Heterogenization of homogeneous photocatalysts utilizing synthetic and natural support materials

Mak, Chun Hong; Han, Xu; Du, Minshu; Kai, Ji‐Jung; Tsang, Kim Fung; Jia, Guohua; Cheng, Kuan‐Chen; Shen, Hsin‐Hui; Hsu, Hsien‐Yi

doi:10.1039/d0ta08334h

Cited by 72 publications

(41 citation statements)

References 210 publications

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“…However, to our knowledge, no heterogenization approach exists with broad scope both in the kinds of dyes incorporated and in the types of catalytic materials accessible. Although several examples of photocatalyst immobilization on insoluble solids have been demonstrated 21 , each strategy addresses only a small subset of chromophore structures, and the vast majority of supported catalysts lack solution-processability, severely limiting the operational modes that are available (typically only particles or dispersions).…”

Section: Introductionmentioning

confidence: 99%

“…First, the solubility of organic polymers enables simple characterization of structure, molecular weight distribution, photocatalyst loading, defect concentration, and batch-to-batch quality variations, all of which are often impractical to analyze for conventional insoluble catalysts. Second, traditional materials relying on non-covalent interactions for dye attachment, or labile covalent bonds such as Si–O or Al–O bonds, can exhibit poor chemical stability 21 . In contrast, the polymers developed in this work exhibit exceptional thermal stability and inertness toward a variety of chemical conditions.…”

Section: Introductionmentioning

confidence: 99%

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Solution-processable microporous polymer platform for heterogenization of diverse photoredox catalysts

et al. 2022

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In contemporary organic synthesis, substances that access strongly oxidizing and/or reducing states upon irradiation have been exploited to facilitate powerful and unprecedented transformations. However, the implementation of light-driven reactions in large-scale processes remains uncommon, limited by the lack of general technologies for the immobilization, separation, and reuse of these diverse catalysts. Here, we report a new class of photoactive organic polymers that combine the flexibility of small-molecule dyes with the operational advantages and recyclability of solid-phase catalysts. The solubility of these polymers in select non-polar organic solvents supports their facile processing into a wide range of heterogeneous modalities. The active sites, embedded within porous microstructures, display elevated reactivity, further enhanced by the mobility of excited states and charged species within the polymers. The independent tunability of the physical and photochemical properties of these materials affords a convenient, generalizable platform for the metamorphosis of modern photoredox catalysts into active heterogeneous equivalents.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Solution-processable microporous polymer platform for heterogenization of diverse photoredox catalysts

et al. 2022

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“…24,44 An important question is whether such axial-coordination is still beneficial to the activity of CoPc-P4VP/GP/GCE systems. In our systems with added GP, strong interaction between the CoPc and the GP particles are likely necessary to facilitate efficient charge transport, 33,56,59,60 and these CoPc-GP interaction might be inhibited by axial coordination of the CoPc to the polymer or other pyridyl species. To help address this question, we measured the activity and selectivity of the CO2RR as we modulated the extent of axial coordination through systematic modifications of the CoPc-polymer-GP system.…”

Section: Resultsmentioning

confidence: 97%

Enhancing Electrochemical Carbon Dioxide Reduction by Polymer-Encapsulated Cobalt Phthalocyanine through Incorporation of Graphite Powder

Soucy

Liu

Eisenberg

et al. 2021

Preprint

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Cobalt phthalocyanine (CoPc) has been extensively studied as a catalyst for the electrochemical reduction of CO2 to value-added products. Previous studies have shown that CoPc is a competent and efficient catalyst when immobilized onto carbon-based electrodes using a polymer binder, especially when immobilized with a graphitic carbon powder support to increase charge transport. In this study, we systematically explore the influence of incorporating graphite powder (GP) into a polymer-encapsulated CoPc on the system’s activity for the electrochemical reduction of CO2. We report a protocol for incorporating GP into CoPc/polymer/GP catalyst films that facilitates physisorption of CoPc to GP, leading to increased activity for CO2 reduction. We show that the activity for CO2 reduction increases with GP loading at low GP loadings, but at sufficiently high GP loadings the activity plateaus as charge transfer is sufficiently fast to no longer be rate limiting. We also demonstrate that axial coordination is still important even in the presence of GP, suggesting that CoPc does not fully coordinate to heteroatoms on the GP surface. We develop a set of optimized conditions under which the CoPc/polymer/GP catalyst systems reduce CO2 with higher activity and similar selectivity to previously reported CoPc/polymer films on edge-plane graphite electrodes. The procedures outlined in this study will be used in future studies to optimize catalyst, polymer, and carbon support loadings for other polymer-catalyst composite systems for electrocatalytic transformations.

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“…Post-annealing modication is always an effective method for changing the surface and bulk properties of photoelectrodes. In this section, gas-based annealing under various atmospheres, such as H 2 , 7,98-107 NH 3 , 18,108-114 N 2 , [115][116][117] Ar, 118,119 CO, 120 O 2 , 24,121,122 and (NH 4 ) 2 S, 123 and other unique annealing techniques including solid-based annealing, employing S, 124 Mg 16 and Zn, 125,126 and ame annealing 11,127 as well as vacuum annealing 21,128 have been introduced. It should be noted that this section does not include studies of the two-step annealing process, for instance, dip-coating followed by annealing, 129 to avoid complexity and confusion.…”

Section: Post-annealing Treatmentsmentioning

confidence: 99%

Recent progress on post-synthetic treatments of photoelectrodes for photoelectrochemical water splitting

et al. 2021

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Heterogenization of homogeneous photocatalysts utilizing synthetic and natural support materials

Abstract: Homogeneous photocatalysis has considerably contributed to green applications such as energy production and environmental decontamination.

Cited by 72 publications

References 210 publications

Solution-processable microporous polymer platform for heterogenization of diverse photoredox catalysts

Solution-processable microporous polymer platform for heterogenization of diverse photoredox catalysts

Enhancing Electrochemical Carbon Dioxide Reduction by Polymer-Encapsulated Cobalt Phthalocyanine through Incorporation of Graphite Powder

Recent progress on post-synthetic treatments of photoelectrodes for photoelectrochemical water splitting

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