Reticular framework materials for photocatalytic organic reactions

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(22), P. 7949 - 8004

Published: Jan. 1, 2023

Photocatalytic organic reactions, harvesting solar energy to produce high value-added chemicals, have attracted increasing attention as a sustainable approach address the global crisis and environmental issues. Reticular framework materials, including metal-organic frameworks (MOFs) covalent (COFs), are widely considered promising candidates for photocatalysis owing their crystallinity, tailorable pore environment extensive structural diversity. Although design synthesis of MOFs COFs been intensively developed in last 20 years, applications photocatalytic transformations still preliminary stage, making systematic summary necessary. Thus, this review aims provide comprehensive understanding useful guidelines exploration suitable MOF COF photocatalysts towards appropriate reactions. The commonly used reactions categorized facilitate identification reaction types. From practical viewpoint, fundamentals experimental design, active species, performance evaluation external conditions, discussed detail easy experimentation. Furthermore, latest advances COFs, composites, comprehensively summarized according actual sites, together with discussion structure-property relationship. We believe that study will be helpful researchers novel reticular various synthetic applications.

Language: Английский

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Synergistic Effect in a Metal–Organic Framework Boosting the Electrochemical CO₂ Overall Splitting

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(4), P. 2439 - 2447

Published: Jan. 19, 2023

It is a very important but still challenging task to develop bifunctional electrocatalysts for highly efficient CO2 overall splitting. Herein, we report stable metal-organic framework (denoted as PcNi-Co-O), composed of (2,3,9,10,16,17,23,24-octahydroxyphthalocyaninato)nickel(II) (PcNi-(O-)8) ligands and the planar CoO4 nodes, When working both cathode anode catalysts (i.e., PcNi-Co-O||PcNi-Co-O), PcNi-Co-O achieved commercial-scale current density 123 mA cm-2 (much higher than reported values (0.2-12 cm-2)) with Faradic efficiency (CO) 98% at low cell voltage 4.4 V. Mechanism studies suggested synergistic effects between two active sites, namely, (i) electron transfer from PcNi sites under electric fields, resulting in raised oxidizability/reducibility CoO4/PcNi respectively; (ii) energy-level matching can reduce energy barrier them improve performance

Language: Английский

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

ACS Nano, Journal Year: 2024, Volume and Issue: 18(9), P. 7192 - 7203

Published: Feb. 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.

Language: Английский

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CO₂-Based Stable Porous Metal–Organic Frameworks for CO₂ Utilization

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(21), P. 14835 - 14843

Published: May 10, 2024

The transformation of carbon dioxide (CO2) into functional materials has garnered considerable worldwide interest. Metal–organic frameworks (MOFs), as a distinctive class materials, have made great contributions to CO2 capture and conversion. However, facile conversion stable porous MOFs for utilization remains unexplored. Herein, we present methodology using synthesize zirconium-based MOFs. Two CO2–Zr-DEP CO2–Zr-DEDP with face-centered cubic topology were obtained via sequential desilylation–carboxylation–coordination reaction. exhibit excellent crystallinity, verified through powder X-ray diffraction high-resolution transmission electron microscopy analyses. They also notable porosity high surface area (SBET up 3688 m2 g–1) good adsorption capacity (up 12.5 wt %). resulting abundant alkyne moieties, confirmed 13C cross-polarization/magic angle spinning nuclear magnetic resonance Fourier transform infrared spectra. Leveraging the catalytic prowess Ag(I) in diverse CO2-involved reactions, incorporated MOFs, capitalizing on their interactions carbon–carbon π-bonds alkynes, thereby forming heterogeneous catalyst. This catalyst demonstrates outstanding efficiency catalyzing propargylic alcohols cyclic carbonates, achieving >99% yield at room temperature atmospheric pressure conditions. Thus, this work provides dual strategy, encompassing synthesis CO2-based (20–24 % from CO2) subsequent application processes. approach significantly enhances overall utilization.

Language: Английский

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Boosting Electrochemical CO₂ Reduction on Copper‐Based Metal‐Organic Frameworks via Valence and Coordination Environment Modulation

Small, Journal Year: 2024, Volume and Issue: 20(27)

Published: Jan. 29, 2024

Abstract Cu‐based metal‐organic frameworks (MOFs) have attracted much attention for electrocatalytic CO 2 reduction to high value‐added chemicals, but they still suffer from low selectivity and instability. Here, an associative design strategy the valence coordination environment of metal node in MOFs is employed regulate CO2 electroreduction ethylene. A novel “reduction‐cleavage‐recrystallization” method developed modulate Cu(II)‐Trimesic acid (BTC) framework form a Cu(I)‐BTC structure enriched with free carboxyl groups secondary (SCE). In contrast Cu(II)‐BTC, shows higher catalytic activity better ethylene (≈2.2‐fold) electroreduction, which further enhanced by increasing content groups, resulting Faraday efficiency up 57% durability catalyst could last 38 h without performance decline. It indicates that synergistic effect between Cu(I)‐O coordinated considerably enhances dimerization *CO intermediates hinders hydrogenation these competitive pathways. This work unravels strong dependence on Cu state provides platform designing highly selective catalysts.

Language: Английский

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An Overview of Metal‐Organic Framework Based Electrocatalysts: Design and Synthesis for Electrochemical Hydrogen Evolution, Oxygen Evolution, and Carbon Dioxide Reduction Reactions

The Chemical Record, Journal Year: 2023, Volume and Issue: 23(12)

Published: Dec. 1, 2023

Abstract Due to the increasing global energy demands, scarce fossil fuel supplies, and environmental issues, pursued goals of technologies are being sustainable, more efficient, accessible, produce near zero greenhouse gas emissions. Electrochemical water splitting is considered as a highly viable eco‐friendly technology. Further, electrochemical carbon dioxide (CO 2 ) reduction reaction RR) cleaner strategy for CO utilization conversion stable (fuels). One critical issues in these development efficient economical electrocatalyst. Among various materials, metal‐organic frameworks (MOFs) becoming increasingly popular because their structural tunability, such pre‐ post‐ synthetic modifications, flexibility ligand design its functional groups, incorporation different metal nodes, that allows suitable MOFs with desired quality required each process. In this review, MOF was discussed specific process together methods effects on properties. The electrocatalysts were highlighted performances from aspects hydrogen evolution (HER), oxygen (OER), RR. Finally, challenges opportunities field discussed.

Language: Английский

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Simultaneous Defect and Size Control of Metal–Organic Framework Nanostructures for Highly Efficient Carbon Dioxide Electroreduction to Multicarbon Products

ACS Materials Letters, Journal Year: 2023, Volume and Issue: 5(8), P. 2121 - 2130

Published: July 11, 2023

Electrocatalytic carbon dioxide (CO2) reduction reaction (CO2RR) has offered a sustainable approach in converting an anthropogenic CO2 source to chemicals and fuels promote neutral. However, it remains challenging prepare high-performance catalysts for efficient selective electroreduction, especially toward the high-vaule multicarbon products. Here we report facile synthesis of four kinds nearly monodispersed CuTrz (HTrz = 1H,1,2,4-triazole) metal–organic framework (MOF) nanostructures with different sizes by controlling kinetics. Significantly, small demonstrate much superior CO2RR performance over large counterparts production neutral electrolytes, optimized Faradaic efficiency 55.4% 81.8% ethylene products, respectively. Detailed structural characterizations reveal that are polycrystalline rich grain boundaries, while ones single crystalline. This work highlights importance simultaneous defect size control MOFs boosting their production.

Language: Английский

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Isolated Tin(IV) Active Sites for Highly Efficient Electroreduction of CO₂ to CH₄ in Neutral Aqueous Solution

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(22)

Published: Feb. 24, 2023

The development of efficient electrocatalysts with non-copper metal sites for electrochemical CO2 reduction reactions (eCO2 RR) to hydrocarbons and oxygenates is highly desirable, but still a great challenge. Herein, stable metal-organic framework (DMA)4 [Sn2 (THO)2 ] (Sn-THO, THO6- = triphenylene-2,3,6,7,10,11-hexakis(olate), DMA dimethylammonium) isolated distorted octahedral SnO62- active reported as an electrocatalyst eCO2 RR, showing exceptional performance RR the CH4 product rather than common products formate CO Sn-based catalysts. partial current density reaches high value 34.5 mA cm-2 , surpassing most copper-based all non-Cu metal-based Our experimental theoretical results revealed that site favors formation key *OCOH species produce can greatly inhibit *OCHO *COOH *HCOOH *CO, respectively.

Language: Английский

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Recent strategies to improve the electroactivity of metal–organic frameworks for advanced electrocatalysis

Deleted Journal, Journal Year: 2024, Volume and Issue: 1(2), P. 181 - 206

Published: Aug. 4, 2024

Abstract Metal–organic frameworks (MOFs) have emerged as promising materials in the realm of electrocatalysis due to their high surface area, tunable porosity, and versatile chemical functionality. However, practical application has been hampered by inherent limitations such low electrical conductivity a limited number active metal sites. Researchers addressed these challenges through various strategies, including enhancing incorporating conductive nanoparticles, modifying structure composition MOFs replacing nodes functionalizing linkers, preparing catalysts thermal processes decarburization conversion into oxides, phosphides (MPs), sulfides (MSs). This review provided comprehensive summary strategies that were employed enhance electroactivity for improved electrocatalytic performance recent years. It also explored future directions potential innovations design synthesis MOF‐based electrocatalysts, offering valuable insights advancing sustainable energy technologies.

Language: Английский

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Restructuring multi-phase interfaces from Cu-based metal–organic frameworks for selective electroreduction of CO₂ to C₂H₄

Chemical Science, Journal Year: 2024, Volume and Issue: 15(24), P. 9173 - 9182

Published: Jan. 1, 2024

Directional in situ reconfiguration of Ag incorporating HKUST-1 frameworks was introduced to restructure multi-phase Ag/Cu/Cu 2 O electrocatalysts for the selective electro-reduction CO C H 4 .

Language: Английский

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