Manipulating the Spin State of Co Sites in Metal–Organic Frameworks for Boosting CO₂ Photoreduction

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(5), С. 3241 - 3249

Опубликована: Янв. 26, 2024

Photocatalytic CO2 reduction holds great potential for alleviating global energy and environmental issues, where the electronic structure of catalytic center plays a crucial role. However, spin state, key descriptor properties, is largely overlooked. Herein, we present simple strategy to regulate states Co centers by changing their coordination environment exchanging species into stable Zn-based metal–organic framework (MOF) afford Co-OAc, Co-Br, Co-CN photoreduction. Experimental DFT calculation results suggest that distinct sites give rise different charge separation abilities barriers adsorption/activation in photocatalysis. Consequently, optimized Co-OAc with highest spin-state presents an excellent photocatalytic activity 2325.7 μmol·g–1·h–1 selectivity 99.1% CO, which are among best all reported MOF photocatalysts, absence noble metal additional photosensitizer. This work underlines MOFs as ideal platform manipulation toward improved

Язык: Английский

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Construction of Single Ni Atom-Immobilized ZIF-8 with Ordered Hierarchical Pore Structures for Selective CO₂ Photoreduction

ACS Catalysis, Год журнала: 2023, Номер 13(10), С. 6630 - 6640

Опубликована: Май 1, 2023

The rational construction of single-atom-modified porous metal–organic frameworks (MOFs) for efficient CO2 photoconversion is a promising avenue, yet the one that poses significant challenge. In this study, we demonstrate successful Ni single-atom-immobilized ZIF-8 with an ordered hierarchical (macro–micro) pore structure highly photocatalytic reduction to CO. interpenetrated macroporous in microporous built up by employing polystyrene (PS) opal as hard template, while high stability framework achieved through double-solvent-induced crystallization. enables rapid mass transport and strong adsorption CO2, single atoms active sites electron-trapping optimize reaction energy hinder competitive H2 evolution. As result, achieves activity 4.2 mmol g–1 h–1 CO yield electronic selectivity 94%, which shows 47-fold ZIF-8. This work highlights significance constructing MOFs single-atom-active improve photoreduction realizing carbon neutralization.

Язык: Английский

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Construction of Low-Cost Z-Scheme Heterojunction Cu₂O/PCN-250 Photocatalysts Simultaneously for the Enhanced Photoreduction of CO₂ to Alcohols and Photooxidation of Water

Inorganic Chemistry, Год журнала: 2023, Номер 62(39), С. 15963 - 15970

Опубликована: Сен. 19, 2023

Solar-driven high-efficiency conversion of CO2 with water vapor into high-value-added alcohols is a promising approach for reducing emissions and achieving carbon neutrality. However, the rapid recombination photogenerated carriers low adsorption capacity photocatalysts are usually factors that limit their applicability. Herein, series low-cost Z-scheme heterostructures Cu2O/PCN-250-x constructed by in situ growth ultrasmall Cu2O nanoparticles on PCN-250. A systematic investigation revealed there strong interaction between The resulting Cu2O/PCN-250-2 exhibits excellent carrier separation efficiency capacity, which dramatically promote alcohols. Notably, total yield 268 μmol gcat-1 production CH3OH CH3H2OH superior to isolated PCN-250 Cu2O. This study provides new perspective design nanoparticle/metal-organic framework heterojunction reduction vapor.

Язык: Английский

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Precise Regulation of the Coordination Environment of Single Co(II) Sites in a Metal–Organic Framework for Boosting CO₂ Photoreduction

ACS Catalysis, Год журнала: 2023, Номер 13(13), С. 8760 - 8769

Опубликована: Июнь 16, 2023

While the coordination environment around catalytic metal sites plays a crucial role in catalysis, its precise design and modulation still remain challenge. Herein, coordinated N atom number single Co installed on UiO-type metal–organic framework has been modulated to afford UiO-Co-Nx (x = 2, 3, 4) for photocatalytic CO2 reduction. Significantly, performance is affected by site, which UiO-Co-N3 exhibits superior activity other counterparts. Photo-/electrochemical results support fastest charge transfer kinetics between photosensitizer UiO-Co-N3. Theoretical calculations, together with acquired from situ diffuse reflectance infrared Fourier transform spectra, manifest lowest energy barriers of rate-determining step desorption CO* over among all samples.

Язык: Английский

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Metal–organic frameworks for organic transformations by photocatalysis and photothermal catalysis

Chemical Society Reviews, Год журнала: 2024, Номер 53(18), С. 9378 - 9418

Опубликована: Янв. 1, 2024

Organic transformation by light-driven catalysis, especially, photocatalysis and photothermal denoted as photo(thermal) is an efficient, green, economical route to produce value-added compounds. In recent years, owing their diverse structure types, tunable pore sizes, abundant active sites, metal-organic framework (MOF)-based catalysis has attracted broad interest in organic transformations. this review, we provide a comprehensive systematic overview of MOF-based for First, the general mechanisms, unique advantages, strategies improve performance MOFs are discussed. Then, outstanding examples transformations over introduced according reaction type. addition, several representative advanced characterization techniques used revealing charge kinetics intermediates presented. Finally, prospects challenges field proposed. This review aims inspire rational design development materials with improved catalysis.

Язык: Английский

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Molecular‐Level Regulation Strategies Toward Efficient Charge Separation in Donor−Acceptor Type Conjugated Polymers for Boosted Energy‐Related Photocatalysis

Advanced Energy Materials, Год журнала: 2023, Номер 14(5)

Опубликована: Дек. 11, 2023

Abstract The development of efficient photocatalysts for artificial photocatalytic energy conversion is an intriguing strategy. Promisingly, conjugated polymers (CPs) have been actively investigated as alternatives to traditional inorganic semiconductors photocatalysis due their molecularly tunable optoelectronic properties, thus providing a great platform molecular design. Incorporating donor (D) and acceptor (A) units into the backbone CPs ensures adequate D−A interface, which essential facilitating charge separation. This approach also allows bandgaps leading significant progress in conversions recent years. Here, fundamentals D–A type are initially outlined, followed by advanced experimental methods density functional theory (DFT) calculations investigating carrier dynamics. Then, detailed exposition synthetic strategies carried out. Their extensive applications diverse energy‐related conversions, such hydrogen evolution, oxygen overall water splitting, CO 2 reduction, N H O evolution comprehensively presented. review provides new comprehensive insights molecular‐level design catalysts boosted conversion, expected further advance photocatalysis.

Язык: Английский

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MOF-on-MOF-derived CuO@In2O3 s-scheme heterojunction with core–shell structure for efficient photocatalytic CO2 reduction

Chemical Engineering Journal, Год журнала: 2024, Номер 485, С. 149855 - 149855

Опубликована: Фев. 21, 2024

Язык: Английский

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Generation of Lattice Strain in CdS Promotes Photocatalytic Reduction of CO₂

ACS Catalysis, Год журнала: 2024, Номер 14(7), С. 4648 - 4655

Опубликована: Март 13, 2024

The key to photocatalysis lies in the efficient separation and migration of photogenerated carriers surface for participation reaction. However, recombination electrons holes is a major hindrance that reduces activity. Herein, we developed method introduce lattice strain by regulating crystallinity material, thus resulting an intensive polarization internal electric field, which can promote process improve efficiency photocatalysis. degree be controlled solvothermal temperature. Compared with CdS-160 °C, CdS-100 °C larger field contributed 7-fold enhanced photocatalytic CO evolution from CO2; addition, CO/H2 ratio was also increased 4 times. This study reports important effects on carrier migration, providing valuable insights designing photocatalysts.

Язык: Английский

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Accelerated Photocatalytic Carbon Dioxide Reduction and Water Oxidation under Spatial Synergy

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(7)

Опубликована: Дек. 29, 2023

Abstract Photocatalytic conversion of CO 2 and H O into fuels oxygen is a highly promising solution for carbon‐neutral recycling. Traditionally, researchers have studied reduction oxidation separately, overlooking potential synergistic interplay between these processes. This study introduces an innovative approach, spatial synergy, which encourages progress by bringing the two half‐reactions atomic proximity. To facilitate this, we developed defective ZnIn S 4 ‐supported single‐atom Cu catalyst (Cu−SA/D−ZIS), demonstrates remarkable catalytic performance with rates 112.5 μmol g −1 h water 52.3 , exhibiting six‐fold enhancement over D−ZIS. The structural characterization results indicated that trapping effect vacancy associates on copper led to formation unsaturated coordination structure, Cu‐S 3 consequently giving rise Zn ′ V ⋅⋅ “ defect complexes. FT‐IR studies coupled theoretical calculations reveal spatially ”, where breakage O−H in synchronized *COOH, significantly lowering energy barrier. Notably, this and, first time, substantiates synergy through combination experimental analyses, providing fresh insight optimizing photocatalytic system.

Язык: Английский

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Ultrafast Synthesis of Graphene‐Embedded Cyclodextrin‐Metal‐Organic Framework for Supramolecular Selective Absorbency and Supercapacitor Performance

Advanced Science, Год журнала: 2023, Номер 10(31)

Опубликована: Авг. 27, 2023

Limited by preparation time and ligand solubility, synthetic protocols for cyclodextrin-based metal-organic framework (CD-MOF), as well subsequent derived materials with improved stability properties, still remains a challenge. Herein, an ultrafast, environmentally friendly, cost-effective microwave method is proposed, which induced graphene oxide (GO) to design CD-MOF/GOs. This applicable technique can control the crystal size of CD-MOFs from macro- nanocrystals. CD-MOF/GOs are investigated new type supramolecular adsorbent. It selectively adsorb dye molecule methylene green (MG) owing synergistic effect between hydrophobic nanocavity CDs, abundant O-containing functional groups GO in composites. Following high temperature calcination, resulting N, S co-doped porous carbons exhibit capacitance 501 F g-1 at 0.5 A , stable cycling 90.1% capacity retention after 5000 cycles. The carbon exhibits good electrochemical performance due its surface containing numerous electrochemically active sites adsorption carbonization. strategy incorporating variety molecules into optimizes properties their materials, furthering development toward fabrication zeitgeisty high-performance energy storage devices.

Язык: Английский

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