Atomically Dispersed Cu Active Centers: Local Structure and Mechanism Modulation for Carbon Dioxide Reduction

Advanced Functional Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 10, 2025

Abstract Reducing carbon dioxide （CO 2 ）to high‐value products using green renewable energy is a promising approach for addressing and greenhouse effect issues. Consequently, electrocatalytic CO reduction reaction (CO RR) technology has become current research hotspot. Since the discovery of high activity selectivity copper in RR, atomically dispersed Cu catalysts have garnered widespread attention due to their efficient atom utilization, unique electronic structure, outstanding catalytic performance. However, great challenge remains providing rational catalyst design principles achieve regulation product distribution. A clear understanding materials an in‐depth interpretation mechanism as well elucidation strategy progress toward different are keys building solving above problem. Therefore, this review starts with introduction advanced characterization techniques reveal structure mechanisms. Then, various optimization strategies applications producing targeted summarized discussed. Finally, perspectives on RR field future development offered.

Language: Английский

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Coupling Photocatalytic Reduction and Biosynthesis Towards Sustainable CO₂ Upcycling

Angewandte Chemie International Edition, Journal Year: 2025, Volume and Issue: unknown

Published: March 11, 2025

Abstract Upcycling carbon dioxide (CO 2 ) into long‐chain compounds has attracted considerable attention with respect to mitigating environmental problems and obtaining value‐added feedstocks, but remains a great challenge. Herein, we report tandem photocatalysis‐biosynthesis strategy for efficient CO reduction energy‐rich sucrose or α‐farnesene. Firstly, photocatalytic of CH 4 was optimized over the transitional metal doped ZnO (M−ZnO). The as‐prepared Ni−ZnO preferentially reduces production rate 1539.1 μmol g −1 h selectivity 90 %, owing unique interface structure (Zn δ + −O−Ni β ). Subsequently, Methylomicrobium buryatense 5GB1C genetically engineered produce α‐farnesene using photocatalytically‐obtained as sole source, titer 96.3 43.9 mg L , respectively. This study provides green, low‐energy pathway synthesis from which sheds new light on tackling long‐term energy demands sustainable upcycling.

Language: Английский

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Recent Advances and Developments in Solar-driven photothermal catalytic CO2 reduction into C2+ products

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

Published: Jan. 1, 2025

Solar-driven catalytic conversion of carbon dioxide (CO2) into value-added C2+ chemicals and fuels has attracted significant attention over the past decades, propelled by urgent environmental energy demands. However, reduction CO2 continues to face challenges due inherently slow kinetics. This review traces historical development current state photothermal reduction, detailing mechanisms which is transformed products. A key focus on catalyst design, emphasizing surface defect engineering, bifunctional active site co-catalyst coupling enhance efficiency selectivity solar-driven synthesis. Key reaction pathways both C1 products are discussed, ranging from CO, CH4 methanol (CH3OH) synthesis production C2-4 such as hydrocarbons, ethanol, acetic acid, various carbonates. Notably, advanced C5+ hydrocarbons exemplifies remarkable potential technologies effectively upgrade CO2-derived products, thereby delivering sustainable liquid fuels. provides a comprehensive overview fundamental mechanisms, recent breakthroughs, pathway optimizations, culminating in valuable insights for future research industrial-scale prospect reduction.

Language: Английский

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Constructing an Active Sulfur‐Vacancy‐Rich Surface for Selective *CH₃‐CH₃ Coupling in CO₂‐to‐C₂H₆ Conversion With 92% Selectivity

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

Published: Nov. 6, 2024

Abstract To achieve high selectivity in photocatalytic CO 2 reduction to C 2+ products, increasing the number of adsorption sites and lowering energy barriers for key intermediates are critical. A ZnIn S 4 (ZIS)/MoO 3‐x (Z‐M) photocatalyst is presented, which plasmonic MoO generates hot electrons, creating a multielectron environment ZIS that facilitates efficient C─C coupling reactions. Density functional theory (DFT) calculations reveal reduces formation sulfur vacancies (S V ) ZIS, thereby enhancing activation. The ‐rich surface lowers barrier forming HCOO * −0.33 eV whereas COOH 0.77 eV. Successive hydrogenation leads CH , converts 3 with an −0.63 ‐CH 0.54 eV, lower than 0.73 form H . Thus, Z‐M preferentially produces 6 over Under visible light, achieves ‐to‐C conversion rate 467.3 µmol g −1 h 92.0% selectivity. This work highlights dual role photocatalysts improving production reduction.

Language: Английский

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Amides Enable Room-Temperature CO₂ Conversion: Simple Organic Molecules Challenging Metal Catalysts

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 5, 2025

The conversion of carbon dioxide (CO2) into valuable chemicals has been intensively pursued for sustainable chemistry. It is highly desirable to achieve the under ambient conditions using organocatalysts instead precious or pollutive metal catalysts. Herein, we disclose a new class direct C(sp)-H carboxylation with CO2. Amide molecules such as N-methylacetamide and valerolactam behave efficient bifunctional catalysts promote aromatic alkynes propiolic acids. In particular, simple organic enable reaction occur at room temperature, which achieved only complex transition prior this report. presence optimal base Cs2CO3, adjacent nitrogen oxygen sites amide group concurrently activate CO2 position them in favor C-C coupling, affording high catalytic activity on par those work sheds light chemistry also illustrates great potential discovering from molecules.

Language: Английский

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Fundamentals and Perspectives of Positively Charged Single-Metal Site Catalysts for CO₂ Electroreduction

ACS Applied Materials & Interfaces, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 8, 2025

Single-atom catalysts (SACs) show superior efficiency in electrocatalytic carbon dioxide reduction, a key stage achieving neutrality. Atomically dispersed single-metal sites of SACs are invariably positive valence state; namely, they positively charged (PCSSs). The PCSS generally possess distinctive and asymmetric electronic structure, which enables the activation linear molecules stabilizes miscellaneous intermediates during electrocatalysis. Herein, this review summarizes manner coordination environment, neighboring atoms or groups, interaction with substrate modulate properties PCSSs. Additionally, we overview recently reported theoretical experimental advances terms structure–performance relationship. Furthermore, emphasize previously underappreciated durability CO2 reduction. Finally, discuss several pending issues potential breakthroughs PCSSs for

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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Coupling Photocatalytic Reduction and Biosynthesis Towards Sustainable CO₂ Upcycling

Angewandte Chemie, Journal Year: 2025, Volume and Issue: unknown

Published: March 11, 2025

Abstract Upcycling carbon dioxide (CO 2 ) into long‐chain compounds has attracted considerable attention with respect to mitigating environmental problems and obtaining value‐added feedstocks, but remains a great challenge. Herein, we report tandem photocatalysis‐biosynthesis strategy for efficient CO reduction energy‐rich sucrose or α‐farnesene. Firstly, photocatalytic of CH 4 was optimized over the transitional metal doped ZnO (M−ZnO). The as‐prepared Ni−ZnO preferentially reduces production rate 1539.1 μmol g −1 h selectivity 90 %, owing unique interface structure (Zn δ + −O−Ni β ). Subsequently, Methylomicrobium buryatense 5GB1C genetically engineered produce α‐farnesene using photocatalytically‐obtained as sole source, titer 96.3 43.9 mg L , respectively. This study provides green, low‐energy pathway synthesis from which sheds new light on tackling long‐term energy demands sustainable upcycling.

Language: Английский

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Selective Photoconversion of CO₂ to C₂H₄ on Asymmetrical CeO₂─Cu₂O Interfaces Driven by Oxygen Vacancies

Advanced Functional Materials, Journal Year: 2025, Volume and Issue: unknown

Published: March 25, 2025

Abstract Photocatalytic conversion of CO 2 into valuable C H 4 is desirable for achieving a carbon‐neutral future, yet faces sluggish kinetics C─C dimerization and insufficient electron deliverability. Herein, an effective top‐down etching route presented to construct interfacial asymmetric oxygen vacancies (Ov) in CeO ─Cu O supported on the copper foam (CeO O/CF). In situ characterizations theoretical calculations demonstrate that nanointerface‐based heterojunctions serve as rapid electron‐transfer pathways, promoting efficiency without need sacrificial agents. Moreover, sites (Ce‐Ov‐Cu) with different charge distributions can effectuate coupling reaction through stabilization key * COCO intermediates, thus making reduction become more favorable process. Accordingly, optimized O/CF demonstrates remarkable performance 93% selectivity toward generation impressive production rate 26.1 µmol g −1 h . Such strongly coupled heterogeneous catalysts finely tailored structure interaction, containing polarized metal at interface, will provide some inspiration constructing efficient photocatalysts convert high value‐added multi‐carbon products solar energy.

Language: Английский

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In Situ Transformation of Hybrid Bismuth Halide into Rhombohedral Bismuth for Electrochemical CO2 Reduction to Formate

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(23)

Published: Aug. 22, 2024

Abstract Bi‐based electrocatalysts have attracted high attention due to their selectivity for formate, low cost, and biocompatibility. Surface modification with halides can adjust the surface charge distribution of metal catalysts, thereby regulating binding force intermediate. Organic‐inorganic hybrid bismuth provide an alternative, especially dimensional structures. Herein, zero‐dimensional containing Bi 4 I 16 units (denoted as ) was recommended pre‐catalyst ⋅ spacing in is 4.760 Å, nearly equaling rhombohedral (4.750 Å). The equal may be more beneficial electricity‐driven situ conversion rearrangement atoms catalytic process. As a contrast, halide 2 9 shorter (4.2415 Å) prepared. working electrode prepared by ink measured CO RR, partial formate current density reach 8.2 mA cm −2 at −1.1 V vs RHE. catalyst delivers maximum Faradaic Efficiency (FE, ~80 %) −0.86 RHE maintain FE higher than 78.5 % after h.

Language: Английский

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