Polymer photocatalysts for solar-to-chemical energy conversion

Nature Reviews Materials, Journal Year: 2020, Volume and Issue: 6(2), P. 168 - 190

Published: Nov. 5, 2020

Language: Английский

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Confining and Highly Dispersing Single Polyoxometalate Clusters in Covalent Organic Frameworks by Covalent Linkages for CO₂ Photoreduction

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(4), P. 1861 - 1871

Published: Jan. 20, 2022

Single clusters have attracted extensive research interest in the field of catalysis. However, achieving a highly uniform dispersion single-cluster catalyst is challenging. In this work, for first time, we present versatile strategy uniformly dispersed polyoxometalates (POMs) covalent organic frameworks (COFs) through confining POM cluster into regular nanopores COF by linkage. These COF-POM composites combine properties light absorption, electron transfer, and suitable catalytic active sites; as result, they exhibit outstanding activity artificial photosynthesis: that is, CO2 photoreduction with H2O donor. Among them, TCOF-MnMo6 achieved highest CO yield (37.25 μmol g-1 h-1 ca. 100% selectivity) gas-solid reaction system. Furthermore, mechanism study based on density functional theory (DFT) calculations demonstrated photoinduced transfer (PET) process occurs from to POM, then reduction oxidation occur COF, respectively. This work developed method single which also shows potential using materials photocatalysis.

Language: Английский

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Molecular catalysis of CO₂ reduction: recent advances and perspectives in electrochemical and light-driven processes with selected Fe, Ni and Co aza macrocyclic and polypyridine complexes

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 49(16), P. 5772 - 5809

Published: Jan. 1, 2020

Recent developments in (photo)electrochemical CO₂ reduction combining Fe, Ni, and Co molecular complexes (semi)conductive materials have led to high catalytic performances.

Language: Английский

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Fundamentals and challenges of ultrathin 2D photocatalysts in boosting CO₂ photoreduction

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 49(18), P. 6592 - 6604

Published: Jan. 1, 2020

Carbon dioxide photoreduction currently suffers from low photoconversion efficiency and poor product selectivity. Ultrathin two-dimensional materials, which possess highly active sites with high density uniformity, can serve as ideal models to tailor three crucial parameters that determine the carbon In this review, we summarize extended absorption spectrum range enabled by ultrathin semiconductors defect levels intermediate bands, well conductors special partially occupied bands. Moreover, overview boosted carrier separation aroused states, surface polarization states built-in electric fields. We also review accelerated redox reaction kinetics induced in-plane heterostructures, isolated single atoms abundant low-coordinated dual-metal sites. Finally, end an outlook on unsolved issues concerning selective efficient photo-conversion of into C2+ products materials dual or multiple

Language: Английский

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Metal-Free Catalysis: A Redox-Active Donor–Acceptor Conjugated Microporous Polymer for Selective Visible-Light-Driven CO₂ Reduction to CH₄

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(39), P. 16284 - 16292

Published: Sept. 21, 2021

Achieving more than a two-electron photochemical CO2 reduction process using metal-free system is quite exciting and challenging, as it needs proper channeling of electrons. In the present study, we report rational design synthesis redox-active conjugated microporous polymer (CMP), TPA-PQ, by assimilating an electron donor, tris(4-ethynylphenyl)amine (TPA), with acceptor, phenanthraquinone (PQ). The TPA-PQ shows intramolecular charge-transfer (ICT)-assisted catalytic activity for visible-light-driven photoreduction to CH4 (yield = 32.2 mmol g–1) impressive rate (2.15 h–1 high selectivity (>97%). Mechanistic analysis based on experimental results, in situ DRIFTS, computational studies reveals that potential catalyzing was energetically driven photoactivated ICT upon surface adsorption CO2, wherein adjacent keto groups PQ unit play pivotal role. critical role stimulating photocatalysis further illustrated synthesizing another CMP (TEB-PQ), bearing triethynylbenzene (TEB) PQ, 8-fold lesser toward 4.4 compared TPA-PQ. results demonstrate novel concept efficient, sustainable, recyclable robust organic photocatalyst.

Language: Английский

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Metal-organic framework membranes with single-atomic centers for photocatalytic CO2 and O2 reduction

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: May 11, 2021

Abstract The demand for sustainable energy has motivated the development of artificial photosynthesis. Yet catalyst and reaction interface designs directly fixing permanent gases (e.g. CO 2 , O N ) into liquid fuels are still challenged by slow mass transfer sluggish catalytic kinetics at gas-liquid-solid boundary. Here, we report that gas-permeable metal-organic framework (MOF) membranes can modify electronic structures properties metal single-atoms (SAs) to promote diffusion, activation, reduction gas molecules 2, produce under visible light mild conditions. With Ir SAs as active centers, defect-engineered MOF activated NH -UiO-66) particles reduce HCOOH with an apparent quantum efficiency (AQE) 2.51% 420 nm on interface. promoted diffusion porous gas-solid interfaces, SA/MOF convert humid a near-unity selectivity significantly increased AQE 15.76% nm. A similar strategy be applied photocatalytic -to-H conversions, suggesting wide applicability our designs.

Language: Английский

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Surface sites engineering on semiconductors to boost photocatalytic CO2 reduction

Nano Energy, Journal Year: 2020, Volume and Issue: 75, P. 104959 - 104959

Published: May 24, 2020

Language: Английский

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CeO2/3D g-C3N4 heterojunction deposited with Pt cocatalyst for enhanced photocatalytic CO2 reduction

Applied Surface Science, Journal Year: 2020, Volume and Issue: 537, P. 147891 - 147891

Published: Sept. 15, 2020

Language: Английский

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Carbon Nitride‐Based Ruthenium Single Atom Photocatalyst for CO₂ Reduction to Methanol

Small, Journal Year: 2021, Volume and Issue: 17(16)

Published: March 19, 2021

Abstract With increasing concerns for global warming, the solar‐driven photocatalytic reduction of CO 2 into chemical fuels like methanol is a propitious route to enrich energy supplies, with concomitant abundant stockpiles. Herein, novel single atom‐confinement and strategy are reported toward ruthenium atoms dispersion over porous carbon nitride surface. Ruthenium atom character well confirmed by EXAFS absorption spectrometric analysis unveiling cationic coordination environment single‐atomic‐site center, that formed Ru‐N/C intercalation in first shell, attaining synergism N–Ru–N connection interfacial carrier transfer. From time resolved fluorescence decay spectra, average lifetime RuSA–mC 3 N 4 system found be higher compared m‐C ; fact uncovering crucial role Ru promoting reaction system. A high yield (1500 µmol g ‐1 cat. after 6 h reaction) using water as an electron donor reusability developed catalyst without any significant change efficiency represent superior aspects its potential application real industrial technologies.

Language: Английский

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Synergistic Modulation of the Separation of Photo‐Generated Carriers via Engineering of Dual Atomic Sites for Promoting Photocatalytic Performance

Advanced Materials, Journal Year: 2021, Volume and Issue: 33(52)

Published: Oct. 18, 2021

The separation efficiency of photo-generated carriers is still a great challenge that restricts the practical application photocatalytic technology. design spatial path for at atomic level provides an innovative approach to address this challenge. Herein, facile dual sites strategy, consisting Cu-N4 and C-S-C active moieties decorated on polymeric carbon nitride (Cu SAs/p-CNS) reported simultaneously achieve highly efficient electrons holes boosting performance. As proof concept, Cu SAs/p-CNS successfully applied photo-oxidation 5-hydroxymethylfurfural (HMF) 2,5-diformylfuran (DFF), which exhibits 77.1% HMF conversion 85.6% DFF selectivity under visible light irradiation. activity considerably higher than bulk p-CN, S doped p-CN supported single atom catalysts. Theoretical calculations experimental results suggest that, during reaction, isolated directly capture electrons, while surrounding atoms bear holes, synergistically facilitates thus in enhanced activity. This study new perspective rational high performance photocatalysts level.

Language: Английский

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