| 1. |
- Huang, Shiyu, et al.
(författare)
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Single-Atom Metal Sites Anchored Hydrogen-Bonded Organic Frameworks for Superior “Two-In-One” Photocatalytic Reaction
- 2023
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Ingår i: Advanced Functional Materials. - : Wiley. - 1616-301X .- 1616-3028. ; 33:21
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Tidskriftsartikel (refereegranskat)abstract
- Photoredox catalysis is a green solution for organics transformation and CO2 conversion into valuable fuels, meeting the challenges of sustainable energy and environmental concerns. However, the regulation of single-atomic active sites in organic framework not only influences the photoredox performance, but also limits the understanding of the relationship for photocatalytic selective organic conversion with CO2 valorization into one reaction system. As a prototype, different single-atomic metal (M) sites (M2+ = Fe2+, Co2+, Ni2+, Cu2+, and Zn2+) in hydrogen-bonded organic frameworks (M-HOF) backbone with bridging structure of metal-nitrogen are constructed by a typical “two-in-one” strategy for superior photocatalytic C-N coupling reactions integrated with CO2 valorization. Remarkably, Zn-HOF achieves 100% conversion of benzylamine oxidative coupling reactions, 91% selectivity of N-benzylidenebenzylamine and CO2 conversion in one photoredox cycle. From X-ray absorption fine structure analysis and density functional theory calculations, the superior photocatalytic performance is attributed to synergic effect of atomically dispersed metal sites and HOF host, decreasing the reaction energy barriers, enhancing CO2 adsorption and forming benzylcarbamic acid intermediate to promote the redox recycle. This work not only affords the rational design strategy of single-atom active sites in functional HOF, but also facilitates the fundamental insights upon the mechanism of versatile photoredox coupling reaction systems.
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| 2. |
- Li, Zhuwei, et al.
(författare)
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Atomically dispersed Ni active sites on covalent organic frameworks for heterogeneous metallaphotocatalytic C–N cross-coupling
- 2024
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Ingår i: Applied Catalysis B. - : Elsevier BV. - 0926-3373 .- 1873-3883. ; 345
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Tidskriftsartikel (refereegranskat)abstract
- Covalent organic frameworks (COFs) have been acknowledged as a potential platform for heterogeneous photoredox cross-coupling due to their excellent chemical stability, admirable controllability, and extremely prominent surface area. However, synthesizing COFs with bidentate ligand units and utilizing active sites remain a grand challenge. Herein, we report a promising new family of 2,6-pyridinedicarboxaldehyde-bis-(p-aminophenylimine)-based two-dimensional (2D) COFs (PP-COF) using an amine monomer and classic tri-aldehydes. On this basis, dispersed Ni single-atom sites were immobilized on three-types imine-based bi-coordinated 2D COFs (Ni SAS-PP-COF) as heterogeneous dual photoredox catalysts for photo/Ni dual-catalyzed C–N cross-coupling between aryl bromides and alkyl/sulfo amines. Under solar energy irradiation, PP-COF could absorb light to generate electrons and holes, then the photogenerated electrons are transferred to Ni sites to reduce divalent nickel to monovalent nickel. Monovalent nickel is necessary to drive the nickel catalytic cycle. Due to the increased charge separation and abundant active sites, the state-of-the-art Ni SAS-PP-COFs catalyst achieves excellent catalytic performance in comparison of pristine PP-COF. The heterogeneous Ni SAS-PP-COF catalytic system not only confirms the prospect of COFs as potential photoredox/transition-metal dual catalysts, but also provides in-depth insights into the synthesis of functional COFs toward practical metallaphotocatalytic application.
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| 3. |
- Li, Zhuwei, et al.
(författare)
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Engineering single-atom active sites anchored covalent organic frameworks for efficient metallaphotoredox C-N cross-coupling reactions
- 2022
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Ingår i: Science Bulletin. - : Elsevier BV. - 2095-9273. ; 67:19, s. 1971-1981
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Tidskriftsartikel (refereegranskat)abstract
- Photoredox catalysis has become an indispensable solution for the synthesis of small organic molecules. However, the precise construction of single-atomic active sites not only determines the catalytic performance, but also avails the understanding of structure-activity relationship. Herein, we develop a facile approach to immobilize single-atom Ni sites anchored porous covalent organic framework (COF) by use of 4,40,400-(1,3,5-triazine-2,4,6-triyl)trianiline and 2,6-diformylpyridine (Ni SAS/TD-COF). Ni SAS/TDCOF catalyst achieves excellent catalytic performance in visible-light-driven catalytic carbon-nitrogen cross-coupling reaction between aryl bromides and amines under mild conditions. The reaction provides amine products in excellent yields (71%-97%) with a wide range of substrates, including aryl and heteroaryl bromides with electron-deficient, electron-rich and neutral groups. Notably, Ni SAS/TD-COF could be recovered from the reaction mixture, corresponding to the negligible loss of photoredox performance after several cycles. This work provides a promising opportunity upon rational design of single-atomic active sites on COFs and the fundamental insight of photoredox mechanism for sustainable organic transformation.
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| 4. |
- Li, Zhuwei, et al.
(författare)
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Integrated nickel/polymer dual catalytic system for visible-light-driven sulfonamidation between aryl halides and aryl sulfonamides
- 2022
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Ingår i: CHEM CATALYSIS. - : Elsevier BV. - 2667-1093. ; 2:12, s. 3546-3558
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Tidskriftsartikel (refereegranskat)abstract
- By merging transition metal and heterogeneous photocatalyst, a metal-photoredox system has attracted more attention for cross -coupling of various dual photoredox catalysis. However, there is a grand challenge for the attenuated nucleophilicity of sulfonamides relative to alkyl amines. Herein, an integrated dual catalytic system of porous carbon nitride nanosheet with nitrogen vacancies (NV-P-C3N4)as a conjugated polymer semiconductor host in combination with transition-metal nickel (Ni) was constructed by a defect and morphology regulation strategy toward visible-light-driven sulfona-midation between aryl halides and aryl sulfonamides. The excellent nickel/photoredox-catalyzed C-N coupling reaction performance is ascribed to the large specific surface area, abundant active sites, long carrier lifetime, and efficient transfer and separation of photo -excited electrons and holes. This work highlights the opportunity to cooperate with heterogeneous catalysts and active metal sites for challenging cross-coupling reactions.
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| 5. |
- Shao, Teng, et al.
(författare)
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A chemically bonded and plasmonic Z-scheme junction for high-performance artificial photosynthesis of hydrogen peroxide
- 2022
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Ingår i: Journal of Materials Chemistry A. - : Royal Society of Chemistry (RSC). - 2050-7488 .- 2050-7496. ; 11:3, s. 1199-1207
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Tidskriftsartikel (refereegranskat)abstract
- Artificial photosynthesis has been regarded as a promising solution for the clean, sustainable, and efficient production of hydrogen peroxide (H2O2). However, rigorous regulation of light absorption, charge transfer, and surface kinetics is significant for catalytic performance. As a proof of concept, we report a chemically bonded and plasmonic Z-scheme junction as a model material prepared by the in situ assembly of nonstoichiometric W18O49 (WO) onto two-dimensional carbon nitride nanosheets (CNs) for high-performance artificial photosynthesis of H2O2. Notably, this typical Z-scheme photocatalyst exhibits the highest H2O2 generation rate of 732.4 μmol g−1 h−1, higher than that of individual catalysts, even maintaining 140.5 μmol g−1 h−1 under broad-spectrum response irradiation (λ > 700 nm). From the analysis of experimental characterization and density functional theory calculations, the superior performance of CN/WO heterostructures is ascribed to an intense localized surface plasmon resonance absorption, appropriate band alignment, and strong internal electric field. This work not only elucidates the key role of chemically bonded and plasmonic heterostructures but also paves an avenue for the rational design and construction of Z-scheme photocatalysts for solar energy conversion.
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| 6. |
- Song, Yurou, et al.
(författare)
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Metal-Organic Framework Glass Catalysts from Melting Glass-Forming Cobalt-Based Zeolitic Imidazolate Framework for Boosting Photoelectrochemical Water Oxidation
- 2023
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Ingår i: Angewandte Chemie International Edition. - : Wiley. - 1433-7851 .- 1521-3773. ; 62:32
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Tidskriftsartikel (refereegranskat)abstract
- Sluggish oxygen evolution kinetics and serious charge recombination restrict the development of photoelectrochemical (PEC) water splitting. The advancement of novel metal–organic frameworks (MOFs) catalysts bears practical significance for improving PEC water splitting performance. Herein, a MOF glass catalyst through melting glass-forming cobalt-based zeolitic imidazolate framework (Co-agZIF-62) was introduced on various metal oxide (MO: Fe2O3, WO3 and BiVO4) semiconductor substrates coupled with NiO hole transport layer, constructing the integrated Co-agZIF-62/NiO/MO photoanodes. Owing to the excellent conductivity, stability and open active sites of MOF glass, Co-agZIF-62/NiO/MO photoanodes exhibit a significantly enhanced photoelectrochemical water oxidation activity and stability in comparison to pristine MO photoanodes. From experimental analyses and density functional theory calculations, Co-agZIF-62 can effectively promote charge transfer and separation, improve carrier mobility, accelerate the kinetics of oxygen evolution reaction (OER), and thus improve PEC performance. This MOF glass not only serves as an excellent OER cocatalyst on tunable photoelectrodes, but also enables promising opportunities for PEC devices for solar energy conversion.
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| 7. |
- Zhao, Yue, et al.
(författare)
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Boosting Charge Mediation in Ferroelectric BaTiO3−x-Based Photoanode for Efficient and Stable Photoelectrochemical Water Oxidation
- 2023
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Ingår i: Small Structures. - : Wiley. - 2688-4062. ; 4:9
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Tidskriftsartikel (refereegranskat)abstract
- Oxygen evolution reaction (OER) is a bottleneck to photoelectrochemical (PEC) water splitting; however, there remains an impressive challenge for intrinsic charge transport for the development of integrated photoanodes. Herein, covalent triazine frameworks as conjugated molecules are grafted on the surfaces of ferroelectric BaTiO3−x (CTF/BTO) nanorod array, and then oxyhydroxide oxygen evolution cocatalyst (OEC) is constructed as an integrated photoanode. The OEC/CTF/BTO array not only achieves a high photocurrent density of 0.83 mA cm−2 at 1.23 V versus reversible hydrogen electrode (vs RHE) and low onset potential of ≈0.23 VRHE, but also optimizes outstanding stability. To disclose the origin, the enhanced PEC activity can be contributed to the integration of CTF and OEC, enhancing light-harvesting capability, boosting charge carrier mediation, and promoting water oxidation kinetics through electrochemical analysis and density functional theory calculations. This study not only provides an alternative to accelerate charge transfer, but also paves the rational design and fabrication of integrated photoanodes for boosting PEC water splitting performance.
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