Enhancing C-C Coupling in CO2 Electroreduction by Engineering Pore Size of Porous Carbon-Supported Cu Catalysts

Catalysts, Journal Year: 2025, Volume and Issue: 15(3), P. 199 - 199

Published: Feb. 20, 2025

The electroreduction of CO2 (CO2RR) is a promising and environmentally sustainable approach to closing the carbon cycle. However, achieving high activity selectivity for multicarbon (C2₊) products remains significant challenge due complexity reaction pathways. In this study, porous carbon-supported copper catalysts (CuHCS) with pore sizes 120 nm (CuHCS120) 500 (CuHCS500) were synthesized tailor microenvironment at electrode–electrolyte interface enhance product selectivity. CuHCS120 achieved maximum faradaic efficiency (FE) C2₊ 46%, double that CuHCS500 (23%). contrast, showed higher FE CO (36%) compared (14%) same potential. In-depth ex situ in investigations revealed smaller pores promote enrichment adsorption *CO intermediates, thereby enhancing C–C coupling formation products. These findings underscore critical role structural confinement modulating catalytic provide valuable insights rational design advanced CO2RR.

Language: Английский

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Electronic metal-support interaction modulates Cu electronic structures for CO2 electroreduction to desired products

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Feb. 25, 2025

In this work, the Cu single-atom catalysts (SACs) supported by metal-oxides (Al2O3-CuSAC, CeO2-CuSAC, and TiO2-CuSAC) are used as theoretical models to explore correlations between electronic structures CO2RR performances. For these catalysts, metal-support interaction (EMSI) induced charge transfer sites supports subtly modulates structure form different highest occupied-orbital. The occupied 3dyz orbital of Al2O3-CuSAC enhances adsorption strength CO weakens C-O bonds through 3dyz-π* electron back-donation. This reduces energy barrier for C-C coupling, thereby promoting multicarbon formation on Al2O3-CuSAC. 3dz2 TiO2-CuSAC accelerates H2O activation, lowers reaction forming CH4. over activated H2O, in turn, intensifies competing hydrogen evolution (HER), which hinders high-selectivity production CH4 TiO2-CuSAC. CeO2-CuSAC with 3dx2-y2 promotes CO2 activation its localized state inhibits coupling. moderate water activity facilitates *CO deep hydrogenation without excessively activating HER. Hence, exhibits Faradaic efficiency 70.3% at 400 mA cm−2. Rational regulation control electroreduction pathways is challenging. Here, authors report modulating single-sites via interaction, enabling switchable selectivity multicarbons methane.

Language: Английский

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Advances in Cu nanocluster catalyst design: recent progress and promising applications

Nanoscale Horizons, Journal Year: 2023, Volume and Issue: 8(11), P. 1509 - 1522

Published: Jan. 1, 2023

We present an in-depth study of Cu NC catalysts, encompassing design strategies, atomic-level tuning, and diverse catalytic applications.

Language: Английский

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Novel Cu nanocluster superlattice/MBene-induced ECL enhancement strategy for miRNA-221 detection

Chemical Engineering Journal, Journal Year: 2023, Volume and Issue: 478, P. 147512 - 147512

Published: Nov. 19, 2023

Language: Английский

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Heterostructure construction of covalent organic frameworks/Ti₃C₂-MXene for high-efficiency electrocatalytic CO₂ reduction

Green Chemistry, Journal Year: 2023, Volume and Issue: 26(3), P. 1454 - 1461

Published: Dec. 21, 2023

The in situ fabrication of imine-bonded porphyrin COFs and an MXene heterostructure can accelerate the electron transfer at interfaces, exhibiting superior electrocatalytic CO 2 reduction selectivity with 97.28% TOF value (CO -to-CO) a bias −0.6 V vs. RHE.

Language: Английский

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Advancements in Atomically Precise Nanocluster Protected by Thiacalix[4]arene

Advanced Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 3, 2024

Abstract Coinage metal nanoclusters (NCs), comprising a few to several hundred atoms, are prized for their size‐dependent properties crucial in catalysis, sensing, and biomedicine. However, practical application is often hindered by stability reactivity challenges. Thiacalixarene, macrocyclic ligand, shows promise stabilizing silver, copper, bimetallic NCs, enhancing structural integrity chemical stability. This investigation delves into the unique of thiacalix[4]arene role bolstering NC stability, catalytic efficiency, sensing capabilities. The current challenges future prospects critically evaluated, underscoring transformative impact nanoscience. review aims broaden utilization atomically precise coinage unlocking new avenues across scientific industrial applications.

Language: Английский

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Capture-Intensified Electrocatalytic Reduction of Postcombustion CO₂ in Transporting and Catalytic Channels of Covalent Organic Frameworks

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(14), P. 11076 - 11086

Published: July 9, 2024

Language: Английский

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Experimental and Theoretical Insights into Single Atoms, Dual Atoms, and Sub‐Nanocluster Catalysts for Electrochemical CO₂ Reduction (CO₂RR) to High‐Value Products

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(52)

Published: Nov. 26, 2024

Abstract Electrocatalytic carbon dioxide (CO 2 ) conversion into valuable chemicals paves the way for realization of recycling. Downsizing catalysts to single‐atom (SACs), dual‐atom (DACs), and sub‐nanocluster (SNCCs) has generated highly active selective CO transformation reduced products. This is due introduction numerous sites, unsaturated coordination environments, efficient atom utilization, confinement effect compared their nanoparticle counterparts. Herein, recent Cu‐based SACs are first reviewed newly emerged DACs SNCCs expanding catalysis electrocatalytic reduction RR) high‐value products discussed. Tandem SAC–nanocatalysts (NCs) (SAC–NCs) also discussed RR Then, non‐Cu‐based SACs, DACs, SAC–NCs, theoretical calculations various transition‐metal summarized. Compared previous achievements less‐reduced products, this review focuses on double objective achieving full increasing selectivity formation rate toward C–C coupled with additional emphasis stability catalysts. Finally, through combined experimental research, future outlooks offered further develop over isolated atoms sub‐nanometal clusters.

Language: Английский

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Total Structure, Structural Transformation and Catalytic Hydrogenation of [Cu₄₁(SC₆H₃F₂)₁₅Cl₃(P(PhF)₃)₆(H)₂₅]²⁻ Constructed from Twisted Cu₁₃ Units

Advanced Science, Journal Year: 2023, Volume and Issue: 11(7)

Published: Dec. 8, 2023

Abstract Herein, a remarkable achievement in the synthesis and characterization of an atomically precise copper‐hydride nanocluster, [Cu 41 (SC 6 H 3 F 2 ) 15 Cl (P(PhF) (H) 25 ] 2− via mild one‐pot reaction is presented. Through X‐ray crystallography analysis, it revealed that exhibits unique shell–core–shell structure. The inner Cu 29 kernel composed three twisted 13 units, connected through 4 face sharing. Surrounding metal core, two shells, resembling protective sandwich structure are observed. This arrangement, along with intracluster π ··· interactions intercluster C─H···F─C interactions, contributes to enhanced stability . presence, number, location hydrides within nanocluster established combination experimental density functional theory investigations. Notably, addition phosphine ligand triggers fascinating nanocluster‐to‐nanocluster transformation , resulting generation nanoclusters, 14 (PPh 8 10 + 7 0 Furthermore, demonstrated catalytic activity hydrogenation nitroarenes. intriguing provides opportunity explore assembly M similar other coinage investigate thiol co‐protected copper nanoclusters.

Language: Английский

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Ligand-controlled exposure of active sites on the Pd₁Ag₁₄ nanocluster surface to boost electrocatalytic CO₂ reduction

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(23), P. 3162 - 3165

Published: Jan. 1, 2024

Advancing catalyst design requires meticulous control of nanocatalyst selectivity at the atomic level. Here, we synthesized two Pd

Language: Английский

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