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

Abstract

Organic conjugated polymer dots (Pdots) are emerging as promising photocatalysts for solar‐driven hydrogen production. However, organic solvents are commonly used as cosolvents in photocatalytic systems to promote the dispersion of organic materials and improve the overall efficiency of the photocatalytic process. Herein, two naphthalenediimide (NDI)‐based Pdots, with and without surfactant, are fabricated and presented as highly efficient and stable photocatalysts for visible‐light‐driven hydrogen generation in a solvent‐free organic system for the first time. The prepared Pdots exhibit high photocatalytic activity and remarkable photostability. Achieving high efficiency and long‐term photostability is essential for the future commercialization of large‐scale hydrogen production. Furthermore, the NDI‐BTF‐PS‐PEG‐COOH Pdots of the dual acceptor (A1‐D‐A2‐D system) consisting of a strong acceptor (NDI, A1) and a weak acceptor (BTF, A2), exhibited high photocatalytic efficiencies and stabilities with Pt‐cocatalyst over 72 hours. Thus, constructing A1‐D‐A2‐D NDI‐based Pdots is a promising approach to developing efficient and stable photocatalysts for solar‐driven hydrogen production.This article is protected by copyright. All rights reserved.

Influence of Vinyl Bridging on Transistor Properties of Naphthalenediimide-Based Dual-Acceptor Copolymers

“…All the commercially available reagents were purchased from Signa-Aldrich unless otherwise noted. The monomers including 2,7-bis­(8-(methyldioctylsilyl)­octyl)-4,9-bis­(tributylstannyl)­benzo­[lmn]­[3,8]­phenanthroline-1,3,6,8­(2H, 7H)-tetraone ( NDI ), 4,7-bis­(5-bromoselenophen-2-yl)-5,6-difluorobenzo­[c]­[1,2,5]­thiadiazole ( S ), and 4,7-bis­(5-bromo-selenophen-2-yl)-2-(2-ethylhexyl)-5,6-difluoro-2H-benzo­[d]­[1,2,3]­triazole ( N ) are synthesized based on the reported literature . The detailed synthesis of 2,7-bis­(8-(methyldioctylsilyl)­octyl)-4,9-bis­((E)-2-(tributylstannyl) vinyl)­benzo­[lmn]­[3,8]­phenanthroline-1,3,6,8­(2H,7H)-tetraone ( v-NDI ) is described in the Supporting Information, and the process is based on methods reported in the literature.…”

“…NDI-S/N was prepared according to methods reported in the literature . The monomers v-NDI, S / N , and the catalyst Pd­(PPh 3 ) 4 (5 mol % relative to v-NDI ) were added into a microwave vessel containing chlorobenzene (0.1 M).…”

“…This results in better planarity of the backbone when attached to highly planar vinyl-bonded NDI, which improves the resulting ambipolar charge carrier transport properties. 43 The detailed synthesis of 2,7bis(8-(methyldioctylsilyl)octyl)-4,9-bis((E)-2-(tributylstannyl) vinyl)benzo[lmn] [3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone (v-NDI) is described in the Supporting Information, and the process is based on methods reported in the literature.…”

“…NDI-S/N was prepared according to methods reported in the literature. 43 The monomers v-NDI, S/N, and the catalyst Pd(PPh 3 ) 4 (5 mol % relative to v-NDI) were added into a microwave vessel containing chlorobenzene (0.1 M). The vessel was then sealed in a nitrogen-filled glovebox, followed by a 90 min Stille coupling polymerization reaction at 160 °C under microwave heating.…”

Push–pull–pull interactions of 2D imide–imine-based covalent organic framework to promote charge separation in photocatalytic hydrogen production

“…26 Recently, our group reported that the incorporation of a donor into dual acceptor systems (D–A–A) offers a promising approach for overcoming the limitations of traditional photocatalysts in H 2 evolution. 27,28 Consequently, the D–A–A system, which results in the push–pull–pull approach able to enhance light absorption, suppress charge recombination, tune redox potentials, improve stability, and integrate with other systems, makes them a valuable tool for the development of efficient and sustainable solar-driven H 2 production technologies, while it is still rarely explored for COFs thus far. In this context, the incorporation of imide and imine moieties into 2D COFs was constructed for the first time while converting 1D ribbons into 2D COFs but without a further study of the catalytic applications.…”