) are analyzed, key factors proposed optimize performance (e.g., selectivity, activity, Faradaic efficiency (FE), rate, productivity) inhibit side reactions. Then, ex situ spectroscopic tools study intermediates interpret mechanisms introduced. Third, based knowledge mechanisms, introduce catalyst principles detail adoption reactants intermediates, promote formation H* from electrolysis, evolution reactions, improve FEs, space-time productivity products. We then some typical examples. (i) P- S-modified Pd decrease C═C adsorption enabling semihydrogenation alkynes high selectivity FEs at lower potentials. creating high-curvature nanotips concentrate substrates further speeds up process. (ii) By introducing low-coordination sites into Fe combining fluorine modify Co facilitate nitriles N-heterocycles activity obtained. (iii) forming isolated induce specific σ-alkynyl steering S vacancies Co3S4-x preferentially adsorb reduced group-decorated nitroarenes chemoselectivity realized. (iv) For reactant participated designing hydrophobic diffusion layer-supported ultrasmall Cu nanoparticles enhance mass transfer, activation, H2 ethylene ampere-level production 97.7% FE accomplished. Finally, provide outlook current challenges promising opportunities area. believe that summarized here paradigm highly selective nanomaterials achieve fascinating performances.

Язык: Английский

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Mechanistic Insights into Surfactant-Modulated Electrode–Electrolyte Interface for Steering H₂O₂ Electrosynthesis

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(11), С. 7575 - 7583

Опубликована: Март 11, 2024

Electrocatalytic reactions taking place at the electrified electrode–electrolyte interface involve processes of proton-coupled electron transfer. Interfacial protons are delivered to electrode surface via a H2O-dominated hydrogen-bond network. Less efforts made regulate interfacial proton transfer from perspective Here, we present quaternary ammonium salt cationic surfactants as electrolyte additives for enhancing H2O2 selectivity oxygen reduction reaction (ORR). Through in situ vibrational spectroscopy and molecular dynamics calculation, it is revealed that irreversibly adsorbed on response given bias potential range, leading weakening This decreases kinetics, particularly high potentials, thus suppressing 4-electron ORR pathway achieving highly selective 2-electron toward H2O2. These results highlight opportunity steering H2O-involved electrochemical modulating

Язык: Английский

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Steering Selectivity in Electrocatalytic Furfural Reduction via Electrode–Electrolyte Interface Modification

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(17), С. 11876 - 11886

Опубликована: Апрель 16, 2024

Electrocatalytic reduction of biomass-derived furfural (FF) represents a sustainable route to produce furfuryl alcohol (FA) and 2-methylfuran (MF) as value-added chemical biofuel, respectively. However, achieving high selectivity for MF well tuning the between FA within one reaction system remain challenging. Herein, we have reported an electrode-electrolyte interface modification strategy, enabling steering under same conditions. Specifically, by modifying copper (Cu) electrocatalysts with butyl trimethylammonium bromide (BTAB), achieved dramatic shift in from producing (selectivity: 83.8%; Faradaic efficiency, FE: 68.9%) 80.1%; 74.8%). We demonstrated that BTAB adsorption over Cu modulates electrical double layer (EDL) structure, which repels interfacial water weakens hydrogen-bond (H-bond) network proton transfer, thus impeding FF-to-FA conversion suppression hydrogen atom transfer (HAT) process. On contrary, FF-to-MF was less affected. This work shows potential engineering control electrocatalysis.

Язык: Английский

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Rh-dispersed Cu nanowire catalyst for boosting electrocatalytic hydrogenation of 5-hydroxymethylfurfural

Science Bulletin, Год журнала: 2023, Номер 68(19), С. 2190 - 2199

Опубликована: Июль 25, 2023

Язык: Английский

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Cu Single‐Atom Catalysts for High‐Selectivity Electrocatalytic Acetylene Semihydrogenation

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(33)

Опубликована: Июнь 28, 2023

Abstract The site isolation strategy has been employed in thermal catalytic acetylene semihydrogenation to inhibit overhydrogenation and C−C coupling. However, there is a dearth of analogous investigations electrocatalytic systems. In this work, density functional theory (DFT) simulations demonstrate that isolated Cu metal sites have higher energy barriers on Following result, we develop single‐atom catalysts highly dispersed nitrogen‐doped carbon matrix, which exhibit high ethylene selectivity (>80 % Faradaic efficiency for ethylene, <1 C 4 , no ethane) at concentrations acetylene. superior performance observed the selective hydrogenation can be attributed weak adsorption intermediates coupling sites, as confirmed by both DFT calculations experimental results. This study provides comprehensive understanding inhibiting side reactions semihydrogenation.

Язык: Английский

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Microenvironment regulation breaks the Faradaic efficiency-current density trade-off for electrocatalytic deuteration using D2O

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Июнь 19, 2024

Abstract The high Faradaic efficiency (FE) of the electrocatalytic deuteration organics with D 2 O at a large current density is significant for deuterated electrosynthesis. However, FE and are two ends seesaw because severe evolution side reaction nearly industrial densities. Herein, we report combined scenario nanotip-enhanced electric field surfactant-modified interface microenvironment to enable arylacetonitrile in an 80% −100 mA cm −2 . increased concentration low activation energy due along tips accelerated transfer suppressed by surfactant-created deuterophobic contribute breaking trade-off between density. Furthermore, application our strategy other reactions improved efficiencies rationalizes design concept.

Язык: Английский

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Surfactant Directionally Assembled at the Electrode‐Electrolyte Interface for Facilitating Electrocatalytic Aldehyde Hydrogenation

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(31)

Опубликована: Май 22, 2024

Abstract Electrocatalytic hydrogenation of unsaturated aldehydes to alcohols is a promising alternative conventional thermal processes. Both the catalyst and electrolyte deeply impact performance. Designing electrode‐electrolyte interface remains challenging due its compositional structural complexity. Here, we employ electrocatalytic 5‐hydroxymethylfurfural (HMF) as reaction model. The typical cationic surfactant, cetyltrimethylammonium bromide (CTAB), analogs are employed additives tune interfacial microenvironment, delivering high‐efficiency HMF inhibition hydrogen evolution (HER). surfactants experience conformational transformation from stochastic distribution directional assembly under applied potential. This oriented arrangement hampers transfer water molecules promotes enrichment reactants. In addition, near 100 % 2,5‐bis(hydroxymethyl)furan (BHMF) selectivity achieved, faradaic efficiency (FE) BHMF improved 61 74 at −100 mA cm −2 . Notably, microenvironmental modulation strategy applies range reactions involving aldehyde substrates. work paves way for engineering advanced interfaces boosting alcohol electrosynthesis efficiency.

Язык: Английский

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Tandem Electrocatalytic Alkyne Semihydrogenation over Bicomponent Catalysts through Hydrogen Spillover

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(15)

Опубликована: Фев. 7, 2024

Electrocatalytic alkyne semihydrogenation under mild conditions is a more attractive approach for alkene production than industrial routes but suffers from either low efficiency or high energy consumption. Here, we describe tandem catalytic concept that overcomes these challenges. Component (i), which can trap hydrogen effectively, partnered with component (ii), readily release hydrogenation, to enable efficient generation of active on (i) at overpotentials and timely (i)-to-(ii) spillover facile desorptive hydrogenation (ii). We examine this over bicomponent palladium-copper catalysts the representative 2-methyl-3-butene-2-ol (MBE) 2-methyl-3-butyne-2-ol (MBY) achieve record MBE rate 1.44 mmol h

Язык: Английский

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