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

Abstract

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.

Pathways towards Boosting Solar‐Driven Hydrogen Evolution of Conjugated Polymers

“…Similarly, the bisulfone and pyrene are copolymerized into 1D and 3D geometry via adjusting the pyrene-linking pattern. [95] The linear polymer PySEO-1 shows a slightly broader visible light absorption and better hydrogen production than PySEO-2.…”

Structure evolution of thiophene-containing conjugated polymer photocatalysts for high-efficiency photocatalytic hydrogen production

“…Compared with inorganic semiconductor materials, organic semiconductor materials recently attract more interest because of their flexible structural design, diverse synthetic strategies and tunable electronic properties [9][10][11][12][13][14]. To date, the developed organic polymer photocatalysts mainly include graphitic carbon nitrides [15][16][17], linear conjugated polymers [18][19][20][21][22], conjugated microporous polymers (CMPs) [23][24][25][26][27], crystalline covalent organic frameworks (COFs) [28][29][30][31] and covalent triazine-based frameworks (CTFs) [32][33][34][35].…”

Photocatalytic H2 Evolution from Ammonia Borane: Improvement of Charge Separation and Directional Charge Transmission

“…Hydrogen energy is a globally recognized clean energy, which helps to solve the energy crisis, achieves energy transformation, curbs global warming and environmental pollution, therefore, hydrogen energy development and utilization has attracted worldwide attention. [1][2][3][4][5][6] Hydrogen is difficult to store in the form of compression or liquefaction, which has become the main difficulty in establishing hydrogen economy. [7,8] Solid-state hydrogen storage is a kind of hydrogen storage method, which uses physical or chemical changes between hydrogen and hydrogen storage materials to store hydrogen.…”

“…[26][27][28][29] LDHs were widely used in environmental purification, energy storage, industrial catalysis and biomedicine. LDHs could be expressed by the general chemical formula 3 + represent metallic cations, and A nÀ represent the exchangeable interlayer anions. [26][27][28][29][30][31][32] The main structure of LDH is based on MO 6 octahedron shared by layered edges of brucite-like hydroxide layers, surrounded by oxo-bridges and hydroxy groups.…”

“…However, fossil energy is increasingly exhausted. Hydrogen energy is a globally recognized clean energy, which helps to solve the energy crisis, achieves energy transformation, curbs global warming and environmental pollution, therefore, hydrogen energy development and utilization has attracted worldwide attention . Hydrogen is difficult to store in the form of compression or liquefaction, which has become the main difficulty in establishing hydrogen economy .…”