Covalent organic frameworks: emerging high-performance platforms for efficient photocatalytic applications

Wang, Guang-Bo; Li, Sha; Yan, Cai-Xin; Zhu, Furong; Lin, Qianqian; Xie, Ke-Hui; Geng, Yanfang; Dong, Yu‐Bin

doi:10.1039/d0ta00556h

Cited by 221 publications

(151 citation statements)

References 137 publications

(95 reference statements)

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“… 66 In addition, despite their heterogeneity, the controlled, high porosity of 2D-COFs ensures great accessibility to active sites, offering excellent catalytic performance and the potential for higher reaction selectivity by means of pore size tailoring. 65 , 67 Thus, 2D-COFs could lead to the development of photoactive materials for optoelectronics, photovoltaics, and visible light photocatalysis. 67 − 70 For COFs, the 2D versus 3D distinction is easier to define because it evolves from the simplified symmetry of the specific building blocks used to construct the framework.…”

Section: Two-dimensional Metal-free Photocatalysts: Protagonists Minmentioning

confidence: 99%

Metal-Free Photocatalysis: Two-Dimensional Nanomaterial Connection toward Advanced Organic Synthesis

et al. 2021

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Two-dimensional (2D) nanostructures are a frontier in materials chemistry as a result of their extraordinary properties. Metal-free 2D nanomaterials possess extra appeal due to their improved cost-effectiveness and lower toxicity with respect to many inorganic structures. The outstanding electronic characteristics of some metal-free 2D semiconductors have projected them into the world of organic synthesis, where they can function as high-performance photocatalysts to drive the sustainable synthesis of high-value organic molecules. Recent reports on this topic have inspired a stream of research and opened up a theme that we believe will become one of the most dominant trends in the forthcoming years.

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Section: Two-dimensional Metal-free Photocatalysts: Protagonists Minmentioning

confidence: 99%

Metal-Free Photocatalysis: Two-Dimensional Nanomaterial Connection toward Advanced Organic Synthesis

et al. 2021

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“…Recently, because of the crystalline and porous features, covalent organic frameworks (COFs) have attracted considerable attention in gas storage, catalysis, and photoelectric areas. [29][30][31][32][33][34][35][36][37][38] Particularly, integration of topologically identical and catalytically active building blocks into the porous extended structures could endow COFs to bridge a gap between homogeneous and heterogeneous catalysis. [39] Despite several COFs have been reported for CO 2 RR, the insulating nature usually leads to low current density and thus limits their application.…”

Section: Introductionmentioning

confidence: 99%

Conductive Phthalocyanine‐Based Covalent Organic Framework for Highly Efficient Electroreduction of Carbon Dioxide

Zhang

et al. 2020

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The electroreduction of CO2 to value‐added chemicals such as CO is a promising approach to realize carbon‐neutral energy cycle, but still remains big challenge including low current density. Covalent organic frameworks (COFs) with abundant accessible active single‐sites can offer a bridge between homogeneous and heterogeneous electrocatalysis, but the low electrical conductivity limits their application for CO2 electroreduction reaction (CO2RR). Here, a 2D conductive Ni‐phthalocyanine‐based COF, named NiPc‐COF, is synthesized by condensation of 2,3,9,10,16,17,23,24‐octa‐aminophthalocyaninato Ni(II) and tert‐butylpyrene‐tetraone for highly efficient CO2RR. Due to its highly intrinsic conductivity and accessible active sites, the robust conductive 2D NiPc‐COF nanosheets exhibit very high CO selectivity (>93%) in a wide range of the applied potentials of −0.6 to −1.1 V versus the reversible hydrogen electrode (RHE) and large partial current density of 35 mA cm−2 at −1.1 V versus RHE in aqueous solution that surpasses all the conventional COF electrocatalysts. The robust NiPc‐COF that is bridged by covalent pyrazine linkage can maintain its CO2RR activity for 10 h. This work presents the implementation of the conductive COF nanosheets for CO2RR and provides a strategy to enhance energy conversion efficiency in electrocatalysis.

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“…[ 1,2 ] 2D COFs with a variety of ordered π systems provide a desirable platform for developing visible‐light responsive photocatalysts for solar energy storage and conversion and have already shown potential applications in photocatalytic water splitting, CO 2 reduction, and organic synthesis. [ 3–11 ] In regardless of suitable bandgap and band structure, COFs in most cases afforded very low quantum efficiency in photocatalysis. Considering that the separation and transportation of the photogenerated charges is the key step in photosynthesis, the fast extraction of photogenerated electrons confined in π orbitals of COFs is very important for efficient photosynthesis.…”

Section: Methodsmentioning

confidence: 99%

Fabrication of NanoCOF/Polyoxometallate Composites for Photocatalytic NADH Regeneration via Cascade Electron Relay

Liu

Wang

et al. 2020

Solar RRL

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Covalent organic frameworks (COFs) are novel crystalline polymers with a unique designable feature at molecular level via weaving chemistry. [1,2] 2D COFs with a variety of ordered π systems provide a desirable platform for developing visible-light responsive photocatalysts for solar energy storage and conversion and have already shown potential applications in photocatalytic water splitting, CO 2 reduction, and organic synthesis. [3-11] In regardless of suitable bandgap and band structure, COFs in most cases afforded very low quantum efficiency in photocatalysis. Considering that the separation and transportation of the photogenerated charges is the key step in photosynthesis, the fast extraction of photogenerated electrons confined in π orbitals of COFs is very important for efficient photosynthesis. In natural photosynthesis, the photogenerated holes and electrons are spacially separated in PS II (catalyze H 2 O oxidation to H þ and O 2) and PS I (photoenzymatic reduction of NAD(P) þ to NAD(P)H). [12] The excited electrons are transferred from PS II to PS I through multistep with the assistance of mediators to inhibit the charge recombination. Inspired by natural photosynthesis, the utilization of an electron mediator is an efficient strategy to enhance the charge separation of COFs for efficient artificial photosynthesis. A good electron mediator should possess redox potentials alignment with the band structure of COFs and the properties of easy electron acception and donation. Polyoxometallates (POMs) could be reduced to heteropolyblue (HPB) via accepting electrons. [13] More interestingly, HPB can be excited by visible and near-infrared light at about 700 nm via intervalence charge transfer to regain the energy that is lost in the reduction process and the excited HPB* facilely denotes electrons to electron acceptors, e.g., H þ , O 2 , and metal complexes to drive the photocatalytic reductive reactions. Previous studies showed that the photocatalytic activity of semiconductors, e.g., C 3 N 4 , TiO 2 were greatly promoted by coupling with POM in photocatalytic CO 2 reduction, water oxidation, and organic pollutants removal due to the enhanced charge separation. [14-17] Though POM is a good candidate as electron mediator and electron storage tank, the coupling of COFs and POM has not been reported yet for artificial photosynthesis as far as we know, possibly related with the difficulty in hybridizing of the POM and COFs. Herein, we report the fabrication of nanoCOF/POM composites for the first time by simply mixing the cetyltrimethylammonium bromide/sodium dodecyl sulfate (CTAB/SDS, molar ratio of 97/3) micelle stabilized nanoCOF colloid solution with Na 3 PW 12 O 40 (Scheme 1). NanoCOF/POM composites possess visible-light responsive properties inherited from nanoTp-TTA COF (synthesized using 1,3,5-triformylphloroglucinol and 4,4 0 ,4 00-(1,3,5-triazine-2,4,6-triyl)trianiline as precursors). The transfer of photogenerated electrons from nanoTp-TTA COF to

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Covalent organic frameworks: emerging high-performance platforms for efficient photocatalytic applications

Abstract: In this review, a comprehensive summary of the potential photocatalytic applications realized to date in the fast-growing field of COFs is provided with the aim to present a full blueprint of COFs for photochemical energy conversion and reactions.

Cited by 221 publications

References 137 publications

Metal-Free Photocatalysis: Two-Dimensional Nanomaterial Connection toward Advanced Organic Synthesis

Metal-Free Photocatalysis: Two-Dimensional Nanomaterial Connection toward Advanced Organic Synthesis

Conductive Phthalocyanine‐Based Covalent Organic Framework for Highly Efficient Electroreduction of Carbon Dioxide

Fabrication of NanoCOF/Polyoxometallate Composites for Photocatalytic NADH Regeneration via Cascade Electron Relay

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