Dynamic Reconstitution Between Copper Single Atoms and Clusters for Electrocatalytic Urea Synthesis

Advanced Materials, Год журнала: 2023, Номер 35(18)

Опубликована: Фев. 6, 2023

Electrocatalytic CN coupling between carbon dioxide and nitrate has emerged to meet the comprehensive demands of footprint closing, valorization waste, sustainable manufacture urea. However, identification catalytic active sites design efficient electrocatalysts remain a challenge. Herein, synthesis urea catalyzed by copper single atoms decorated on CeO2 support (denoted as Cu1 -CeO2 ) is reported. The catalyst exhibits an average yield rate 52.84 mmol h-1 gcat.-1 at -1.6 V versus reversible hydrogen electrode. Operando X-ray absorption spectra demonstrate reconstitution (Cu1 clusters (Cu4 during electrolysis. These electrochemically reconstituted Cu4 are real for electrocatalytic synthesis. Favorable reactions formation validated using operando synchrotron-radiation Fourier transform infrared spectroscopy theoretical calculations. Dynamic transformations single-atom configurations occur when applied potential switched open-circuit potential, endowing with superior structural electrochemical stabilities.

Язык: Английский

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Boosting Electroreduction Kinetics of Nitrogen to Ammonia via Tuning Electron Distribution of Single‐Atomic Iron Sites

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(16), С. 9078 - 9085

Опубликована: Фев. 15, 2021

Abstract Electrocatalytic nitrogen reduction reaction (NRR) plays a vital role for next‐generation electrochemical energy conversion technologies. However, the NRR kinetics is still limited by sluggish hydrogenation process on noble‐metal‐free electrocatalyst. Herein, we report rational design and synthesis of hybrid catalyst with atomic iron sites anchored N,O‐doped porous carbon (Fe SA ‐NO‐C) matrix an inverse opal structure, leading to remarkably high NH 3 yield rate 31.9 μg h −1 mg cat. Faradaic efficiency 11.8 % at −0.4 V electrocatalysis, outperformed almost all previously reported atomically dispersed metal‐nitrogen‐carbon catalysts. Theoretical calculations revealed that observed catalytic activity Fe ‐NO‐C stemmed mainly from optimized charge‐transfer between adjacent O atoms homogenously distributed support, which could not only significantly facilitate transportation N 2 ions but also effectively decrease binding isolated atom *N intermediate thermodynamic Gibbs free rate‐determining step (*N → *NNH).

Язык: Английский

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Development of Electrocatalysts for Efficient Nitrogen Reduction Reaction under Ambient Condition

Advanced Functional Materials, Год журнала: 2020, Номер 31(11)

Опубликована: Дек. 27, 2020

Abstract As one of the most important chemicals and an energy carrier, synthetic ammonia has been widely studied to meet increasing demand. Among various strategies, electrochemical nitrogen reduction reaction (e‐NRR) is a promising way because its green nature easy set‐up on large‐scale. However, practical application extremely limited very‐low production rate, which strongly dependent electrocatalysts used. Therefore, searching novel efficient for e‐NRR essential promote technology. In this review, it highlights insights mechanism NH 3 synthesis, recommend reliable protocol detection, systematically summarize recent development electrocatalysts, including noble metal‐based materials, single‐metal‐atom catalysts, non‐noble metal, their compounds, metal‐free in both experimental theoretical studies. Various strategies improve catalytic performance by exposed active sites or tuning electronic structures, surface control, defect engineering, hybridization, are carefully discussed. Finally, perspectives challenges outlined. It can be expected that review provides insightful guidance advanced systems produce through N 2 reduction.

Язык: Английский

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Defect engineering for electrochemical nitrogen reduction reaction to ammonia

Nano Energy, Год журнала: 2020, Номер 77, С. 105126 - 105126

Опубликована: Июль 18, 2020

Язык: Английский

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Density functional theory studies of transition metal carbides and nitrides as electrocatalysts

Chemical Society Reviews, Год журнала: 2021, Номер 50(22), С. 12338 - 12376

Опубликована: Янв. 1, 2021

Transition metal carbides and nitrides are interesting non-precious materials that have been shown to replace or reduce the loading of precious metals for catalyzing several important electrochemical reactions. The purpose this review is summarize density functional theory (DFT) studies, describe reaction pathways, identify activity selectivity descriptors, present a future outlook in designing carbide nitride catalysts hydrogen evolution (HER), oxygen (OER), reduction (ORR), nitrogen (N2RR), CO2 (CO2RR) alcohol oxidation This topic high interest scientific communities working field electrocatalysis should provide theoretical guidance rational design improved electrocatalysts.

Язык: Английский

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