Molecularly Tunable Heterostructured Co-Polymers Containing Electron-Deficient and -Rich Moieties for Visible-Light and Sacrificial-Agent-Free H2O2 Photosynthesis.

As an alternative to hydrogen peroxide (H2O2) production by complex anthraquinone oxidation process, photosynthesis of H2O2 from water and oxygen without sacrificial agents is highly demanded. Herein, a covalently connected molecular heterostructure is synthesized via sequential C-H arylation and Knoevenagel polymerization reactions for visible-light and sacrificial-agent-free H2O2 synthesis. The subsequent copolymerization of the electron-deficient benzodithiophene-4,8-dione (BTD) and the electron-rich biphenyl (B) and p-phenylenediacetonitrile (CN) not only expands the π-conjugated domain but also increases the molecular dipole moment, which largely promotes the separation and transfer of the photoinduced charge carriers. The optimal heterostructured BTDB-CN0.2 manifested an impressive photocatalytic H2O2 production rate of 1920 µmol g-1 h-1, which is 2.2 and 11.6 times that of BTDB and BTDCN. As revealed by the femtosecond transient absorption (fs-TA) and theoretical calculations, the linkage serves as a channel for the rapid transfer of photogenerated charge carriers, enhancing the photocatalytic efficiency. Further, in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) uncovers that the oxygen reduction reaction occurs through the step one-electron pathway and the mutual conversion between C=O and C-OH with the anchoring of H+ during the catalysis favored the formation of H2O2. This work provides a novel perspective for the design of efficient organic photocatalysts.

Promoting Solar-driven Hydrogen Peroxide Production over Thiazole-based Conjugated Polymers via Generating and Converting Singlet Oxygen.

Solar-driven synthesis of hydrogen peroxide (H2 O2 ) from water and air provides a low-cost and eco-friendly alternative route to the traditional anthraquinone method. Herein, four thiazole-based conjugated polymers (Tz-CPs: TTz, BTz, TBTz and BBTz) are synthesized via aldimine condensation. BBTz exhibits the highest H2 O2 production rate of 7274 µmol g-1 h-1 in pure water. Further, the reaction path is analyzed by electron paramagnetic resonance (EPR), in situ diffuse reflectance infrared Fourier transform (DRIFT) and theoretical calculation, highlighting the prominent role of singlet oxygen (1 O2 ). The generation of 1 O2 occurs through the oxidation of superoxide radical (⋅O2 - ) and subsequent conversion into endoperoxides via [4+2] cycloaddition over BBTz, which promotes charge separation and reduces the barrier for H2 O2 production. This work provides new insight into the mechanism of photocatalytic O2 reduction and the molecular design of superior single-polymer photocatalysts.

Correction: EDOT-based conjugated polymers accessed via C-H direct arylation for efficient photocatalytic hydrogen production.

[This corrects the article DOI: 10.1039/D1SC05784G.].

EDOT-based conjugated polymers accessed via C-H direct arylation for efficient photocatalytic hydrogen production.

3,4-Ethylene dioxythiophene (EDOT), as a monomer of commercial conductive poly(3,4-ethylene dioxythiophene) (PEDOT), has been facilely incorporated into a series of new π-conjugated polymer-based photocatalysts, i.e., BSO2-EDOT, DBT-EDOT, Py-EDOT and DFB-EDOT, through atom-economic C-H direct arylation polymerization (DArP). The photocatalytic hydrogen production (PHP) test shows that donor-acceptor (D-A)-type BSO2-EDOT renders the highest hydrogen evolution rate (HER) among the linear conjugated polymers (CPs) ever reported. A HER up to 0.95 mmol h-1/6 mg under visible light irradiation and an unprecedented apparent quantum yield of 13.6% at 550 nm are successfully achieved. Note that the photocatalytic activities of the C-H/C-Br coupling-derived EDOT-based CPs are superior to those of their counterparts derived from the classical C-Sn/C-Br Stille coupling, demonstrating that EDOT is a promising electron-rich building block which can be facilely integrated into CP-based photocatalysts. Systematic studies reveal that the enhanced water wettability by the integration of polar BSO2 with hydrophilic EDOT, the increased electron-donating ability by O-C p-π conjugation, the improved electron transfer by D-A architecture, broad light harvesting, and the nano-sized colloidal character in a H2O/NMP mixed solvent rendered BSO2-EDOT as one of the best CP photocatalysts toward PHP.

Novel Diketopyrrolopyrrole-Based π-Conjugated Molecules Synthesized Via One-Pot Direct Arylation Reaction.

Diketopyrrolopyrrole (DPP) is an important type of π-conjugated building block for high-performance organic electronic materials. DPP-based conjugated materials are usually synthesized via Suzuki, Stille, or Negishi cross-coupling reactions, which require organometallic precursors. In this paper, a series of novel phenyl-cored DPP molecules, including five meta-phenyl-cored molecules and four para-phenyl-cored molecules, have been synthesized in moderate to good yields, in a facile manner, through the Pd-catalyzed direct arylation of C-H bonds, and their optoelectrical properties have been investigated in detail. All new molecules have been fully characterized by NMR, MALDI-TOF MS, elemental analysis, UV-visible spectroscopy, and cyclic voltammetry. This synthetic strategy has evident advantages of atom- and step-economy and low cost, compared with traditional cross-coupling reactions.