Application of MOFs and COFs for photocatalysis in CO2 reduction, H2 generation, and environmental treatment

EnergyChem, Год журнала: 2022, Номер 4(4), С. 100078 - 100078

Опубликована: Июнь 25, 2022

Язык: Английский

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Metal–Organic Frameworks for Photocatalytic Water Splitting

Solar RRL, Год журнала: 2021, Номер 5(7)

Опубликована: Май 20, 2021

Various photocatalysts have been developed for photocatalytic water splitting—one of the most important processes that produces dihydrogen as clean energy fuel cells. The successful achievements this application are based mainly on transition metal oxides and some sulfides/nitrides. Recently, metal–organic frameworks (MOFs), a class hybrid functional materials comprising organic backbone tethered infinitively in limitless way by metal‐oxide clusters, both which can be customized accurately at molecular level targeted applications, able to photocatalytically degrade water. Herein, it is first aimed comprehensively review fundamentals splitting catalyzed semiconductor photocatalysts, casts light understanding challenges area, thus providing strategies development, if not rational design, visible‐light‐driven MOFs capable degrading hydrogen oxygen. recent advancements using MOF further described benchmark limitations considered so readers imagine big picture field pay considerable attention future solutions.

Язык: Английский

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Understanding the unique S-scheme charge migration in triazine/heptazine crystalline carbon nitride homojunction

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Июль 3, 2023

Understanding charge transfer dynamics and carrier separation pathway is challenging due to the lack of appropriate characterization strategies. In this work, a crystalline triazine/heptazine carbon nitride homojunction selected as model system demonstrate interfacial electron-transfer mechanism. Surface bimetallic cocatalysts are used sensitive probes during in situ photoemission for tracing S-scheme photogenerated electrons from triazine phase heptazine phase. Variation sample surface potential under light on/off confirms dynamic transfer. Further theoretical calculations an interesting reversal path light/dark conditions, which also supports experimental evidence transport. Benefiting unique merit electron transfer, shows significantly enhanced activity CO2 photoreduction. Our work thus provides strategy probe mechanisms design delicate material structures towards efficient

Язык: Английский

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Dislocated Bilayer MOF Enables High‐Selectivity Photocatalytic Reduction of CO₂ to CO

Advanced Materials, Год журнала: 2023, Номер 35(10)

Опубликована: Янв. 2, 2023

The highly selective photoreduction of CO2 into valuable small-molecule chemical feedstocks such as CO is an effective strategy for addressing the energy crisis and environmental problems. However, it remains a challenge because complex process usually generates multiple possible products requires subsequent separation step. In this paper, 2D monolayer bilayer porphyrin-based metal-organic frameworks (MOFs) are successfully constructed by adjusting reaction temperature solvent polarity with 5,10,15,20-tetrakis(4-pyridyl)porphyrin light-harvesting ligand. MOF low-dimensional special structure in which upper lower layers arranged dislocation bridged halogen ions. This exhibits 100% ultra-high selectivity reduction to under simulated sunlight without any cocatalyst or photosensitizer can be recycled at least three times. intrinsic mechanism photocatalytic explored through experimental characterization density functional theory (DFT) calculations. work shows that rational design number structures tune stability these opens new avenue photocatalysts.

Язык: Английский

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Metal–Organic Frameworks for Photo/Electrocatalysis

Advanced Energy and Sustainability Research, Год журнала: 2021, Номер 2(8)

Опубликована: Март 14, 2021

Metal–organic frameworks (MOFs), constructed from metal clusters/ions and organic ligands, are ideal materials for photo/electrocatalysis, mainly due to the advantages of large surface areas, high porosity, easily tunable optical electronic structures. Herein, recent important advances on MOF‐based photo/electrocatalysts including pristine MOFs, MOF composites, derivatives summarized. The novel strategies improve photo/electrocatalytic performances highlighted. Finally, current challenges future development MOFs photo/electrocatalysis discussed ad outlined.

Язык: Английский

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Photoelectron Transfer Mediated by the Interfacial Electron Effects for Boosting Visible-Light-Driven CO₂ Reduction

ACS Catalysis, Год журнала: 2022, Номер 12(6), С. 3550 - 3557

Опубликована: Март 4, 2022

Imine-linked covalent organic frameworks (COFs) are popular candidates for photocatalytic CO2 reduction, but high polarization of the imine bond is less efficient π-electron delocalization between linked building units, leading to low intramolecular electron transfer and poor efficiency. Herein, we present a structural electronic engineering strategy through integrating imine-linked COF consisting Zn–porphyrin Co–bipyridyl units with cadmium sulfide (CdS) nanowires form CdS@COF core–shell structure. The experimental theoretical results have validated that CdS serves as channel interfacial effects, which induces photoelectron from subsequent injection into reduction. as-prepared generates 4057 μmol g–1 CO in 8 h under visible-light irradiation, considerably higher than those its neat counterparts. This work provides protocols tackle charge across polar linkages photosensitizers active sites solar-to-chemical energy conversion.

Язык: Английский

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Covalent Organic Frameworks as Emerging Platforms for CO₂ Photoreduction

ACS Catalysis, Год журнала: 2021, Номер 11(15), С. 9809 - 9824

Опубликована: Июль 20, 2021

Covalent organic frameworks (COFs) are an emerging class of porous crystalline materials consisting purely linking units stitched by strong covalent bonds to form extended with various networks and pore structures. Because the highly stacking layers, COFs adopt semiconductive properties exhibit promising catalytic performance in CO2 photoreduction. In this Perspective, we would like cast some light on photoreduction catalyzed COFs—emerging advanced photocatalytic platforms. Especially, direct our discussion linkages COFs, principles structural designs, viewpoints most recent advancements using (mainly two-dimensional structures) for This manuscript, therefore, acts as informative reference designing but not limited any kinds hybrid materials, suited CO2.

Язык: Английский

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Rational Design of Novel COF/MOF S-Scheme Heterojunction Photocatalyst for Boosting CO₂ Reduction at Gas–Solid Interface

ACS Applied Materials & Interfaces, Год журнала: 2022, Номер 14(21), С. 24299 - 24308

Опубликована: Май 20, 2022

Solar-driven photoreduction of CO2 into valuable fuels offers a sustainable technology to relieve the energy crisis as well greenhouse effect. Yet exploration highly efficient, selective, stable, and environmental benign photocatalysts for reduction remains major issue challenge. The interfacial engineering heterojunction could be valid approach boost efficiency catalytic process. Herein, we propose novel covalent organic framework/metal framework (COF/MOF) photocatalyst, using olefin (C═C) linked (TTCOF) NH2-UiO-66 (Zr) (NUZ) representative building blocks, enhanced CO. optimized TTCOF/NUZ exhibited superior CO yield (6.56 μmol g-1 h-1) in gas-solid system when irradiated by visible light only with H2O (g) weak reductant, it was 4.4 5 times higher than pristine TTCOF NUZ, respectively. photogenerated electrons transfer route proposed follow typical step-scheme (S-scheme), which affirmed XPS, situ XPS EPR characterizations. boosting activity credited special charge carrier separation S-scheme heterojunction, can accelerate transportation improve redox ability at interface. This work paves way design preparation COF/MOF heterostructure reduction.

Язык: Английский

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Encapsulated CdSe/CdS nanorods in double-shelled porous nanocomposites for efficient photocatalytic CO2 reduction

Nature Communications, Год журнала: 2022, Номер 13(1)

Опубликована: Окт. 29, 2022

Colloidal quantum dots have been emerging as promising photocatalysts to convert CO2 into fuels by using solar energy. However, the above usually suffer from low adsorption capacity because of their nonporous structures, which principally reduces catalytic efficiency. Here, we show that synchronizing imine polycondensation reaction self-assembly colloidal CdSe/CdS nanorods can produce micro-meso hierarchically porous nanocomposites with double-shelled nanocomposites. Owing hierarchical pores and ability separate photoexcited electrons, self-assembled exhibit remarkably higher activity (≈ 64.6 μmol g-1 h-1) toward CO in solid-gas regime than solids under identical conditions. Importantly, length is demonstrated be crucial correlate long-distance separation photogenerated electrons holes along axial direction. Overall, this approach provides a rational strategy optimize conversion integrating inorganic organic semiconductors.

Язык: Английский

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Selective CO₂ Photoreduction to CH₄ via Pd^δ+‐Assisted Hydrodeoxygenation over CeO₂ Nanosheets

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(30)

Опубликована: Май 20, 2022

Here, noble-metal-doped two-dimensional metal oxide nanosheets are designed to realize selective CO2 photoreduction CH4 . As a prototype, Pd-doped CeO2 fabricated, where the active sites of Pdδ+ (2<δ<4) and Ce3+ -Ov revealed by quasi in situ X-ray photoelectron spectra electron paramagnetic resonance spectra. Moreover, Fourier-transform infrared D2 O photodissociation desorption verify existence Pd-OD bond, implying that can participate water oxidation deliver H* species for facilitating protonation intermediates. Furthermore, theoretical calculations suggest Pd doping could regulate formation energy barrier key intermediates CO* CH3 O*, thus making reduction become favorable process. Accordingly, achieve nearly 100 % selectivity photoreduction, with raising evolution rate 41.6 μmol g-1 h-1

Язык: Английский

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