Significant improvement of photocatalytic hydrogen evolution of diketopyrrolopyrrole-based donor–acceptor conjugated polymers through side-chain engineering

Diao, Ruimin; Ye, Haonan; Yang, Zhicheng; Zhang, Shicong; Kong, Kangyi; Hua, Jianli

doi:10.1039/c9py01404g

Cited by 20 publications

(20 citation statements)

References 48 publications

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“…In another strategy, hydrophilic functional groups (e.g., ethylene glycol, carboxylic acid, amino and ionic electrolyte groups) are incorporated on the side-chain of hydrophobic CPs to intrinsically improve the hydrophilicity of the CPs 23 – 26 . Although all previous studies introduced such hydrophilic groups on the side-chains of CPs, the backbones of side-chain-engineered CPs are hydrophobic, similar to those of conventional CPs.…”

Section: Introductionmentioning

confidence: 99%

Main-chain engineering of polymer photocatalysts with hydrophilic non-conjugated segments for visible-light-driven hydrogen evolution

et al. 2022

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Photocatalytic water splitting is attracting considerable interest because it enables the conversion of solar energy into hydrogen for use as a zero-emission fuel or chemical feedstock. Herein, we present a universal approach for inserting hydrophilic non-conjugated segments into the main-chain of conjugated polymers to produce a series of discontinuously conjugated polymer photocatalysts. Water can effectively be brought into the interior through these hydrophilic non-conjugated segments, resulting in effective water/polymer interfaces inside the bulk discontinuously conjugated polymers in both thin-film and solution. Discontinuously conjugated polymer with 10 mol% hexaethylene glycol-based hydrophilic segments achieves an apparent quantum yield of 17.82% under 460 nm monochromatic light irradiation in solution and a hydrogen evolution rate of 16.8 mmol m −2 h −1 in thin-film. Molecular dynamics simulations show a trend similar to that in experiments, corroborating that main-chain engineering increases the possibility of a water/polymer interaction. By introducing non-conjugated hydrophilic segments, the effective conjugation length is not altered, allowing discontinuously conjugated polymers to remain efficient photocatalysis.

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Section: Introductionmentioning

confidence: 99%

Main-chain engineering of polymer photocatalysts with hydrophilic non-conjugated segments for visible-light-driven hydrogen evolution

et al. 2022

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“…Recently, organic photocatalysts have drawn much attention because of their structural diversity, mild synthesis conditions, and easy functionalization while comparing with their inorganic counterparts. The reported organic photocatalysts include covalent triazine-based frameworks, − linear polymers, − covalent organic frameworks (COFs), − and conjugated microporous polymers (CMPs), − and some of them show high hydrogen evolution rate (HER). Nevertheless, organic photocatalysts with HER larger than 8000 μmol g –1 h –1 are still rare.…”

Section: Introductionmentioning

confidence: 99%

Enhanced Photocatalytic Performance of Donor–Acceptor-Type Polymers Based on a Thiophene-Contained Polycyclic Aromatic Unit

et al. 2021

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Donor–acceptor (D–A)-type photocatalysts containing the polycyclic aromatic donor (BTT-CPP) and nonpolycyclic aromatic donor (TTB-CPP) are designed and synthesized. Their physicochemical properties are thoroughly investigated. The photocatalytic hydrogen generation experiments show that both polymers exhibit distinct photocatalytic performance. BTT-CPP displays an attractive hydrogen evolution rate (HER) of 37,866 μmol g–1 h–1 without further addition of the metal co-catalyst, one of the highest values reported for organic photocatalysts. The optimal HER of TTB-CPP is 8466 μmol g–1 h–1. These results highlight the important role of the donor unit on the performance of D–A-type photocatalysts and demonstrate that thiophene-contained polycyclic aromatic unit BTT is an excellent donor unit for high HER photocatalysts.

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“…As presented in Figure S4, Supporting Information, PFNH‐Br showed relatively narrow crystalline peaks at 2 θ = ≈19°, while broad peaks at around 20° are observed for PFN‐Br and PFPABr, likely due to the strong stacking of the conjugated backbone in the aggregate state of PFNH‐Br, respectively. [ 33 ]…”

Section: Resultsmentioning

confidence: 99%

“…As presented in Figure S4, Supporting Information, PFNH-Br showed relatively narrow crystalline peaks at 2θ ¼ %19°, while broad peaks at around 20°are observed for PFN-Br and PFPABr, likely due to the strong stacking of the conjugated backbone in the aggregate state of PFNH-Br, respectively. [33] The optical gaps (E opt,g ) of polyelectrolytes were evaluated from the onset of UV absorption edge and were calculated to be 2.86 eV for PFNH-Br, 2.88 eV for PFN-Br, and 2.84 eV for PFPABr, respectively. The types of grafted groups in the main chain of polyfluorene-based polyelectrolyte also influence their photoluminescence (PL) properties.…”

Section: Optical Propertiesmentioning

confidence: 99%

Grafted Groups’ Modification in the Main Chain of Polyfluorene‐Based Conjugated Polyelectrolytes to Greatly Boost Solar Hydrogen Production from Natural Seawater

Dai

Deng

et al. 2022

Adv Energy and Sustain Res

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Hydrogen represents an ideal fuel with environmental‐friendly properties and high energy density. It is attractive to directly produce clean hydrogen from inexhaustible solar energy and the most abundant seawater on the earth. Nevertheless, the search for highly efficient and stable photocatalysts remains a big challenge so far because of the dissolved salts in natural seawater, which may result in the decomposition of photocatalysts and undesirable side reactions. Herein, three polyfluorene‐based conjugated polyelectrolytes (CPEs) with different grafted groups in the polymer backbone for hydrogen production in natural seawater under solar light illumination are reported. The change in the grafted groups on the main chain of CPEs provides them very similar UV light absorption, but PFNH‐Br grafted with H group exhibits significantly improved charge transport and lower emission intensity compared with PFN‐Br (grafted with C8H17) and PFPABr (grafted with CH2CH2N(CH3)3Br). As a result, PFNH‐Br yield the highest hydrogen evolution rate (HER) of 1806 μmol h−1 g−1 without external cocatalysts under simulated solar light, while lower HERs of 356 and 225 μmol h−1 g−1 are found for PFN‐Br and PFPABr, respectively. This study shows that grafted group optimization is a powerful strategy to maximize the activity of polyfluorene‐based CPEs for direct photocatalytic seawater splitting.

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Significant improvement of photocatalytic hydrogen evolution of diketopyrrolopyrrole-based donor–acceptor conjugated polymers through side-chain engineering

Abstract: The hydrogen evolution rate of PDPP3B-O4 with butoxy chain was 5.53 mmol h−1 g−1 with 1% Pt loading (λ > 400 nm), increased 110 times than PDPP3B-C8 with octyl chain due to wider absorption spectrum and better wettability via side chain engineering.

Cited by 20 publications

References 48 publications

Main-chain engineering of polymer photocatalysts with hydrophilic non-conjugated segments for visible-light-driven hydrogen evolution

Main-chain engineering of polymer photocatalysts with hydrophilic non-conjugated segments for visible-light-driven hydrogen evolution

Enhanced Photocatalytic Performance of Donor–Acceptor-Type Polymers Based on a Thiophene-Contained Polycyclic Aromatic Unit

Grafted Groups’ Modification in the Main Chain of Polyfluorene‐Based Conjugated Polyelectrolytes to Greatly Boost Solar Hydrogen Production from Natural Seawater

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