Covalent Organic Framework with Donor¹‐Acceptor‐Donor² Motifs Regulating Local Charge of Intercalated Single Cobalt Sites for Photocatalytic CO₂ Reduction to Syngas

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

Published: May 22, 2024

Covalent organic framework (COF) has attracted increasing interest in photocatalytic CO

Language: Английский

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Ionic Liquid‐Induced Product Switching in CO₂ Electroreduction on Copper Reaction Interface

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

Published: May 13, 2024

Abstract The electrochemical reduction of CO 2 (CO RR) mainly occurs at the three‐phase interface, and properties an interface can directly affect RR pathway. Cu‐based materials produce considerable amounts alcohols hydrocarbons, but it is hard to precisely regulate reaction obtain specific target products. Herein, Cu surface through a facile strategy ionic liquid modification are successfully adjusted. According theoretical calculations in situ Raman FTIR spectra characterizations, revealed that introduction liquids (e.g., [Bmim][PF 6 ]) control energy barriers distribution density key intermediates on thus totally change pathway electroreduction. Consequently, dominant products from catalyst will be dramatically switched between C H 4 with 71.1% Faraday efficiency (FE) CH 67.2% FE. It rarely seen previous reports fundamentally changed simple modifications. This work offers straightforward approach tune interfacial understand mechanisms various electrocatalytic reactions.

Language: Английский

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Highly Selective CO2 Electroreduction to C2H4 Using a Dual‐Sites Cu(II) Porphyrin Framework Coupled with Cu2O Nanoparticles via a Synergetic‐Tandem Strategy

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

Published: June 6, 2024

Abstract Low *CO coverage on the active sites is a major hurdle in tandem electrocatalysis, resulting unsatisfied C 2 H 4 production efficiencies. In this work, we developed synergetic‐tandem strategy to construct copper‐based composite catalyst for electroreduction of CO , which was constructed via template‐directed polymerization ultrathin Cu(II) porphyrin organic framework incorporating atomically isolated and bipyridine carbon nanotube (CNT) scaffold, then Cu O nanoparticles were uniformly dispersed CNT scaffold. The presence dual within create synergetic effect, leading an increase local availability enhance C−C coupling step implemented adjacent further production. Accordingly, resultant affords exceptional ‐to‐C Faradaic efficiency (FE C2H4 ) 71.0 % at −1.1 V vs reversible hydrogen electrode (RHE), making it one most effective catalysts reported date. superior performance confirmed through operando infrared spectroscopy theoretic calculations.

Language: Английский

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Promoting CO2 Electroreduction to Hydrocarbon Products via Sulfur‐Enhanced Proton Feeding in Atomically Precise Thiolate‐Protected Cu Clusters

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(48)

Published: Aug. 22, 2024

Abstract Thiolate‐protected Cu clusters with well‐defined structures and stable low‐coordinated + species exhibit remarkable potential for the CO 2 RR are ideal model catalysts establishing structure‐electrocatalytic property relationships at atomic level. However, extant employed in predominantly yield 2e − products. Herein, two 4 (MMI) 8 ( t BuS) (MMI=2‐mercapto‐1‐methylimidazole) prepared to investigate synergistic effect of adjacent S sites on RR. can reduce deep‐reduced products a 91.0 % Faradaic efficiency (including 53.7 CH ) while maintaining stability. Conversely, shows preference C 2+ products, achieving maximum FE 58.5 current density 152.1 mA⋅cm −2 . In situ XAS ex XPS spectra reveal preservation during RR, extensively enhancing adsorption capacity *CO intermediate. Moreover, kinetic analysis theoretical calculations confirm that facilitate H O dissociation into *H species, which directly participate protonation process *CHO. This study highlights important role Cu−S dual provides mechanistic insights pathway

Language: Английский

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Electrochemical CO2 Reduction: Advances, Insights, Challenges, and Future Directions

Materials Today Sustainability, Journal Year: 2025, Volume and Issue: unknown, P. 101089 - 101089

Published: Feb. 1, 2025

Language: Английский

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Single-atom Cu sites on covalent organic frameworks with Kagome lattices for visible-light-driven CO2 reduction to propylene

Applied Catalysis B Environment and Energy, Journal Year: 2024, Volume and Issue: 361, P. 124587 - 124587

Published: Sept. 11, 2024

Language: Английский

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Covalent Organic Framework with Donor¹‐Acceptor‐Donor² Motifs Regulating Local Charge of Intercalated Single Cobalt Sites for Photocatalytic CO₂ Reduction to Syngas

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(31)

Published: May 22, 2024

Abstract Covalent organic framework (COF) has attracted increasing interest in photocatalytic CO 2 reduction, but it remains a challenge to achieve high conversion efficiency owing the insufficient active site and fast charge recombination. Rationally optimizing electronic structures of COF regulate local sites precisely is key point improving catalytic performance. Herein, intercalated single Co coordinated by imine‐N motifs have been designed using trinuclear copper‐based imine‐COFs with distinct moieties via molecular engineering strategy. It confirmed that delivery property distribution these heterometallic frameworks can be profoundly influenced structures. Among featured mixed‐state copper clusters, Co/Cu 3 ‐TPA‐COF stands out for an exceptional reduction activity tunable syngas (CO/H ) ratio changing various bipyridines. Experimental theoretical results indicate interlayer Co‐imine N on donor 1 ‐acceptor‐donor facilitate formation highly separated electron‐hole state, which effectively induces oriented electron transfer from dual donors centers, achieving enhanced activation reduction. This work opens up avenue design high‐performance COF‐based catalysts

Language: Английский

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Advances and Challenges of Carbon‐Free Gas‐Diffusion Electrodes (GDEs) for Electrochemical CO₂ Reduction

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

Published: Oct. 26, 2024

Abstract Electrochemical CO 2 reduction reaction (CO RR) coupled with renewable electricity holds promises for efficient mitigation of carbon emission impacts on the environment and turning into valuable chemicals. One important task in RR development is design fabrication electrodes stable operation long term. Gas‐diffusion (GDEs) have been employed to continuously feed electrolyzers. Despite significant advances GDE tailoring properties, present GDEs often suffer from critical issue flooding due electrowetting carbon‐based substrates, which hinders transition industrial application. To address flooding, intrinsically hydrophobic polymeric substrates recently fabricated shown promising performances. Herein, challenges associated carbon‐free are reviewed RR. This review first briefly outlines electrolyzers basics. Through discussion around shortcomings conventional GDEs, most recent efforts resolve summarized. Subsequently, advances, advantages, elaborated. Finally, priorities future studies suggested, aim support advancement scale‐up extend them other electrochemical systems where gas electrolyte contact.

Language: Английский

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Rational design of organic ligands for metal-organic frameworks as electrocatalysts for CO2 reduction

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(67), P. 8824 - 8839

Published: Jan. 1, 2024

Electrocatalytic carbon dioxide (CO

Language: Английский

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Fabrication of Ultrahigh‐Loading Dual Copper Sites in Nitrogen‐Doped Porous Carbons Boosting Electroreduction of CO₂ to C₂H₄ Under Neutral Conditions

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

Published: Nov. 16, 2024

Abstract Synthesis of high‐loading atomic‐level dispersed catalysts for highly efficient electrochemical CO 2 reduction reaction (eCO RR) to ethylene (C H 4 ) in neutral electrolyte remain challenging tasks. To address common aggregation issues, a host‐guest strategy is employed, by using metal‐azolate framework ( MAF‐4 with nanocages as the host and dinuclear Cu(I) complex guest, form precursors pyrolysis into series nitrogen‐doped porous carbons (NPCs) varying loadings dual copper sites, namely NPC ‐Cu ‐21 (21.2 wt%), ‐11 (10.6 ‐7 (6.9 wt%). Interestingly, loading sites increased from 6.9 21.2 wt%, partial current density eCO RR yield C also gradually 38.7 93.6 mA cm −2 . In 0.1 m KHCO 3 electrolyte, at −1.4 V versus reversible hydrogen electrode vs RHE), exhibits excellent performance Faradaic efficiency 52% 180 Such can be attributed presence ultrahigh‐loading which promotes C─C coupling formation products. The findings demonstrate confinement effect conducive preparation catalysts.

Language: Английский

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