Modulation of Topological Order in Structural Unit of Nitrides for Enhanced Electrosynthesis of Nitrile DOI Open Access
Lei Zhao,

Keke Mao,

Jing Xu

et al.

Advanced Functional Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 5, 2025

Abstract The electrochemical oxidation of amines has emerged as a promising alternative to traditional energy‐intensive industrial processes for the green synthesis nitriles, and rational design efficient electrocatalysts is crucial due sluggish reaction kinetics. Herein, it reported that modulating topological order within same structural unit can boost catalytic activity electrooxidation benzylamine benzonitrile (BOR). Using nickel nitride model, Cu atoms are introduced into pristine N─Ni framework, inducing change in units resulting formation Ni 3 CuN with an antiperovskite structure. As result, exhibits 2‐fold enhancement BOR compared N, despite fact coordination polyhedra both almost identical. Theoretical calculations demonstrate modulation strategy successfully weakens Ni─N bonding interactions, induces downward shift d‐band centers, optimizes desorption products, which ultimately contributes more superior electrocatalytic CuN. This work provides new perspective on developing advanced through modulation.

Language: Английский

Electrochemical hydrogenation and oxidation of organic species involving water DOI
Cuibo Liu, Fanpeng Chen, Bo‐Hang Zhao

et al.

Nature Reviews Chemistry, Journal Year: 2024, Volume and Issue: 8(4), P. 277 - 293

Published: March 25, 2024

Language: Английский

Citations

61
Boosting Hydrogen Peroxide Electrosynthesis via Modulating the Interfacial Hydrogen‐Bond Environment DOI

Yushuang Fang,

Fan Yu, Kunchi Xie

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(27)

Published: May 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.

Language: Английский

Citations

58
Designed Nanomaterials for Electrocatalytic Organic Hydrogenation Using Water as the Hydrogen Source DOI
Cuibo Liu, Yongmeng Wu, Bo‐Hang Zhao

et al.

Accounts of Chemical Research, Journal Year: 2023, Volume and Issue: 56(13), P. 1872 - 1883

Published: June 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.

Language: Английский

Citations

53
Mechanistic Insights into Surfactant-Modulated Electrode–Electrolyte Interface for Steering H2O2 Electrosynthesis DOI
Fan Yu, Yuxin Chen,

Wangxin Ge

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(11), P. 7575 - 7583

Published: March 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

Language: Английский

Citations

25
Steering Selectivity in Electrocatalytic Furfural Reduction via Electrode–Electrolyte Interface Modification DOI

Kaiyue Ji,

Y. Liu, Ye Wang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(17), P. 11876 - 11886

Published: April 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.

Language: Английский

Citations

24
Rh-dispersed Cu nanowire catalyst for boosting electrocatalytic hydrogenation of 5-hydroxymethylfurfural DOI
Wenfei Zhang,

Yanbin Qi,

Yuan Zhao

et al.

Science Bulletin, Journal Year: 2023, Volume and Issue: 68(19), P. 2190 - 2199

Published: July 25, 2023

Language: Английский

Citations

33
Cu Single‐Atom Catalysts for High‐Selectivity Electrocatalytic Acetylene Semihydrogenation DOI
Xiaoli Jiang, Lei Tang,

Lei Dong

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(33)

Published: June 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.

Language: Английский

Citations

29
Microenvironment regulation breaks the Faradaic efficiency-current density trade-off for electrocatalytic deuteration using D2O DOI Creative Commons
Meng He, Rui Li, Chuanqi Cheng

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: June 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.

Language: Английский

Citations

13
Surfactant Directionally Assembled at the Electrode‐Electrolyte Interface for Facilitating Electrocatalytic Aldehyde Hydrogenation DOI
Wenfei Zhang,

Wangxin Ge,

Yanbin Qi

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(31)

Published: May 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.

Language: Английский

Citations

12
Tandem Electrocatalytic Alkyne Semihydrogenation over Bicomponent Catalysts through Hydrogen Spillover DOI

Qiang Tan,

Linsen Li,

Yuefei Li

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(15)

Published: Feb. 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

Language: Английский

Citations

11