Alloying and confinement effects on hierarchically nanoporous CuAu for efficient electrocatalytic semi-hydrogenation of terminal alkynes

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

Опубликована: Июль 17, 2024

Abstract Electrocatalytic alkynes semi-hydrogenation to produce alkenes with high yield and Faradaic efficiency remains technically challenging because of kinetically favorable hydrogen evolution reaction over-hydrogenation. Here, we propose a hierarchically nanoporous Cu 50 Au alloy improve electrocatalytic performance toward alkynes. Using Operando X-ray absorption spectroscopy density functional theory calculations, find that modulate the electronic structure Cu, which could intrinsically inhibit combination H* form H 2 weaken alkene adsorption, thus promoting alkyne hampering Finite element method simulations experimental results unveil catalysts induce local microenvironment abundant K + cations by enhancing electric field within nanopore, accelerating water electrolysis more H*, thereby conversion As result, electrocatalyst achieves highly efficient 94% conversion, 100% selectivity, 92% over wide potential window. This work provides general guidance rational design for high-performance transfer catalysts.

Язык: Английский

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Promoting Electrocatalytic Semihydrogenation of Alkynols to Alkenols over a Bimetallic CuAu Alloy Catalyst

ACS Catalysis, Год журнала: 2024, Номер 14(8), С. 5675 - 5684

Опубликована: Апрель 1, 2024

Electrocatalytic semihydrogenation of alkynols to alkenols under ambient conditions using H2O as a hydrogen source is highly attractive in synthetic chemistry. However, it still challenging achieve high Faradaic efficiency (FE) wide potential window. Herein, we reported bimetallic Cu3Au alloy an efficient catalyst for electrocatalytic alkenols. Specifically, during 2-butyne-1,4-diol (BYD) 2-butene-1,4-diol (BED), the achieves 12.6-fold greater reaction rate and higher FE compared with pure Cu (99 vs 63%). Moreover, maintains >96% FEs window from −0.19 −0.59 V RHE. We demonstrate that competitive adsorptions reactive (H*) BYD greatly influence processes. The presence Au facilitates H* formation reduces adsorption on Cu, thus enhancing hydrogenation performance. affords broad substrate scope aromatic alkynes, producing corresponding alkenes good selectivities. Finally, coupled glycerol oxidation replace oxygen evolution two-electrode system, showing 40% energy saving at 200 mA BED production coproduction valuable formate anode, demonstrating economical manner.

Язык: Английский

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Lattice Strain and Mott–Schottky Effect of the Charge-Asymmetry Pd₁Fe Single-Atom Alloy Catalyst for Semi-Hydrogenation of Alkynes with High Efficiency

ACS Nano, Год журнала: 2024, Номер 18(20), С. 13286 - 13297

Опубликована: Май 10, 2024

The ideal interface design between the metal and substrate is crucial in determining overall performance of alkyne semihydrogenation reaction. Single-atom alloys (SAAs) with isolated dispersed active centers are media for study reaction effects. Herein, a charge-asymmetry "armor" SAA (named Pd1Fe SAA@PC), which consists alloy core semiconducting P-doped C (PC) shell, rationally designed as an catalyst selective hydrogenation alkynes high efficiency. Multiple spectroscopic analyses density functional theory calculations have demonstrated that SAA@PC dual-regulated by lattice tensile Schottky effects, govern selectivity activity hydrogenation, respectively. (1) PC shell layer applied external traction force causing 1.2% strain inside to increase selectivity. (2) P doping into C-shell realized transition from p-type semiconductor n-type semiconductor, thereby forming unique junction advancing activity. dual regulation effect ensures excellent phenylethylene, achieving conversion rate 99.9% 98.9% at 4 min. These well-defined modulation strategies offer practical approach rational optimization catalysts.

Язык: Английский

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High‐Density Rare‐Earth Single‐Atom‐Triggered Unconventional Transition of Adsorption Configuration on La₁Pd Monatomic Alloy Metallene for Sustainable Electrocatalytic Alkynol Semi‐Hydrogenation

Advanced Functional Materials, Год журнала: 2024, Номер 34(44)

Опубликована: Май 17, 2024

Abstract Electrocatalytic alkynol semi‐hydrogenation for the high‐value chemicals alkenol with mild conditions and carbon‐free emission is a potentially green sustainable alternative to conventional thermocatalytic routes, which generally involves design of electrocatalysts high activity selectivity. Here, rare‐earth single‐atom (Ln = La, Nd, Pr) coordinated Pd metallene 1 Pdene) reported electrocatalytic 2‐methyl‐3‐butyn‐2‐ol (MBY) reaction (MBY ESHR) synthesis 2‐methyl‐3‐buten‐2‐ol (MBE). Typically, in alkaline medium containing 0.1 m MBY, MBY conversion MBE selectivity La Pdene are as ≈97% ≈95%, respectively, excellent stability. Meanwhile, situ infrared spectra reveal during dynamic process. Theoretical calculations that interaction between host triggers an unconventional transformation intermediate MBE* adsorption configuration hydrogenation, achieving optimal desorption energy target product optimizing barriers inhibit over‐hydrogenation MBE. Moreover, active site hydrogen supplier H 2 O effectively reduces competition reactants O, rendering synergistic co‐catalytic sites promote reaction.

Язык: Английский

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Lewis-base ligand-reshaped interfacial hydrogen-bond network boosts CO2 electrolysis

National Science Review, Год журнала: 2024, Номер 11(8)

Опубликована: Июнь 22, 2024

ABSTRACT Both the catalyst and electrolyte strongly impact performance of CO2 electrolysis. Despite substantial progress in catalysts, it remains highly challenging to tailor compositions understand their functions at interface. Here, we report that ethylenediaminetetraacetic acid (EDTA) its analogs, featuring strong Lewis acid-base interaction with metal cations, are selected as additives reshape catalyst-electrolyte interface for promoting Mechanistic studies reveal EDTA molecules dynamically assembled toward regions response bias potential due EDTA4–-K+. As a result, original hydrogen-bond network among interfacial H2O is disrupted, gap layer electrified established. The EDTA-reshaped K+ solvation structure promotes protonation *CO2 *COOH suppressing *H2O dissociation *H, thereby boosting co-electrolysis carbon-based products. In particular, when 5 mM added into electrolytes, Faradaic efficiency CO on commercial Ag nanoparticle increased from 57.0% 90.0% an industry-relevant current density 500 mA cm−2. More importantly, Lewis-base ligand-reshaped allows range catalysts (Ag, Zn, Pd, Bi, Sn, Cu) deliver substantially selectivity products both H-type flow-type electrolysis cells.

Язык: Английский

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Regulating the cobalt phthalocyanine molecules by introducing adjacent cubic molybdenum carbide nanoparticles for accelerated proton transfer towards efficient CO2 reduction reaction

National Science Review, Год журнала: 2025, Номер unknown

Опубликована: Янв. 10, 2025

The electrochemical CO2 reduction reaction (CO2RR) is an important application that can considerably mitigate environmental and energy crises. However, the slow proton-coupled electron transfer process continues to limit overall catalytic performance. Fine-tuning microenvironment by accurately constructing local structure of catalysts provides a novel approach enhancing kinetics. Here, cubic-phase α-MoC1-x nanoparticles were incorporated into carbon matrix coupled with cobalt phthalocyanine molecules (α-MoC1-x-CoPc@C) for co-reduction H2O, achieving impressive Faradaic efficiency CO close 100%. Through combination in-situ spectroscopies, measurements, theoretical simulations, it demonstrated CoPc optimized configuration serve as active centers H2O activation reduction, respectively. interfacial water rearranged, forming dense hydrogen bond network on catalyst surface. This at electrode-electrolyte interface synergistically enhanced dissociation, accelerated proton transfer, improved performance CO2RR.

Язык: Английский

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Promoting electrocatalytic oxidation of methanol to formate through interfacial interaction in NiMo oxide-CoMo oxide mixture-derived catalysts

CHINESE JOURNAL OF CATALYSIS (CHINESE VERSION), Год журнала: 2024, Номер 56, С. 139 - 149

Опубликована: Янв. 1, 2024

Язык: Английский

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Hydrogen Spillover Accelerates Electrocatalytic Semi-hydrogenation of Acetylene in Membrane Electrode Assembly Reactor

ACS Applied Materials & Interfaces, Год журнала: 2024, Номер 16(7), С. 8668 - 8678

Опубликована: Фев. 12, 2024

Electrocatalytic acetylene semi-hydrogenation (EASH) offers a promising and environmentally friendly pathway for the production of C2H4, widely used petrochemical feedstock. While economic feasibility this route has been demonstrated in three-electrode systems, its viability practical device remains unverified. In study, we designed highly efficient electrocatalyst based on PdCu alloy system utilizing hydrogen spillover mechanism. The catalyst achieved an operational current density 600 mA cm−2 zero-gap membrane electrode assembly (MEA) reactor, with C2H4 selectivity exceeding 85%. This data confirms EASH real-world applications. Furthermore, through situ Raman spectroscopy theoretical calculations, elucidated catalytic mechanism involving interfacial spillover. Our findings underscore potential as greener scalable approach production, thus advancing field electrocatalysis sustainable chemical synthesis.

Язык: Английский

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Surfactant‐modified electrode–electrolyte interface for steering CO₂ electrolysis on Cu electrodes

AIChE Journal, Год журнала: 2023, Номер 70(1)

Опубликована: Окт. 17, 2023

Abstract Cu‐based catalysts exhibit the unique ability to generate high‐order products from electrochemical CO 2 reduction reaction (CO RR). The performance of systems is jointly influenced by and local microenvironment electrode–electrolyte interface. Here, Cu nanowires as a model catalyst, in combination with cetyl trimethyl ammonium bromide (CTAB) electrolyte additives, are designed steer RR. By using rotating disc electrode situ vibrational spectroscopy, it revealed that hydrophobic interface built, interaction interfacial water surface‐adsorbed disrupted CTAB, which dramatically improve formate selectivity (from 5% 63%) high partial current density (13‐fold increase) at −1.0 V vs. reversible hydrogen electrode. understanding surfactant‐modified established here offers distinct perspective control on promoting electrosynthesis performance.

Язык: Английский

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Ru‐supported Cu nanowire catalyst enabling to suppress C–C coupling for high‐selectivity ethylamine electrosynthesis

AIChE Journal, Год журнала: 2024, Номер 70(5)

Опубликована: Фев. 6, 2024

Abstract Electrochemical acetonitrile hydrogenation compared with thermocatalytic provides a potential route to produce ethylamine in mild conditions. It is challenging suppress the C–C coupling for improving selectivity. Here, Ru‐supported Cu nanowire catalysts (Ru‐Cu NWs) are designed achieve nearly 100% specific selectivity of without byproducts. In situ vibrational spectroscopy and electron spin resonance results reveal that Ru‐Cu NWs provide high active adsorption hydrogen (H*) coverage at electrified interface so imine intermediates more readily hydrogenated generate ethylamine, thus suppressing coupling. Density functional theory calculations disclose formation H* occurs over than NWs. Moreover, presence Ru changes potential‐determining step facilitates entire process. The strategy understanding established here can be extended other electrocatalytic reactions.

Язык: Английский

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