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

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(13), P. 8760 - 8769

Published: June 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.

Language: Английский

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Improved Plasmonic Hot-Electron Capture in Au Nanoparticle/Polymeric Carbon Nitride by Pt Single Atoms for Broad-Spectrum Photocatalytic H2 Evolution

Nano-Micro Letters, Journal Year: 2023, Volume and Issue: 15(1)

Published: May 20, 2023

Rationally designing broad-spectrum photocatalysts to harvest whole visible-light region photons and enhance solar energy conversion is a "holy grail" for researchers, but still challenging issue. Herein, based on the common polymeric carbon nitride (PCN), hybrid co-catalysts system comprising plasmonic Au nanoparticles (NPs) atomically dispersed Pt single atoms (PtSAs) with different functions was constructed address this challenge. For dual decorated PCN (PtSAs-Au2.5/PCN), photoexcited generate electrons under UV short-wavelength visible light, synergetic NPs PtSAs not only accelerate charge separation transfer though Schottky junctions metal-support bond also act as H2 evolution. Furthermore, absorb long-wavelength light owing its localized surface plasmon resonance, adjacent trap hot-electrons evolution via direct electron effect. Consequently, PtSAs-Au2.5/PCN exhibits excellent photocatalytic activity rate of 8.8 mmol g-1 h-1 at 420 nm 264 μmol 550 nm, much higher than that Au2.5/PCN PtSAs-PCN, respectively. This work provides new strategy design reaction.

Language: Английский

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Enhancing Photocatalytic‐Transfer Semi‐Hydrogenation of Alkynes Over Pd/C₃N₄ Through Dual Regulation of Nitrogen Defects and the Mott–Schottky Effect

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(41)

Published: July 5, 2023

The selective hydrogenation of alkynes is an important reaction; however, the catalytic activity and selectivity in this reaction are generally conflicting. In study, ultrafine Pd nanoparticles (NPs) loaded on a graphite-like C3 N4 structure with nitrogen defects (Pd/DCN) synthesized. resulting Pd/DCN exhibits excellent photocatalytic performance transfer ammonia borane. rate superior to those Pd/BCN (bulk without defects) under visible-light irradiation. characterization results density functional theory calculations show that Mott-Schottky effect can change electronic NPs, thus enhances toward phenylacetylene. After 1 h, reaches 95%, surpassing (83%). Meanwhile, supports improve response accelerate separation photogenerated charges enhance Pd/DCN. Therefore, higher efficiency visible light, turnover frequency (TOF) 2002 min-1 . This TOF five times dark conditions 1.5 Pd/BCN. study provides new insights into rational design high-performance catalysts.

Language: Английский

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Heteroatom‐Doped Ag₂₅ Nanoclusters Encapsulated in Metal–Organic Frameworks for Photocatalytic Hydrogen Production

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(17)

Published: Feb. 26, 2024

Atomically precise metal nanoclusters (NCs) with unique optical properties and abundant catalytic sites are promising in photocatalysis. However, their light-induced instability the difficulty of utilizing photogenerated carriers for photocatalysis pose significant challenges. Here, MAg

Language: Английский

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Regulating Photocatalytic CO₂ Reduction Kinetics through Modification of Surface Coordination Sphere

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 34(9)

Published: Oct. 28, 2023

Abstract Solar‐driven reduction of CO 2 to value‐added products represents a sustainable strategy for mitigating the greenhouse effect and addressing related green‐energy crisis. Herein, it is demonstrated that modifying surface coordination sphere can significantly enhance reaction kinetics overall efficiency reduction. More specifically, decoration isolated Mn atoms over multi‐edged TiO nano‐pompons (Mn/TONP) upshifts d‐band center allows favorable adsorption. Ultrafast spectroscopy demonstrates greatly accelerated charge transfer between photoexcited TONP newly implanted reactive centers, supplying long‐lifetime electrons reduce absorbed molecules. By integrating adsorption activation functions into decorated sites, developed photocatalyst demonstrate impressive capacity (80.51 mmol g −1 h ). The modulation at atomic level not only opens new avenues regulating toward photocatalytic reduction, but also paves way rational design highly efficient selective photocatalysts clean energy conversion.

Language: Английский

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