Coordination Environment Engineering of Metal Centers in Coordination Polymers for Selective Carbon Dioxide Electroreduction toward Multicarbon Products

ACS Nano, Год журнала: 2024, Номер 18(9), С. 7192 - 7203

Опубликована: Фев. 22, 2024

Electrocatalytic carbon dioxide reduction reaction (CO2RR) toward value-added chemicals/fuels has offered a sustainable strategy to achieve carbon-neutral energy cycle. However, it remains great challenge controllably and precisely regulate the coordination environment of active sites in catalysts for efficient generation targeted products, especially multicarbon (C2+) products. Herein we report engineering metal centers polymers electroreduction CO2 C2+ products under neutral conditions. Significantly, Cu polymer with Cu–N2S2 configuration (Cu–N–S) demonstrates superior Faradaic efficiencies 61.2% 82.2% ethylene respectively, compared selective formic acid on an analogous Cu–I2S2 mode (Cu–I–S). In situ studies reveal balanced formation atop bridge *CO intermediates Cu–N–S, promoting C–C coupling production. Theoretical calculations suggest that can induce electronic modulations sites, where d-band center is upshifted Cu–N–S stronger selectivity Consequently, displays trend while Cu–I–S favors due suppression couplings pathways large barriers.

Язык: Английский

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Product Control in Visible-Light-Driven CO₂ Reduction by Switching Metal Centers of Binuclear Catalysts

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 2522 - 2530

Опубликована: Янв. 27, 2025

Язык: Английский

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Recent advances of metal active sites in photocatalytic CO₂ reduction

Chemical Science, Год журнала: 2024, Номер 15(35), С. 14081 - 14103

Опубликована: Янв. 1, 2024

Photocatalytic CO

Язык: Английский

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Bimetallic effects in the carbon dioxide electroreduction

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

This review systematically summarizes the latest advances in bimetallic effects for reduction of CO 2 to multi-carbon products, discussing structure–activity relationships typical catalysts reaction.

Язык: Английский

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Precise Synthesis of Dual-Atom Catalysts for Better Understanding the Enhanced Catalytic Performance and Synergistic Mechanism

Accounts of Chemical Research, Год журнала: 2025, Номер unknown

Опубликована: Апрель 10, 2025

ConspectusDual-atom catalysts (DACs), featuring two catalytic sites in close proximity, have emerged as a new frontier energy-related catalysis. Compared with single-atom (SACs), DACs more space to optimize the performance by changing dual-atom and their coordination environments. Through adjusting compositions environments of metal DACs, it is possible finely tune electronic geometric properties active centers, then synergistic effects for facilitating substrates activation intermediates stabilization can be strengthened or optimized, consequently tailoring diverse reaction pathways achieving various challenging reactions. The most important yet task studies precise synthesis which crucial understand relationship between structure at atomic level. In cases, were synthesized via pyrolysis mixture salts organic ligands, metals are randomly distributed was difficult control M···M distance (M = ion) uniform dispersion DACs. Hence, developing innovative strategies definite structures high-efficiency urgently needed.In this Account, we tentatively summarize applications conversion small molecules such H2O, CO2, so on. Focusing on three types been put forward systematically introduced. Based strategies, resulting high purity synergistically activating converting concurrently discussed, including cleavage C-C bonds, reduction CO2 Attempts made explain why these functions much higher than what SACs achieved. Efforts revealing influences dual-metal site types, separations dual metals, geometry configurations environments, well ligand performance. Emphasis has placed analysis structure-reactivity mechanism molecular Finally, perspectives current challenges future development forward. We anticipate believe that Account will provide profound insights into structurally defined give

Язык: Английский

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Two‐Dimensional Janus p‐n Heterojunction of Co₃O₄ and CoMoO₄ for Boosting Photocatalytic Oxidative Desulfurization

Chinese Journal of Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 20, 2024

Comprehensive Summary Photocatalytic aerobic oxidative desulfurization (PAODS) is a sustainable alternative technology to traditional, energy‐intensive fuel methods. Nonetheless, its advancement hindered by the notable challenge of inadequate electron‐hole separation efficiency within existing catalytic systems. Herein, Janus 2D/2D heterostructure composed Co 3 O 4 and CoMoO reported for PAODS thiophenic sulfides. Through combination detailed experimental characterizations density functional theory (DFT) calculations, we elucidate formation type II p‐n heterojunction in catalyst, significantly enhancing through electric field force reducing possibility recombination due spatial redox centres. The photocatalyst exhibits exceptional activity demonstrates an impressive performance 10.4 mmol·g –1 ·h oxidation dibenzothiophene (DBT). Moreover, profound capabilities real diesel, reinforcing promising prospects industrial application. These discoveries provide invaluable insights, both scientifically practically, towards development advanced photocatalysts processes.

Язык: Английский

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CO2 Reduction by Transition‐Metal Complex Systems: Effect of Hydrogen Bonding on the Second Coordination Sphere

ChemCatChem, Год журнала: 2024, Номер unknown

Опубликована: Окт. 21, 2024

Abstract Homogeneous electrocatalysts typified by transition‐metal complex show transcendent potency in efficient energy catalysis through molecular design. For example, metal complexes with elaborate design performed wonderful activity and selectivity for electrocatalytic CO 2 reduction. Primary coordination sphere of plays a key role regulating its intrinsic redox properties catalytic activity. However, the overall reduction efficiency is also bound up substrate activation process. Transition‐metal are hoped to exhibit reasonable potential, reactive activity, stability, while binding activating molecules achieve Construction second sphere, especially hydrogen‐bonding network complexes, reported be “kill two birds one stone” strategy realize via systematic catalyst modulation activation. Herein, we present recent progress on construction ligand modification or introduction exogenous organic ligand, resulted productive enhancement performance improvement adsorption capacity , proton transfer rate, stability reaction intermediates, so forth.

Язык: Английский

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Electronic Effect Promoted Visible-Light-Driven CO₂-to-CO Conversion in a Water-Containing System

Inorganic Chemistry, Год журнала: 2023, Номер 62(51), С. 21416 - 21423

Опубликована: Дек. 7, 2023

The design of unsaturated nonprecious metal complexes with high catalytic performance for photochemical CO2 reduction is still an important challenge. In this paper, four coordinatively Co-salen 1-4 were explored in situ using o-phenylenediamine derivatives and 5-methylsalicylaldehyde as precursors the ligands 1-4. It was found that complex 4, bearing a nitro substituent (-NO2) on aromatic ring salen ligand, exhibits highest visible-light-driven CO2-to-CO conversion water-containing system, TONCO CO selectivity values 5300 96%, respectively. DFT calculations experimental results revealed promoted photocatalytic activity 4 ascribed to electron-withdrawing effect group compared 1-3 (with -CH3, -F, -H groups, respectively), resulting lower potential active centers CoII barriers coordination C-O cleavage steps than those catalysts 1-3.

Язык: Английский

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Dynamic covalent bonding for directed construction of molecular cages toward carbon dioxide reduction

Inorganic Chemistry Frontiers, Год журнала: 2024, Номер 11(16), С. 5120 - 5126

Опубликована: Янв. 1, 2024

A strategy for customized synthesis of MOCs by constructing dynamic covalent bonds.

Язык: Английский

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Low-valent molecular cobalt complexes for CO2 reduction

Advances in catalysis, Год журнала: 2024, Номер unknown, С. 181 - 256

Опубликована: Янв. 1, 2024

Язык: Английский

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