Hypercrosslinked Polymers as a Photocatalytic Platform for Visible‐Light‐Driven CO<sub>2</sub>Photoreduction Using H<sub>2</sub>O

Schukraft, Giulia E. M.; Woodward, Robert T.; Kumar, Santosh; Sachs, Michael L.; Eslava, Salvador; Petit, Camille

doi:10.1002/cssc.202002824

Cited by 51 publications

(48 citation statements)

References 43 publications

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“…Recently, organic polymer materials including covalent organic frameworks (COFs) [ 8 ] and covalent microporous polymers (CMPs) [ 9 ] have been suggested as promising photocatalysts owing to their irreplaceable advantages including facile structural controllability, high CO 2 adsorption capacity, excellent structural stability, and wide spectral response range. [ 10 –‐ 12 ] Nevertheless, sacrificial reagents, e.g. triethanolamine, triethylamine, and triisopropanolamine, are still necessary so far to reduce CO 2 for most of organic polymer photocatalytic systems.…”

Section: Introductionmentioning

confidence: 99%

Covalent Microporous Polymer Nanosheets for Efficient Photocatalytic CO₂ Conversion with H₂O

Zhi

Zhou

Liu

et al. 2022

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most promising technologies to solve these problems. [1] However, it is a daunting task for the effective integration of CO 2 reduction reaction (CO 2 RR) and H 2 O oxidation half-reactions in one catalytic system, for which the development of photo catalysts is the most crucial factor. [2] At the initial stage, many inorganic semiconductors, such as TiO 2 , [3] CdS, [4] ZnGa 2 O 4 , [5] and Zn 2 GeO 4 [6] et al., were used to achieve the overall reaction. These inorganic materials usually suffer from low photocatalytic efficiency, unsatisfactory selectivity, and limited visible-light harvesting, [7] therefore energizing to explore new photocatalytic systems. Recently, organic polymer materials including covalent organic frameworks (COFs) [8] and covalent microporous polymers (CMPs) [9] have been suggested as promising photocatalysts owing to their irreplaceable advantages including facile structural controllability, high CO 2 adsorption capacity, excellent structural stability, and wide spectral response range. [10--12] Nevertheless, sacrificial reagents, e.g. triethanolamine, triethylamine, and triisopropanolamine, are still necessary so far to reduce CO 2 for most of organic polymer photocatalytic systems. [13][14][15] Only a few examples among all the organic photocatalysts, such as 5T-15CN/BVNS by Jing's group, [16] sh-COP-P by Zhang's group, [17] TAPBB-COF by Su's group, [18] and TTCOF-Zn by Lan's group, [19] can complete the overall CO 2 reduction reaction, but usually with an unsatisfactory CO 2 reduction efficiency under visible light irradiation. As a result, it is still demanding to develop new high-performance organic polymer-based photocatalysts for CO 2 conversion with H 2 O as an electron donor.Herein, an imide-based 2D covalent organic polymer CoP-cPDA-CMP has been fabricated by the polyimidization reaction of tetraaminophthalocyanatocobalt(II) (CoTAPc) and 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA), which was exfoliated into nanosheets CoPcPDA-CMP NSs used for effective visible-light-driven CO 2 reduction. Our strategy is based on the following considerations: 1) both kinds of chromophores [cobalt phthalocyanine (CoPc) and 3,4,9,10-perylenetetracarboxylic diimide (PDI) moieties] in CoPcPDA-CMP NSs exhibit excellent visible-light-harvesting capacity, [20,21] leading to a wide spectral response range for CoPcPDA-CMP NSs.2) CoPc has a high LUMO energy to drive photoexcited electrons to reduce CO 2 , [22] while PDI and its derivatives with low It is still a challenging target to achieve photocatalytic CO 2 conversion to valuable chemicals with H 2 O as an electron donor. Herein, 2D imide-based covalent organic polymer nanosheets (CoPcPDA-CMP NSs), which integrate cobalt phthalocyanine (CoPc) moiety for reduction half-reaction and 3,4,9,10-perylenetetracarboxylic diimide moiety for oxidation half-reaction, are constructed as a Z-scheme artificial photosynthesis system to complete the overall CO 2 reduction reaction. Owing to the outstanding light absorption capacity, charge separation effic...

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Section: Introductionmentioning

confidence: 99%

Covalent Microporous Polymer Nanosheets for Efficient Photocatalytic CO₂ Conversion with H₂O

Zhi

Zhou

Liu

et al. 2022

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“…20 HCP-based catalysts were employed for a wide array of transformations, ranging from biomass conversion 21,22 to the photocatalytic reduction of CO2. 23,24 High surface areas allow for an abundance of catalytically active sites and hierarchically porous structures are beneficial to the mass transfer of reactants and products. As such, HCPs show excellent ability in catalysis and are ideal candidates for industrial applications in accordance with the principles of green chemistry.…”

Section: Introductionmentioning

confidence: 99%

A One-Pot Route to Fine-Tuned Hypercrosslinked Polymer Solid Acid Catalysts

Blocher

Mayer

Schweng

et al. 2022

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Highly acidic sulfonated polymers are promising heterogeneous catalysts due to their excellent chemical and thermal stability, as well as the possibility of employing low-cost synthesis routes. However, their production is time consuming and control of their chemical and physical properties is often difficult. Here, we produce sulfonated hypercrosslinked polymers using chlorosulfonic acid as a dual polymerisation catalyst and sulfonation agent, consolidating a conventional two-step process into a one-pot reaction. The synthesis time of the networks is reduced from 5-6 days to <24 hours, while significantly lowering or eliminating the requirement of some reagents. Furthermore, these sulfonated networks display superior acid site densities and porous properties to conventional equivalents. By varying the ratio of aromatic monomer with the multifunctional chlorosulfonic acid at the synthetic stage, excellent control over the polymers’ porous properties and sulfonation density is achieved, permitting judicious catalyst design. The ability of these polymers to act as heterogeneous acid catalysts is demonstrated via the hydrolysis of cyclohexyl acetate. Therein, it is shown that fine-tuning polymers has a dramatic effect on their catalytic performance and allows for the identification of key catalyst properties for optimal conversion.

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“…[30] Schukraft et al reported a triazine ring-containing HCPs platform with similar photocatalytic performance toward CO 2 photoreduction to commercial P25 owing to the selective adsorption. [31] Although there are numerous reports of HCPs achieving great progress in the fields of CO 2 capture and storage, their photocatalytic applications for CO 2 conversion are restricted by the low quantum efficiency, relative to semiconductor photocatalysts like TiO 2 , due to the blocked conjugated structure by crosslinked methylene agent. [32,33] To combine the advantages of HCPs and TiO 2 photocatalyst, in the previous work, we proposed an in situ knitting strategy for constructing HCPs on TiO 2 surface using the functionalized graphene (FG) skeleton to provide the open phenyl group for covalent linking with syn-PhPh 3 .…”

Section: Introductionmentioning

confidence: 99%

Grafting Hypercrosslinked Polymers on TiO₂ Surface for Anchoring Ultrafine Pd Nanoparticles: Dramatically Enhanced Efficiency and Selectivity toward Photocatalytic Reduction of CO₂ to CH₄

Zhan

Wang

Huang

et al. 2021

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Metal deposition with photocatalyst is a promising way to surmount the restriction of fast e−/h+ recombination to improve the photocatalytic performance. However, the improvement remains limited by the existing strategies adopted for depositing metal particles due to the serious aggregation and large unconnected area on photocatalyst surface. Here, a strategy is proposed by directly grafting hypercrosslinked polymers (HCPs) on TiO2 surface to construct Pd‐HCPs‐TiO2 composite with uniform dispersion of ultrafine Pd nanoparticles on HCPs surface. This composite with surface area of 373 m2 g−1 exhibits improved photocatalytic CO2 conversion efficiency to CH4 with an evolution rate of 237.4 µmol g−1 h−1 and selectivity of more than 99.9%. The enhancement can be ascribed to the grafted porous HCPs with high surface area and N heteroatom on TiO2 surface for the stabilization of Pd nanoparticles, favoring the electron transfer and CO2 adsorption for selective CH4 production. This strategy may hold the promise for design and construction of porous organic polymer with semiconductor for efficient photocatalytic conversion.

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Hypercrosslinked Polymers as a Photocatalytic Platform for Visible‐Light‐Driven CO₂Photoreduction Using H₂O

Cited by 51 publications

References 43 publications

Covalent Microporous Polymer Nanosheets for Efficient Photocatalytic CO₂ Conversion with H₂O

Covalent Microporous Polymer Nanosheets for Efficient Photocatalytic CO₂ Conversion with H₂O

A One-Pot Route to Fine-Tuned Hypercrosslinked Polymer Solid Acid Catalysts

Grafting Hypercrosslinked Polymers on TiO₂ Surface for Anchoring Ultrafine Pd Nanoparticles: Dramatically Enhanced Efficiency and Selectivity toward Photocatalytic Reduction of CO₂ to CH₄

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Hypercrosslinked Polymers as a Photocatalytic Platform for Visible‐Light‐Driven CO2Photoreduction Using H2O

Cited by 51 publications

References 43 publications

Covalent Microporous Polymer Nanosheets for Efficient Photocatalytic CO2 Conversion with H2O

Covalent Microporous Polymer Nanosheets for Efficient Photocatalytic CO2 Conversion with H2O

A One-Pot Route to Fine-Tuned Hypercrosslinked Polymer Solid Acid Catalysts

Grafting Hypercrosslinked Polymers on TiO2 Surface for Anchoring Ultrafine Pd Nanoparticles: Dramatically Enhanced Efficiency and Selectivity toward Photocatalytic Reduction of CO2 to CH4

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Hypercrosslinked Polymers as a Photocatalytic Platform for Visible‐Light‐Driven CO₂Photoreduction Using H₂O

Covalent Microporous Polymer Nanosheets for Efficient Photocatalytic CO₂ Conversion with H₂O

Covalent Microporous Polymer Nanosheets for Efficient Photocatalytic CO₂ Conversion with H₂O

Grafting Hypercrosslinked Polymers on TiO₂ Surface for Anchoring Ultrafine Pd Nanoparticles: Dramatically Enhanced Efficiency and Selectivity toward Photocatalytic Reduction of CO₂ to CH₄