Diketopyrrolopyrrole-Based Donor–Acceptor Conjugated Microporous Polymers for Visible-Light-Driven Photocatalytic Hydrogen Production from Water

Abstract

Developing efficient and wide spectrally acting photocatalysts for light-driven hydrogen production from water is highly desirable for solar energy conversion. Herein, diketopyrrolopyrrole (DPP) is used to combine with triphenylamine (TPA), bipyridyl (bdy), and biphenyl (bph) units for construction of conjugated microporous polymer photocatalysts. Although the synthesized two polymers, DPP-bdy-TPA and DPP-bph-TPA, have a similar framework structure, the former bearing a hydrophilic bipyridyl unit displays much better photocatalytic performance with hydrogen production rates of 6918 and 2780 μmol g–1 h–1 under a full-arc xenon lamp and visible light (>440 nm) illumination, respectively. Moreover, DPP-bdy-TPA has a wide photoaction spectrum with apparent quantum yields of 9.60% at 420 nm, 7.32% at 500 nm, and 0.31% at 600 nm, the so high values rarely achieved by present-known organic semiconductor photocatalysts. These results undoubtedly prove DPP is an excellent building block, and this work well exemplifies its utilization for construction of high-performance photocatalysts.

Vinylene‐Linked Covalent Organic Frameworks (COFs) with Symmetry‐Tuned Polarity and Photocatalytic Activity

“…Polarity is an attractive character in organic semiconducting molecules,which intrinsically affects their light harvesting, spin-orbital interaction, and photo-induced charge generation and separation. [1] Tu ning molecular polarity in order to boost thermally activated delayed fluorescence (TADF), enlarge absorption cross section, or enhance photo-induced charge separation, is awidely used strategy in organic light emitting diode, [2] two-photo absorption [3] or photocatalysis, [4] respec-tively.T he basic design of an organic molecule with strong dipole moment is to connect an electron-donating moiety (donor, D) with an electron-withdrawing moiety (acceptor, A) by a p-bridge. [5] However,s uch an asymmetric D-A combination tends towards an anti-parallel intermolecular arrangement and counteracts the molecular polarity in the bulk phase,w hich severely impairs the integral polarity and diminishes the material functionality.…”

Vinylene‐Linked Covalent Organic Frameworks (COFs) with Symmetry‐Tuned Polarity and Photocatalytic Activity

“…Polarity is an attractive character in organic semiconducting molecules,which intrinsically affects their light harvesting, spin-orbital interaction, and photo-induced charge generation and separation. [1] Tu ning molecular polarity in order to boost thermally activated delayed fluorescence (TADF), enlarge absorption cross section, or enhance photo-induced charge separation, is awidely used strategy in organic light emitting diode, [2] two-photo absorption [3] or photocatalysis, [4] respec-tively.T he basic design of an organic molecule with strong dipole moment is to connect an electron-donating moiety (donor, D) with an electron-withdrawing moiety (acceptor, A) by a p-bridge. [5] However,s uch an asymmetric D-A combination tends towards an anti-parallel intermolecular arrangement and counteracts the molecular polarity in the bulk phase,w hich severely impairs the integral polarity and diminishes the material functionality.…”

Nanoporous and nonporous conjugated donor–acceptor polymer semiconductors for photocatalytic hydrogen production

“…Motivated by the planar configuration and strong electronacceptor capability of diketopyrrolopyrrole (DPP) [59][60][61], Li and co-workers [62] combined DPP with triphenylamine and bipyridine groups to synthesize D-A polymers. A HER of 9.73 μmol•h −1 (3.5 mg) was achieved for P33 (Figure 4) due to the wide spectral range of the photoresponse.…”