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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Anion Modulation of Ag‐Imidazole Cuboctahedral Cage Microenvironments for Efficient Electrocatalytic CO2 Reduction

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

Published: May 20, 2024

Abstract How to achieve CO 2 electroreduction in high efficiency is a current challenge with the mechanism not well understood yet. The metal‐organic cages multiple metal sites, tunable active centers, and well‐defined microenvironments may provide promising catalyst model. Here, we report self‐assembly of Ag 4 L type cuboctahedral from coordination dynamic + ion triangular imidazolyl ligand 1,3,5‐tris(1‐benzylbenzimidazol‐2‐yl) benzene (Ag‐MOC‐X, X=NO 3 , ClO BF ) via anion template effect. Notably, Ag‐MOC‐NO achieves highest faradaic pH‐universal electrolytes 86.1 % (acidic), 94.1 (neutral) 95.3 (alkaline), much higher than those Ag‐MOC‐ClO Ag‐MOC‐BF just different counter anions. In situ attenuated total reflection Fourier transform infrared spectroscopy observes formation vital intermediate *COOH for ‐to‐CO conversion. density functional theory calculations suggest that adsorption on unsaturated Ag‐site stabilized by C−H⋅⋅⋅O hydrogen‐bonding microenvironment surrounded three benzimidazole rings, activation dependent dynamics Ag‐centers modulated hosted anions through Ag⋅⋅⋅X interactions. This work offers supramolecular electrocatalytic strategy based Ag‐coordination geometry host–guest interaction regulation MOCs as high‐efficient electrocatalysts reduction which key chemical industry process.

Language: Английский

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Atomic Design of Copper Active Sites in Pristine Metal–Organic Coordination Compounds for Electrocatalytic Carbon Dioxide Reduction

Small Methods, Journal Year: 2024, Volume and Issue: 8(11)

Published: May 20, 2024

Abstract Electrocatalytic carbon dioxide reduction reaction (CO 2 RR) has emerged as a promising and sustainable approach to cut emissions by converting greenhouse gas CO value‐added chemicals fuels. Metal–organic coordination compounds, especially the copper (Cu)‐based which feature well‐defined crystalline structures designable metal active sites, have attracted much research attention in electrocatalytic RR. Herein, recent advances of electrochemical RR on pristine Cu‐based compounds with different types Cu sites are reviewed. First, general pathways briefly introduced. Then highly efficient conversion various kinds (e.g., single‐Cu site, dimeric‐Cu multi‐Cu heterometallic site) is systematically discussed, along corresponding catalytic mechanisms. Finally, some existing challenges potential opportunities for this direction provided guide rational design metal–organic their practical application

Language: Английский

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Metal–organic frameworks and their derivatives for the electrochemical CO₂ reduction reaction: insights from molecular engineering

Journal of Materials Chemistry A, Journal Year: 2024, Volume and Issue: 12(32), P. 20578 - 20605

Published: Jan. 1, 2024

Molecular engineering of MOF-based electrocatalysts for the CO 2 RR, computational simulations, and advanced characterization studies are discussed summarized to illustrate correlation between their structure performance.

Language: Английский

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Enhanced CO₂ Adsorption and Conversion in Diethanolamine‐Cu Interfaces Achieving Stable Neutral Ethylene Electrosynthesis

Advanced Energy Materials, Journal Year: 2024, Volume and Issue: 14(43)

Published: Aug. 7, 2024

Abstract Molecular modifications have shown tremendous potential in boosting the electrochemical CO 2 reduction (CO RR) to ethylene. However, key mechanisms of modulation at molecular level remain unclear, especially for adsorption and activation intermediates (e.g., * CO). Here, report that a diethanolamine (DEA)‐modified Cu catalyst can reduce ethylene with faradaic efficiency ≈50.5% partial current density ≈155.7 mA cm −2 neutral conditions, which surpasses without modification (≈28.5% ≈95.6 ). Density functional theory calculations demonstrate DEA on surface boosts following C–C coupling processes during RR‐to‐ethylene process. dynamics simulations suggest molecules distant from site enrichment effect. Operational stability achieved via introduction onto ketjen black, then successively immobilized nanoparticles polytetrafluoroethylene electrodes obtain stable tripe‐phase boundary, realizing constant selectivity 100 operating hours flow cell.

Language: Английский

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Experimental and Theoretical Study of Two 3D Difunctional Electrocatalytic Hybrid Vanadate-Containing Metal–Organic Motifs

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 29, 2025

Two novel 3D inorganic-organic hybrids based on [V6O18]6-/[V3O9]3- clusters, [Cu18(bbpy)18(V6O18)6]·3H2O (1) and [Cu4Ag4(pty)4(V3O9)4]·H2O (2) (bbpy = 3,5-bis(1-benzimidazole) pyridine, pty 4'-(4″-pyridyl)-2,2':6',2″-terpyridine), were isolated in the same POV/Cu/N-heterocycle ligand reaction systems. Hybrids 1 2 possess three-dimensional bimetallic frameworks derived from clusters Cu-organic complexes. In 1, bbpy ligands are grafted by Cu2+ to a grid ribbon 2D sheet, which connected with benzene-like [V6O18]6- yield framework. 2, helical {O-V-O-V-}n chains bridged Cu(II) ions into layer including eight-membered rings {V6Cu2} six-membered {V4Cu2}, adjoining sheets joined Ag-N coordination bonds form framework structure. Moreover, hybrid has superior electrocatalytic properties for nitrite reduction oxidation of ascorbic acid efficiencies 397.2 96%, respectively. Hybrid displays coordinated performance toward through V Cu centers. Meanwhile, corresponding theoretical studies conducted evaluate active sites charge distribution.

Language: Английский

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MOF Nanosheet Enable Accelerated Redox Kinetics and Ultralow Overpotential for Light‐Assisted Li‐CO₂ Battery

Small, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 31, 2025

Lithium-carbon dioxide (Li-CO₂) batteries have attracted much attention due to their high energy density, low cost, and carbon sequestration. However, the sluggish conversion kinetics between CO₂ discharge product lithium carbonate (Li₂CO₃) hindered practical applications. Herein, a flower-like photosensitive metal-organic framework (FJU-115-NS) has been employed as cathodic electrocatalyst for Li-CO₂ batteries. The FJU-115-NS with well-ordered micropores abundant exposed catalytic sites can effectively facilitate ion transport catalyze Li₂CO₃ formation/decomposition, leading improved battery performance. At current density of 200 mA g⁻¹, exhibits substantial capacity 31579.34 h overpotential 1.31 V, stable operation over 3200 h. Importantly, under light irradiation, charging voltage significantly dropped from 4.45 V (without light) 3.43 at 2 A g⁻¹. Additionally, cell demonstrated an exceptionally just 0.45 highlighting its enhanced efficiency light-assisted conditions. This work provides valuable guidance developing MOF catalysts upgrade longevity

Language: Английский

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Boosting selective CO2 reduction via strong spin-spin coupling on dual-atom spin-catalysts

Journal of Colloid and Interface Science, Journal Year: 2025, Volume and Issue: 688, P. 548 - 561

Published: Feb. 25, 2025

Language: Английский

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Progress in Cu‐Based Catalyst Design for Sustained Electrocatalytic CO₂ to C₂₊ Conversion

Advanced Science, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 27, 2025

Abstract The electrocatalytic conversion of CO 2 into valuable multi‐carbon (C 2+ ) products using Cu‐based catalysts has attracted significant attention. This review provides a comprehensive overview recent advances in catalyst design to improve C selectivity and operational stability. It begins with an analysis the fundamental reaction pathways for formation, encompassing both established emerging mechanisms, which offer critical insights design. In situ techniques, essential validating these by real‐time observation intermediates material evolution, are also introduced. A key focus this is placed on how enhance through manipulation, particularly emphasizing catalytic site construction promote C─C coupling via increasing * coverage optimizing protonation. Additionally, challenge maintaining activity under conditions discussed, highlighting reduction active charged Cu species materials reconstruction as major obstacles. To address these, describes strategies preserve sites control including novel utilization mitigation reconstruction. By presenting developments challenges ahead, aims guide future conversion.

Language: Английский

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Target High‐Efficient Ethylene Production from Dilute CO₂ Enabled by Sustainable Contact Electrons

Small, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 28, 2025

Abstract The electrochemical CO 2 reduction reaction (CO RR) exhibits significant potential to efficiently convert into ethylene (C H 4 ). However, achieving high C selectivity remains a considerable challenge due the difficulty in effective C─C coupling and stringent requirements on purity. Herein, novel contact‐electro‐catalysis method for RR is presented by constructing dual‐active‐site catalysts electronegative tribolayer of triboelectric nanogenerator (TENG), including single copper atom anchored polymeric carbon nitride (Cu─PCN) CuO nanoparticle, an outstanding Faradaic efficiency 63.5% dilute . Experimental theoretical studies indicate that Cu─PCN active sites exhibit ability heighten * adsorption facilitate its migration nanoparticles. This process effectively modulates coverage promotes transformation CHO. Subsequently, CHO undergoes dimerization surface, ultimately yielding Furthermore, electric field generated TENG enhances both surfaces, which subsequently reduces energy barrier coupling. work provides new route enhance selective integrating contact electrocatalysis with dual site technologies.

Language: Английский

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