Thiophene-Bridged Donor-Acceptor sp2-Carbon-Linked 2D Conjugated Polymers as Photocathodes for Water Reduction

Photoelectrochemical (PEC) water reduction, converting solar energy into environmentally friendly hydrogen fuel, requires delicate design and synthesis of semiconductors with appropriate bandgaps, suitable energy levels of the frontier orbitals, and high intrinsic charge mobility. In this work, the synthesis of a novel bithiophene‐bridged donor–acceptor‐based 2D sp²‐carbon‐linked conjugated polymer (2D CCP) is demonstrated. The Knoevenagel polymerization between the electron‐accepting building block 2,3,8,9,14,15‐hexa(4‐formylphenyl) diquinoxalino[2,3‐a:2′,3′‐c]phenazine (HATN‐6CHO) and the first electron‐donating linker 2,2′‐([2,2′‐bithiophene]‐5,5′‐diyl)diacetonitrile (ThDAN) provides the 2D CCP‐HATNThDAN (2D CCP‐Th). Compared with the corresponding biphenyl‐bridged 2D CCP‐HATN‐BDAN (2D CCP‐BD), the bithiophene‐based 2D CCP‐Th exhibits a wide light‐harvesting range (up to 674 nm), a optical energy gap (2.04 eV), and highest energy occupied molecular orbital–lowest unoccupied molecular orbital distributions for facilitated charge transfer, which make 2D CCP‐Th a promising candidate for PEC water reduction. As a result, 2D CCP‐Th presents a superb H₂‐evolution photocurrent density up to ≈7.9 µA cm⁻² at 0 V versus reversible hydrogen electrode, which is superior to the reported 2D covalent organic frameworks and most carbon nitride materials (0.09–6.0 µA cm⁻²). Density functional theory calculations identify the thiophene units and cyano substituents at the vinylene linkage as active sites for the evolution of H₂.

Original publication:

Shunqi Xu, Hanjun Sun, Matthew Addicoat, Bishnu P. Biswal, Fan He, SangWook Park, Silvia Paasch, Tao Zhang, Wenbo Sheng, Eike Brunner, Yang Hou, Marcus Richter, Xinliang Feng. Thiophene‐Bridged Donor–Acceptor sp²‐Carbon‐Linked 2D Conjugated Polymers as Photocathodes for Water Reduction.

Advanced Materials, 2020, DOI: 10.1002/adma.202006274

This work was supported financially by the DFG for the CRC 1415 (No. 417590517), the ERC Consolidator Grant (T2DCP, No. 819698), Coordination Networks: Building Blocks for Functional Systems (SPP 1928, COORNET), EU Graphene Flagship (GrapheneCore3; No. 881603), H2020‐MSCA‐ITN (ULTIMATE, No. 813036), and Center of Advancing Electronics Dresden (cfaed).