Benzo[d][1,2,3]thiadiazole-Based Polymer Dots as Photocatalysts for Enhanced Efficiency and Stability of Photocatalytic Hydrogen Evolution under Visible Light Irradiation

Abstract

Organic conjugated polymer dots (Pdots) are emerging as a potential photocatalyst for hydrogen evolution from water. In this work, three organic semiconducting polymer dots (Pdots) based on benzo [d][1,2,3]thiadiazole (isoBT) and surfactant-based poly(ethylene oxide) chains (Triton) are presented as photocatalysts for visible-light-driven hydrogen generation in a completely solvent-free organic system. The resulting Pdots exhibit good photocatalytic activity and excellent photocatalytic stability. Achieving high efficiency with long-term photostability is important for the future commercialization of large-scale hydrogen production. Moreover, PG6 Pdots with a 1-chloro-4-fluorobenzene moiety showed high photocatalytic efficiency with high photocatalytic stability over 100 h. Thus, the introduction of a group with high electronegativity on isoBT-based Pdots is very beneficial for promising photocatalysts in terms of efficiency and stability, even though they could be used in a wide absorption range.

Donor–Acceptor β-Ketoenamine-Based Photocatalysts with a Tuning Band Structure for Selective Oxidation of a Biomass Derivative

“…The obvious chemical shift at 182–185 ppm verifies the generation of the carbonyl group in central β-ketene ring. For TpAn, TpABN, TpPy, and TpPym, the chemical shifts ranging from 98 to 150 ppm were observed, attributed to the carbon atom of the aromatic ring and cyan. , For TpBTD, the signals at 108.3–153.4 ppm are ascribed to the chemical shift of C in the benzo-2,1,3-thiadiazole unit. − In addition, high-resolution XPS was also utilized for clarifying the surface elemental (C, N, O, or S) states of samples. In the C 1s high-resolution XPS result of all samples (Figures S2 and S3), the three peaks at binding energies of 284.8, 286.2, and 288.3 eV are related with aromatic C, the C interacting with the N atom, and that in the carbonyl group, respectively. , The N 1s spectra of TpABN, TpPy, and TpPym show that the peaks at 399.7 and 398.6 eV correspond to the cyan group and −C–NH– linkage, respectively, while the single peak at 398.6 eV of the TpAn spectra implies its sole chemical state of the N element (−C–NH−) and the new peak at 399.1 eV for the N 1s spectra of TpBTD represents the C=N–S group of the 2,1,3-thiadiazole unit.…”

Naphthalenediimide‐Based Polymer Dots with Dual Acceptors as a New Class of Photocatalysts for Photocatalytic Hydrogen Generation under Visible Light Irradiation

“…For example, previous studies have shown that using surfactants such as Triton or PS‐PEG‐COOH and their derivatives to prepare Pdots can significantly improve their dispersibility in water. [ 14,37 ] The conjugated structures of Pdots play a crucial role in photocatalytic activity and efficiency, and naphthalenediimide‐based (NDI) derivatives are of particular interest due to their tunable photophysical properties and respectable charge transport capabilities.…”

3D-Printable and Robust All-in-One Polymer-Entangled Photocatalytic Microreactors for Visible-Light-Driven Hydrogen Evolution

“…However, inorganic photocatalysts aforementioned have been reported that to wash out of hydrogels during the photocatalytic reaction, , causing a loss in photocatalytic efficiency, and leading to the poor long-term stability of hydrogel-based reactors. Polymer photocatalysts are promising candidates for addressing this issue, with options such as linear polymer, − conjugated microporous polymers, − covalent organic frameworks, − and polymer dots. − Polymer photocatalysts have the potential to effectively entangle with hydrogels, minimizing catalyst loss, and improving stability. However, directly incorporating organic photocatalysts into conventional hydrogels may suffer from reduced photocatalytic efficiency as a result of anti-synergetic effects between the polymers and hydrogels.…”