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Conjugated Polymers with Oligoethylene Glycol Side Chains for Improved Photocatalytic Hydrogen Evolution.

ABSTRACT: Conjugated polymers are emerging as promising organic photocatalysts for hydrogen evolution from water. However, it is still very challenging for conjugated polymers to realize highly efficient photocatalytic hydrogen evolution. Herein, we demonstrate an efficient strategy of hydrophilic side chain functionalization to boost the hydrogen evolution rates of conjugated polymers. By functionalizing conjugated polymers with hydrophilic oligo (ethylene glycol) monomethyl ether (OEG) side chains, a 90-fold improvement in hydrogen evolution rate has been achieved than that of alkyl-functionalized conjugated polymer. It is found that the OEG side chains interact robustly with Pt co-catalysts, resulting in more efficient charge transfer. Moreover, OEG side chains in conjugated polymers can adsorb H⁺ from water, resulting in significantly lowered energy levels on the surfaces of conjugated polymers, which enables cascade energy levels and enhances charge separation and photocatalytic performance. Our results indicate that rational side-chain engineering could facilitate the design of improved organic photocatalysts for hydrogen evolution.

SUBMITTER: Hu Z

PROVIDER: S-EPMC6393733 | biostudies-literature | 2019 Mar

REPOSITORIES: biostudies-literature

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Conjugated Polymers with Oligoethylene Glycol Side Chains for Improved Photocatalytic Hydrogen Evolution.

Hu Zhicheng Z Wang Zhenfeng Z Zhang Xi X Tang Haoran H Liu Xiaocheng X Huang Fei F Cao Yong Y

iScience 20190215

Conjugated polymers are emerging as promising organic photocatalysts for hydrogen evolution from water. However, it is still very challenging for conjugated polymers to realize highly efficient photocatalytic hydrogen evolution. Herein, we demonstrate an efficient strategy of hydrophilic side chain functionalization to boost the hydrogen evolution rates of conjugated polymers. By functionalizing conjugated polymers with hydrophilic oligo (ethylene glycol) monomethyl ether (OEG) side chains, a 90 ...[more]

PMID: 30818223

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Project description:Semiconducting polymers are versatile materials for solar energy conversion and have gained popularity as photocatalysts for sunlight-driven hydrogen production. Organic polymers often contain residual metal impurities such as palladium (Pd) clusters that are formed during the polymerization reaction, and there is increasing evidence for a catalytic role of such metal clusters in polymer photocatalysts. Using transient and operando optical spectroscopy on nanoparticles of F8BT, P3HT, and the dibenzo[b,d]thiophene sulfone homopolymer P10, we demonstrate how differences in the time scale of electron transfer to Pd clusters translate into hydrogen evolution activity optima at different residual Pd concentrations. For F8BT nanoparticles with common Pd concentrations of >1000 ppm (>0.1 wt %), we find that residual Pd clusters quench photogenerated excitons via energy and electron transfer on the femto-nanosecond time scale, thus outcompeting reductive quenching. We spectroscopically identify reduced Pd clusters in our F8BT nanoparticles from the microsecond time scale onward and show that the predominant location of long-lived electrons gradually shifts to the F8BT polymer when the Pd content is lowered. While a low yield of long-lived electrons limits the hydrogen evolution activity of F8BT, P10 exhibits a substantially higher hydrogen evolution activity, which we demonstrate results from higher yields of long-lived electrons due to more efficient reductive quenching. Surprisingly, and despite the higher performance of P10, long-lived electrons reside on the P10 polymer rather than on the Pd clusters in P10 particles, even at very high Pd concentrations of 27000 ppm (2.7 wt %). In contrast, long-lived electrons in F8BT already reside on Pd clusters before the typical time scale of hydrogen evolution. This comparison shows that P10 exhibits efficient reductive quenching but slow electron transfer to residual Pd clusters, whereas the opposite is the case for F8BT. These findings suggest that the development of even more efficient polymer photocatalysts must target materials that combine both rapid reductive quenching and rapid charge transfer to a metal-based cocatalyst.

Project description:This paper describes effects of the flexibility, length, and branching of side chains on the mechanical properties of low-bandgap semiconducting polymers. The backbones of the polymer chains comprise a diketopyrrolopyrrole (DPP) motif flanked by two furan rings and copolymerized by Stille polycondensation with thiophene (DPP2FT). The side chains of the DPP fall into three categories: linear alkyl (C8, C14, or C16), branched alkyl (ethylhexyl, EH, or hexyldecyl, HD), and linear oligo(ethylene oxide) (EO3, EO4, or EO5). Polymers bearing C8 and C14 side chains are obtained in low yields and thus not pursued. Thermal, mechanical, and electronic properties are plotted against the number of carbon and oxygen atoms in the side chain. We obtain consistent trends in the thermal and mechanical properties for branched alkyl and linear oligo(ethylene oxide) side chains. For example, the glass transition temperature (T g) and elastic modulus decrease with increasing number of carbon and oxygen atoms, whereas the crack-onset strain increases. Among polymers with side chains of 16 carbon and oxygen atoms (C16, HD, and EO5), C16 exhibits the highest T g and the greatest susceptibility to fracture. Hole mobility, as measured in thin-film transistors, appears to be a poor predictor of electronic performance for polymers blended with [60]PCBM in bulk heterojunction (BHJ) solar cells. For example, while EO3 and EO4 exhibit the lowest mobilities (< 10-2 cm2 V-1 s-1) in thin-film transistors, solar cells made using these materials performed the best (efficiency > 2.6%) in unoptimized devices. Conversely, C16 exhibits the highest mobility (≈ 0.2 cm2 V-1 s-1) but produces poor solar cells (efficiency < 0.01%). We attribute the lack of correlation between mobility and power conversion efficiency to unfavorable morphology in the BHJ solar cells. Given the desirable properties measured for EO3 and EO4, the use of flexible oligo(ethylene oxide) side chains is a successful strategy to impart mechanical deformability to organic solar cells, without sacrificing electronic performance.

Dataset Information

Conjugated Polymers with Oligoethylene Glycol Side Chains for Improved Photocatalytic Hydrogen Evolution.

Publications

Conjugated Polymers with Oligoethylene Glycol Side Chains for Improved Photocatalytic Hydrogen Evolution.

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