Manipulating Grain Boundary Defects in π‐Conjugated Covalent Organic Frameworks Enabling Intrinsic Radical Generation for Photothermal Conversion

Chen, Zhongxin; Su, Yan Kuin; Tang, Xiaohui; Zhang, Xiaojin; Duan, Chunhui; Huang, Fei; Li, Yuan

doi:10.1002/solr.202100762

Cited by 14 publications

(11 citation statements)

References 39 publications

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“…[16] Recently, significant progress has been made in developing COFs for photocatalytic applications, including hydrogen and oxygen evolution reactions (HER, OER), solar-driven water splitting, CO 2 photoreduction, photodegradation of organic pollutants, photothermal conversion, and light-induced selective oxidation. [16,119,120,126] Here, we would like to shortly overview some of the recent achievements of COFs for photocatalytic applications and then provide possible ideas for future perspectives.…”

Section: Cofsmentioning

confidence: 99%

Perspectives and Current Trends on Hybrid Nanocomposite Materials for Photocatalytic Applications

2023

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Photocatalysis can be understood as the acceleration of chemical reactions by incident light, especially when the catalyst is photoactive. These reactions are unachievable or very difficult without photoactivation. Photocatalysis could find applications in a wide range of fields such as renewable energy (water splitting, CO 2 reduction, solar fuel production) and environmental (water treatment by removing pharmaceutic and pesticides contaminant, for instance, and improving air quality by reducing volatile organic compounds [VOCs]). [1] The advance in the photocatalysis field is driven by developing novel, innovative materials that mainly allow light absorption and efficient charge separation. [2] The most developed photocatalysts are inorganic semiconductors such as metal oxides (such as ZnO, TiO 2 , WO 3 , SnO 2 , and CuO) [3,4] and chalcogenides (ZnS, CuS, CdS, Sb 2 S 3 , Cu 2 SnS 3 , and Cu 2 SnSe 3 ). [5,6] In order to enhance the performance of these semiconductor catalysts, different strategies were investigated to reduce the recombination of photogenerated electron-hole pairs and to extend the absorption edge of these catalysts to the visible region of sunlight: 1) tuning of the morphologies, 2) doping to tune the bandgap, 3) junction between several semiconductor materials, [7,8] and 4) combining with metallic and plasmonic nanomaterials (Cu, Pt, Au, Pd). [9,10] An alternative approach to increase the efficiency of these photocatalysts is the design of organic-inorganic hybrid materials. Two classes of hybrid materials were largely investigated: 1) small molecules such as dyes and molecular catalysts known for their sensitizing and photocatalytic properties, and 2) organic macromolecules or polymers are known for tuning the properties of the semiconductor. These polymers also act as a protective layer, tuning the composites' hydrophobicity/hydrophilicity or lipophilicity. Moreover, they could also provide additional photocatalytic, electron transferring, and conductive properties.Different types of polymers were investigated in the literature, such as polydopamine (PDA), polyaniline (PANI), polythiophene, poly(3-hexilthiophene) (P3HT), polyphenylenevinylenes (PPVs), poly(3,4-ethelenedioxythiophene) (PEDOT), chitosan (CS), poly(pyrrole) (PPy), polyvinyl alcohol (PVA), covalent organic polymer (COP), and covalent organic frameworks (COFs). [11] Two of the most well-established aforementioned conductive polymers are CS and PANI. Despite more than a century of ongoing research, these polymers continue to have a large and highimpact on the literature, as shown by the constantly growing research works published each year. This ever-increasing attention is primarily attributed to the extensive application of both

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Section: Cofsmentioning

confidence: 99%

Perspectives and Current Trends on Hybrid Nanocomposite Materials for Photocatalytic Applications

2023

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“…Free radicals are the unpaired electrons on the sample, and the lower energy can make these electrons enter the excited state. Therefore, free radicals have a strong ability to absorb light with longer wavelengths and make the samples show fascinating photothermal conversion properties. ,, The surface defects and higher lattice order may limit the number of electrons entering the excited state and confine the movement of excited electrons, thereby weakening the photoacoustic coupling effect of the material and ultimately reducing the photothermal conversion capability of the sample. , At the same time, surface defects restrict photons from entering the sample, which may prevent electrons from absorbing energy and transitioning to excited states, ultimately reducing heat generation . The highly ordered carbon layer structure is not conducive to heat storage and light absorption, limiting the photothermal conversion performance of the sample .…”

Section: Resultsmentioning

confidence: 99%

Structural and Compositional Modulation of Porous Carbon for High-Performance Photothermal Water Evaporation

Chen

Jiang

et al. 2022

ACS Sustainable Chem. Eng.

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In recent years, carbon materials have been widely used in the field of photothermal conversion due to their high chemical stability, wide range of absorbance and low cost. However, the realization mechanism of photothermal conversion of carbon materials is still not well revealed, which limits the design and preparation of efficient photothermal carbon materials. Herein, an Al-based porous coordination polymer was used to prepare porous carbon materials, and statistical analysis was carried out to investigate the relationship between the structure parameters of the samples and the photothermal conversion efficiency. We found that the photothermal conversion efficiency of the samples shows a highly positive correlation with the free radical concentration and a strong correlation with the degree of graphitization. The volume and surface area of micropores also have a significant influence on the photothermal conversion efficiency of the samples. An evaporator was assembled using the porous carbon material by electrospinning method, the evaporator possesses a high evaporation rate of 1.72 kg/(m2 h) and the evaporation efficiency of ca. 89%, suggesting the highly practical potential of this carbon material in water treatment.

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“…Indeed, Chen et al reported a strategy to manipulate the boundary defects to introduce radicals into the fully conjugated COFs while retaining their crystallinity and porous structure. [ 42 ] This will broaden the NIR absorption of the COFs for light harvesting and give rise to the efficient photothermal conversion through the nonradiative decay.…”

Section: M–z–cs Structure Design Strategies and Preparation Methodsmentioning

confidence: 99%

“…[ 21,40,41 ] In addition, the presence of paramagnetic radicals induced by boundary defects in some COF‐based composites can enhance the nonradiative relaxation of the composites, thus synergistically enhancing the photothermal conversion of the composites with the thermal vibration effect of COFs themselves. [ 42 ] Furthermore, porphyrin organic frameworks (POFs) have great potential for solar vapor generation because of their unique optical properties and their ability to grow uniformly on hydrophilic substrates with different pore sizes. Additionally, it is worth noting that POFs are a type of COFs and therefore exhibit the same photothermal conversion effect as COFs.…”

Section: Photothermal Conversion Mechanism Of M–z–csmentioning

confidence: 99%

Recent Progress on Emerging Porous Materials for Solar‐Driven Interfacial Water Evaporation

Wang

Jia

et al. 2023

Energy Tech

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Solar‐driven interfacial water evaporation (SDIWE) offers a sustainable, environmentally friendly, and promising solution to the global water and energy crisis. Over the last decades, desalination, wastewater purification, power generation, and metal ion recovery and reuse based on SDIWE have been extensively investigated. In particular, considerable attention has been devoted to photothermal materials, as they are a key element of the SDIWE. As a class of crystalline porous materials, featuring diversified and customized structures, precise and tuneable functions, large specific surface area, low thermal conductivity and good light absorption, metal organic frameworks (MOFs), zeolite imidazolium frameworks (ZIFs), covalent organic frameworks (COFs), and their derived composites have been proven to possess great potential in the field of SDIWE. In this review, first the photothermal conversion mechanisms of MOFs, ZIFs, COFs, and their derived photothermal composites (M–Z–Cs) are briefly summarized, and then their structure design strategies and preparation methods from the perspectives of energy intake, energy management, and energy utilization are analyzed. Finally, based on the summary of their practical applications, an outlook in future research on these materials systems is provided, taking into account the current several challenges in the field of SDIWE.

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Manipulating Grain Boundary Defects in π‐Conjugated Covalent Organic Frameworks Enabling Intrinsic Radical Generation for Photothermal Conversion

Cited by 14 publications

References 39 publications

Perspectives and Current Trends on Hybrid Nanocomposite Materials for Photocatalytic Applications

Perspectives and Current Trends on Hybrid Nanocomposite Materials for Photocatalytic Applications

Structural and Compositional Modulation of Porous Carbon for High-Performance Photothermal Water Evaporation

Recent Progress on Emerging Porous Materials for Solar‐Driven Interfacial Water Evaporation

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