Efficient Generation of Hydrogen Peroxide and Formate by an Organic Polymer Dots Photocatalyst in Alkaline Conditions

Wang, Sicong; Cai, Bin; Tian, Haining

doi:10.1002/ange.202202733

Cited by 7 publications

(6 citation statements)

References 35 publications

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“…Moreover, the combination of Pdots with catalase results in the protection of hydrogenase against damage up to 0.3% O 2 in the headspace (Figure S24b in the SI). 81,82 In this case, Pdots and MV 2+ probably reduce molecular oxygen into H 2 O 2 (Figure S24a), 83 while the catalase efficiently dismutates produced H 2 O 2 to half a molecule of O 2 and water as a side product (Section IV in the SI).…”

Section: Preparation Of Pdotsmentioning

confidence: 99%

Polymer Dots as Photoactive Membrane Vesicles for [FeFe]-Hydrogenase Self-Assembly and Solar-Driven Hydrogen Evolution

et al. 2022

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A semiartificial photosynthesis approach that utilizes enzymes for solar fuel production relies on efficient photosensitizers that should match the enzyme activity and enable long-term stability. Polymer dots (Pdots) are biocompatible photosensitizers that are stable at pH 7 and have a readily modifiable surface morphology. Therefore, Pdots can be considered potential photosensitizers to drive such enzyme-based systems for solar fuel formation. This work introduces and unveils in detail the interaction within the biohybrid assembly composed of binary Pdots and the HydA1 [FeFe]-hydrogenase from Chlamydomonas reinhardtii. The direct attachment of hydrogenase on the surface of toroid-shaped Pdots was confirmed by agarose gel electrophoresis, cryogenic transmission electron microscopy (Cryo-TEM), and cryogenic electron tomography (Cryo-ET). Ultrafast transient spectroscopic techniques were used to characterize photoinduced excitation and dissociation into charges within Pdots. The study reveals that implementation of a donor−acceptor architecture for heterojunction Pdots leads to efficient subpicosecond charge separation and thus enhances hydrogen evolution (88 460 μmol H2 •g H2ase −1•h −1 ). Adsorption of [FeFe]-hydrogenase onto Pdots resulted in a stable biohybrid assembly, where hydrogen production persisted for days, reaching a TON of 37 500 ± 1290 in the presence of a redox mediator. This work represents an example of a homogeneous biohybrid system combining polymer nanoparticles and an enzyme. Detailed spectroscopic studies provide a mechanistic understanding of light harvesting, charge separation, and transport studied, which is essential for building semiartificial photosynthetic systems with efficiencies beyond natural and artificial systems.

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Section: Preparation Of Pdotsmentioning

confidence: 99%

Polymer Dots as Photoactive Membrane Vesicles for [FeFe]-Hydrogenase Self-Assembly and Solar-Driven Hydrogen Evolution

et al. 2022

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“… 34 − 36 Therefore, it is also likely that electron transfer to an active Pd site could also happen from an already protonated reduced polymer. 37 In this case, it is possible that the proton would transfer as well, as it has already been shown that BT sites will perform proton-coupled electron transfer reactions. 23 This certainly requires that the residual Pd be close enough to the active site.…”

Section: Results and Discussionmentioning

confidence: 99%

“…However, the reductive quenching of PFBT by SDs to form reduced PFBT also seems to be an important pathway with 20–30% quenching in 30% DEA and 40% in ascorbic acid. , We can also see a clear reductive quenching of PFBT in organic media with ascorbic acid (Figures S14–S15) since this is a condition with sufficiently acidic protons that the reduced polymer is expected to rapidly be protonated. This is even more likely with ascorbic acid as it will also release a proton as it decomposes after being oxidized and therefore works like a proton-coupled electron transfer (PCET) donor and not just a simple reductive agent. − Therefore, it is also likely that electron transfer to an active Pd site could also happen from an already protonated reduced polymer . In this case, it is possible that the proton would transfer as well, as it has already been shown that BT sites will perform proton-coupled electron transfer reactions .…”

Section: Results and Discussionmentioning

confidence: 99%

Role of the Benzothiadiazole Unit in Organic Polymers on Photocatalytic Hydrogen Production

Axelsson,

Xia,

Wang

et al. 2024

JACS Au

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Organic polymers based on the donor–acceptor structure are a promising class of efficient photocatalysts for solar fuel production. Among these polymers, poly(9,9-dioctylfluorene-alt-1,2,3-benzothiadiazole) (PFBT) consisting of fluorene donor and benzothiadiazole acceptor units has shown good photocatalytic activity when it is prepared into polymer dots (Pdots) in water. In this work, we investigate the effect of the chemical environment on the activity of photocatalysis from PFBT Pdots for hydrogen production. This is carried out by comparing the samples with various concentrations of palladium under different pH conditions and with different sacrificial electron donors (SDs). Moreover, a model compound 1,2,3-benzothiadiazole di–9,9-dioctylfluorene (BTDF) is synthesized to investigate the mechanism for protonation of benzothiadiazole and its kinetics in the presence of an organic acid–salicylic acid by cyclic voltammetry. We experimentally show that benzothiadiazole in BTDF can rapidly react with protons with a fitted value of 0.1–5 × 1010 M–1 s–1 which should play a crucial role in the photocatalytic reaction with a polymer photocatalyst containing benzothiadiazole such as PFBT Pdots for hydrogen production in acidic conditions. This work gives insights into why organic polymers with benzothiadiazole work efficiently for photocatalytic hydrogen production.

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“…Polymer dots (PDs) are typically cutting-edge nanosized polymeric materials (including conjugated PDs, carbonized PDs, etc.) that have attracted much attention because of their designable nanoarchitectural features, outstanding biocompatibility, tunable photoluminescent characteristics, and recyclability as nanophase . The common preparation methods for PDs, such as hydrothermal, nanoprecipitation, and miniemulsion, ordinarily lack in situ , real-time, and noncontact operability, and lack convenience from the perspective of material use.…”

Section: Introductionmentioning

confidence: 99%

“…PDs are typically formed by covalent or noncovalent bond linked nano-objects with polymer components up to a diameter of less than 10 nm. − Therefore, for a light-induced synthesis method, particle-template-confined photopolymerization might be valid. Template-confined reactions, which can usually be promoted by molecular aggregation and solid states, have played a powerful role in the construction of various supramolecular or nanoarchitectures, , where the preorganization of the reactants is required for minimal atom displacement during the breaking and making of bonds.…”

Section: Introductionmentioning

confidence: 99%

Highly Efficient Room-Temperature Light-Induced Synthesis of Polymer Dots: A Programming Control Paradigm of Polymer Nanostructurization from Single-Component Precursor

Zhang,

Li,

Luo

et al. 2023

J. Am. Chem. Soc.

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Polymer dots (PDs) have raised considerable research interest due to their advantages of designable nanostructures, high biocompatibility, versatile photoluminescent properties, and recyclability as nanophase. However, there remains a lack of in situ, real-time, and noncontact methods for synthesizing PDs. Here we report a rational strategy to synthesize PDs through a welldesigned single-component precursor (an asymmetrical donor− acceptor−donor′ molecular structure) by photoirradiation at ambient temperature. In contrast to thermal processes that normally lack atomic economy, our method is mild and successive, based on an aggregation-promoted sulfonimidization triggered by photoinduced delocalized intrinsic radical cations for polymerization, followed by photooxidation for termination with structural shaping to form PDs. This synthetic approach excludes any external additives, rendering a conversion rate of the precursor exceeding 99%. The prepared PDs, as a single entity, can realize the integration of nanocore luminescence and precursor-transferred luminescence, showing 41.5% of the total absolute luminescence quantum efficiency, which is higher than most reported PD cases. Based on these photoluminescent properties, together with the superior biocompatibility, a unique membrane microenvironmental biodetection could be exemplified. This strategy with programming control of the single precursor can serve as a significant step toward polymer nanomanufacturing with remote control, high-efficiency, precision, and real-time operability.

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Efficient Generation of Hydrogen Peroxide and Formate by an Organic Polymer Dots Photocatalyst in Alkaline Conditions

Cited by 7 publications

References 35 publications

Polymer Dots as Photoactive Membrane Vesicles for [FeFe]-Hydrogenase Self-Assembly and Solar-Driven Hydrogen Evolution

Polymer Dots as Photoactive Membrane Vesicles for [FeFe]-Hydrogenase Self-Assembly and Solar-Driven Hydrogen Evolution

Role of the Benzothiadiazole Unit in Organic Polymers on Photocatalytic Hydrogen Production

Highly Efficient Room-Temperature Light-Induced Synthesis of Polymer Dots: A Programming Control Paradigm of Polymer Nanostructurization from Single-Component Precursor

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