Rational Designing Microenvironment of Gas‐Diffusion Electrodes via Microgel‐Augmented CO2 Availability for High‐Rate and Selective CO2 Electroreduction to Ethylene DOI Creative Commons
Hesamoddin Rabiee, Mengran Li, Penghui Yan

et al.

Advanced Science, Journal Year: 2024, Volume and Issue: 11(40)

Published: Aug. 29, 2024

Abstract Efficient electrochemical CO 2 reduction reaction (CO RR) requires advanced gas‐diffusion electrodes (GDEs) with tunned microenvironment to overcome low availability in the vicinity of catalyst layer. Herein, for first time, pyridine‐containing microgels‐augmented is presented Cu O‐based GDE high‐rate ethylene, owing presence ‐phil microgels amine moieties. Microgels as three‐dimensional polymer networks act micro‐reservoirs engineer and boost local availability. The superior ethylene production performance modified by 4‐vinyl pyridine microgels, compared diethylaminoethyl methacrylate indicates bifunctional effect pyridine‐based enhance availability, electrocatalytic reduction. While Faradaic efficiency (FE) without was capped at 43% 300 mA cm −2 , showed 56% FE 700 . A similar trend observed zero‐gap design, GDEs 58% −4.0 cell voltage (>350 current density), resulting over 2‐fold improvement production. This study showcases use a higher rate RR‐to‐C 2+ opening an avenue several other more selective efficient electrolysis.

Language: Английский

Sub-1 nm Cu2O Nanosheets for the Electrochemical CO2 Reduction and Valence State–Activity Relationship DOI
Ping Wang,

Senyao Meng,

Botao Zhang

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(48), P. 26133 - 26143

Published: Nov. 17, 2023

The copper-based (Cu-based) electrocatalytic materials effectively carry out the carbon dioxide reduction reaction (CO2RR) toward C2+ products, yet superiority and stability of oxidation state Cu are still worth studying. Herein, we designed prepared three Cu-based electrocatalysts with different states to study valence state-activity relationship. Among these electrocatalysts, Cu2O nanosheets thickness only 0.9 nm show an extremely high Faraday efficiency (FEC2+) ∼81%, FEC2+ has increase 37% compared traditional CuOx phase. ultrathin two-dimensional (2D) nanosheet structure abundant oxygen vacancies can stabilize improve selectivity for products in CO2RR. In situ Raman spectroscopy density functional theory calculations demonstrate that rich Cu+ 2D is most suitable *CO adsorption coverage on catalyst surface, which promotes C-C coupling This work provides excellent CO2RR products.

Language: Английский

Citations

80
Grain boundary-abundant copper nanoribbons on balanced gas-liquid diffusion electrodes for efficient CO2 electroreduction to C2H4 DOI
Lei Bian, Ziyang Zhang, Hao Tian

et al.

CHINESE JOURNAL OF CATALYSIS (CHINESE VERSION), Journal Year: 2023, Volume and Issue: 54, P. 199 - 211

Published: Nov. 1, 2023

Language: Английский

Citations

76
Twin Heterostructure Engineering and Facet Effect Boosts Efficient Reduction CO2-to-Ethanol at Low Potential on Cu2O@Cu2S Catalysts DOI
Jing Li,

Rong Cai,

Haiqiang Mu

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(5), P. 3266 - 3277

Published: Feb. 15, 2024

Copper oxide (Cu2O) is considered a promising catalyst that can effectively reduce the overpotential of CO2 reduction reaction (CO2 RR) and increase selectivity for C2+ products. However, developing high-performance stable CO2-to-ethanol (C2H5OH) based-Cu2O electrocatalysts remains challenging. In this work, Cu2O@Cu2S twin heterojunction catalysts with multitwin boundaries are designed to afford C2H5OH productivity at low potential through electrocatalytic RR, highly dependent on facet nanocubes outperforming octahedra. Detailed electrochemical experiments, density functional theory (DFT) calculations in situ infrared spectroscopy reveals introduction Cu2S boosts high coverage *CO, which easily spillover generate *CHOH_*CO coupling pathway. A production begins an ultralow −0.45 V vs RHE reaches 34 43.9% Faradaic efficiencies (FE) −0.65 H-cell flow cell, respectively. Meanwhile, constructed interface coherent structure suitable band facilitate electron transfer from Cu2O Cu2S, leading stability Cu+ valence states. This work provides avenue precisely design by regulating configuration.

Language: Английский

Citations

28
Low-coordinated copper facilitates the *CH2CO affinity at enhanced rectifying interface of Cu/Cu2O for efficient CO2-to-multicarbon alcohols conversion DOI Creative Commons
Yangyang Zhang, Yanxu Chen, Xiaowen Wang

et al.

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

Published: June 18, 2024

Abstract The carbon−carbon coupling at the Cu/Cu 2 O Schottky interface has been widely recognized as a promising approach for electrocatalytic CO conversion into value-added alcohols. However, limited selectivity of C 2+ alcohols persists due to insufficient control over rectifying characteristics required precise bonding oxyhydrocarbons. Herein, we present an investigation manipulation coordination environment Cu sites through in-situ electrochemical reconstruction strategy, which indicates that construction low-coordinated facilitates enhanced interfaces, and induces asymmetric electronic perturbation faster electron exchange, thereby boosting C-C oxyhydrocarbons towards nucleophilic reaction process *H CCO-CO. Impressively, exhibit superior faradic efficiency 64.15 ± 1.92% energy ~39.32% production, while maintaining stability 50 h (faradic >50%, total current density = 200 mA cm −2 ) in flow-cell electrolyzer. Theoretical calculations, operando synchrotron radiation Fourier transform infrared spectroscopy, Raman experiments decipher can enhance coverage *CO adsorption *CH CH CHO, facilitating formation

Language: Английский

Citations

27
Bottom‐up Growth of Convex Sphere with Adjustable Cu(0)/Cu(I) Interfaces for Effective C2 Production from CO2 Electroreduction DOI
Huan Liu, Cheng‐Han Yang,

Tong Bian

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(28)

Published: May 4, 2024

Abstract One challenge confronting the Cu 2 O catalysts in electrocatalysis of carbon dioxide reduction reaction (CO RR) is active Cu(I) species, resulting low selectivity and quick deactivation. In this study, we for first time introduce a bottom‐up growth convex sphere with adjustable Cu(0)/Cu(I) interfaces (Cu x @Cu spheres). Interestingly, are dynamically modulated by varying hydrothermal time, thus regulating conversion C 1 products. particular, 4 h treatment applied to 0.25 favorable interface results highest products (90.5 %). situ Fourier‐transform infrared spectroscopy measurements density functional theory calculations reveal that lowers energy barrier production ethylene ethanol while increasing coverage localized *CO adsorbate increased dimerization. This work establishes novel approach transforming state valence‐sensitive electrocatalysts into high‐value energy‐related engineering

Language: Английский

Citations

26
Selective Increase in CO2 Electroreduction to Ethanol Activity at Nanograin‐Boundary‐Rich Mixed Cu(I)/Cu(0) Sites via Enriching Co‐Adsorbed CO and Hydroxyl Species DOI
Ting Zhang,

Shenglin Xu,

De‐Li Chen

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: May 31, 2024

Selective producing ethanol from CO

Language: Английский

Citations

24
Spontaneous Reconstruction of Copper Active Sites during the Alkaline CORR: Degradation and Recovery of the Performance DOI
Qiliang Liu, Qike Jiang, Ling Li

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(6), P. 4242 - 4251

Published: Feb. 1, 2024

Understanding the reconstruction of electrocatalysts under operational conditions is essential for studying their catalytic mechanisms and industrial applications. Herein, using spatiotemporally resolved Raman spectroscopy with CO as a probe molecule, we spontaneous Cu active sites during cathodic reduction reactions (CORRs). Quasi-in situ focused ion beam transmission electron microscopy (FIB-TEM) revealed that prolonged electrolysis, surface can reconstruct to form nanometer-sized particles (111)/(100) facets abundant grain boundaries, which strongly favor formation an inactive *CObridge binding site deteriorate CORR performance. A short period anodic oxidation efficiently remove these reconstructed nanoparticles by quick dissolution Cu, thus providing effective strategy regenerate catalysts recover This study provides real-time in observations changes key reaction intermediates, highlighting decisive role local site, rather than macroscopic morphology, on adsorption intermediates

Language: Английский

Citations

19
Urea Synthesis via Coelectrolysis of CO2 and Nitrate over Heterostructured Cu–Bi Catalysts DOI
Xinning Song, Xiaodong Ma, Tianhui Chen

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(37), P. 25813 - 25823

Published: Sept. 5, 2024

Electrocatalytic coupling of CO

Language: Английский

Citations

16
Direct Electrochemical Reduction of CO2 to C2+ Chemicals: Catalysts, Microenvironments, and Mechanistic Understanding DOI
Shichen Guo, J. Wang, Haozhe Zhang

et al.

ACS Energy Letters, Journal Year: 2025, Volume and Issue: 10(1), P. 600 - 619

Published: Jan. 2, 2025

The electrochemical reduction reaction of CO2 (eCO2RR) to chemicals presents a viable solution for addressing climate change and sustainable manufacturing. In this Review, we describe the recent advancements in eCO2RR multicarbon (C2+) production from aspects catalyst structure, microenvironments, mechanistic understanding. We draw experimental theoretical comparisons between systems containing bulk highly dispersed metals, alloys, metal compounds recount new results microenvironmental impacts as well catalytic mechanism. From our own studies, offer some viewpoints on electrocatalytic mechanism during complex multistep proton-coupled electron transfers propose several research directions unlocking full potential scalable industrial CO2-to-C2+ conversion.

Language: Английский

Citations

2
Stabilizing Cu+ Species in Cu2O/CuO Catalyst via Carbon Intermediate Confinement for Selective CO2RR DOI

Haojun Shi,

Lingli Luo,

Congcong Li

et al.

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 34(11)

Published: Dec. 14, 2023

Abstract Copper oxide nanomaterials have been suggested to be efficient for highly selective multi‐carbon (C 2+ ) production in CO 2 reduction reaction (CO RR), due the introduction of surface Cu + species from catalysts. However, on catalyst are prone being reduced 0 under reductive conditions during RR. Here, a network‐structured is developed consisting ultrafine O/CuO nanoparticles that harbor an abundance pores. This synthesized via flame spray pyrolysis (FSP) method and engineered confine carbon intermediates, which subsequently cover local stabilize species. As result, C products Faradaic efficiency (FE) approximately 80.0% at partial current density 320.0 mA cm −2 achieved, large 1 ratio ≈9.7. In situ XRD XPS spectra employed reveal indeed presence RR process, extensively improves adsorption * intermediates thus C─C coupling form products.

Language: Английский

Citations

28