The effect of molecular structure and fluorination on the properties of pyrene-benzothiadiazole-based conjugated polymers for visible-light-driven hydrogen evolution

Cheng, Chang; Wang, Xunchang; Lin, Yun; He, Luying; Jiang, Jia‐Xing; Xu, Yunfeng; Wang, Feng

doi:10.1039/c8py00722e

Cited by 60 publications

(35 citation statements)

References 57 publications

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“…[29] Similar studies also reflect this, whereby the measured surface area showed no relationship to photocatalytic activity. [33,[103][104][105][106][107] Figure 5. Cryo-transmission electron microscopy images of NP HEPs formed from a 3:7 blend of the polymer PTB7-Th (12) and the nonfullerene acceptor EH-IDTBR (13) with 10 wt% photodeposited Pt cocatalyst after 20 h H 2 evolution.…”

Section: Conjugated Network Polymers For Hydrogen Evolutionmentioning

confidence: 99%

“…[108,109,111] This branching can have the effect of reducing planarity and decreasing the extent of conjugation, hence widening the optical bandgap, leading to poorer utilization of visible light and diminished photocatalytic activity. The reduced planarity in polymer backbones caused by high degrees of torsion also impedes intramolecular charge transport along the backbone, [104,109,111] given that conjugated network polymers with greater adjacent unit planarity have improved intramolecular charge transport. [112,113] Taken together, this could explain how the advantages of porosity can be outweighed by these other factors, and contorted porous network polymers are often less photocatalytically active than their low or nonporous linear polymer equivalents.…”

Section: Conjugated Network Polymers For Hydrogen Evolutionmentioning

confidence: 99%

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Photocatalysts Based on Organic Semiconductors with Tunable Energy Levels for Solar Fuel Applications

Koščo

Moruzzi

Willner

et al. 2020

Advanced Energy Materials

116

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development of sustainable energy sources. [1] Among these, solar energy has the greatest potential, with more solar energy irradiating the surface of the Earth in one hour than human society consumes in one year. [2] However, the intermittency of solar energy limits its utility. In order for solar energy to provide power on a scale commensurate with that currently generated from fossil fuels, it must be stored and supplied to users on demand. [3] On short timescales (seconds to days) this is possible to achieve using batteries, which can store electricity generated from solar photovoltaics. [4,5] However, the expensive materials required and their relatively high rates of self-discharge make batteries unsuitable for seasonal energy storage. [6,7] Storing solar energy in the chemical bonds of a fuel, which can be stored indefinitely at low cost, transported, and converted to electrical or heat energy on demand is therefore highly desirable. Solar fuels such as H 2 , CH 3 OH, and CH 4 can be generated from abundant and renewable feedstocks such as water and CO 2 using semiconductor photocatalysts. The vast majority of research to date has focused on photocatalysts fabricated from wide bandgap semiconductors such as TiO 2 , [8] SrTiO 3 , [9] and carbon nitride (CN). [10-14] Photocatalysts based on some of these semiconductors have achieved operational stabilities exceeding 1000 h and maximum external quantum efficiencies (EQEs) of over 50% for overall water splitting. [9,15-18] However, their wide and difficult to tune bandgaps mean that photocatalysts fabricated from these semiconductors are almost exclusively active at UV wavelengths, which carry <5% of solar energy. [19] This fundamentally limits their efficiency below what is required for many practical solar fuels applications. For example, an estimated solar-to-hydrogen efficiency (η STH) of 5-10% would be required to photocatalytically produce H 2 at a cost that meets the U.S. Department of Energy's target of $2-4 kg −1 , which is difficult or impossible to achieve with the aforementioned wide bandgap semiconductors. [20] This has stimulated interest in developing novel photocatalysts based on semiconductors with narrower bandgaps that are able to absorb a greater proportion of the solar spectrum and can therefore achieve higher maximum theoretical solar energy conversion efficiencies. [18] Among these, non-CN organic semiconductors have recently gained prominence due to the Earth abundance of their constituent elements, and their high extinction coefficients and The photocatalytic synthesis of solar fuels such as hydrogen and methane from water and carbon dioxide is a promising strategy to store abundant solar energy in order to overcome its intermittency. Although this approach has been studied for decades using inorganic semiconductor photocatalysts, organic semiconductors have only recently gained notable attention. The tunable energy levels of organic semiconductors can enable the design of photocatalysts with optimized solar light utilization. However,...

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Section: Conjugated Network Polymers For Hydrogen Evolutionmentioning

confidence: 99%

Section: Conjugated Network Polymers For Hydrogen Evolutionmentioning

confidence: 99%

Photocatalysts Based on Organic Semiconductors with Tunable Energy Levels for Solar Fuel Applications

Koščo

Moruzzi

Willner

et al. 2020

Advanced Energy Materials

116

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“…Recently, Wang et al. also developed novel CPs combining pyrene and BT units with either linear or porous networks for hydrogen production and investigated the effects of fluorine substitution on the polymer backbone . Surprisingly, the linear non‐fluorinated polymer (L−PyBT) showed an excellent HER of 1,674 μmol h −1 g −1 with an AQY of 10.3 % at 420 nm under visible light.…”

Section: Conjugated Linear Polymers Containing a Donor‐acceptor (D‐a)mentioning

confidence: 99%

Recent Advances in Visible‐Light‐Driven Hydrogen Evolution from Water using Polymer Photocatalysts

2020

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Efficient polymer photocatalysts that mimic natural photosynthesis to generate H 2 through the visible-light-promoted splitting of water are ideal systems for the conversion of solar energy into usable fuel with high energy density and in an environmentally friendly manner. In this article, we review recent reports on donor-acceptor-based π-conjugated polymers as photocatalysts, including conjugated linear polymers, microporous polymers, triazine frameworks, covalent organic frameworks, polymer dots, and other related organic polymers, which show superior photocatalytic activity and robust stability under visible-light irradiation, for hydrogen production. Moreover, their syntheses and material design strategies, photophysical properties, proposed mechanisms, and applications are systematically summarized. Finally, recent research on and challenges related to organic polymer photocatalysts are discussed. This minireview will help readers to more easily understand the recent advances in and future direction of this field.

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“…1D linear polymers show enhanced conductive performance and higher charge‐transmission ability along the 1D polymer backbone than 3D polymers, and thus exhibit higher photocatalytic activity. The introduction of functional groups (e.g., O=S=O, NH 2 , F, and CN) could modify the surface chemistry and the energy band structure of organic polymer photocatalysts, which significantly affect the photocatalytic performance. Considering the diverse structural variations, flexible molecular design, and wide number of organic building blocks, further improvement in photocatalytic activity for hydrogen generation could be expected by porous organic polymer photocatalysts.…”

Section: Introductionmentioning

confidence: 99%

Bisulfone‐Functionalized Organic Polymer Photocatalysts for High‐Performance Hydrogen Evolution

et al. 2019

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Conjugated polymers show great potential in the application of photocatalysis, particularly for the photoreduction reaction of water to generate hydrogen. Molecular structure design is a key part for building a high‐performance organic photocatalyst. Herein, two bisulfone‐containing conjugated polymer photocatalysts were constructed with 1D or 3D polymer structures, and the effect of polymer geometry on photocatalytic activity was studied. It was found that the linear polymer PySEO‐1 exhibited increased photocatalytic performance compared with the 3D polymer network PySEO‐2 because the enhanced coplanarity of the polymeric chain in PySEO‐1 promoted the photogenerated charge‐carrier transmission along the 1D main chain. As a result, an attractive hydrogen generation rate of 9477 μmol h−1 g−1 was obtained with PySEO‐1 under broadband light irradiation. PySEO‐1 also exhibited a high external quantum efficiency of 4.1 % at an incident light wavelength of 400 nm, demonstrating that the bisulfone‐containing polymers are attractive as organic photocatalysts for hydrogen production.

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The effect of molecular structure and fluorination on the properties of pyrene-benzothiadiazole-based conjugated polymers for visible-light-driven hydrogen evolution

Abstract: The linear non-fluorinated polymer L-PyBT exhibited an impressive hydrogen evolution rate up to 83.7 μmol h−1 under visible light irradiation.

Cited by 60 publications

References 57 publications

Photocatalysts Based on Organic Semiconductors with Tunable Energy Levels for Solar Fuel Applications

Photocatalysts Based on Organic Semiconductors with Tunable Energy Levels for Solar Fuel Applications

Recent Advances in Visible‐Light‐Driven Hydrogen Evolution from Water using Polymer Photocatalysts

Bisulfone‐Functionalized Organic Polymer Photocatalysts for High‐Performance Hydrogen Evolution

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