Triazine-Based Conjugated Microporous Polymers for Efficient Hydrogen Production

Abstract

Developing visible-light-active porous organic polymers with high photocatalytic efficiency is highly desirable. Here, two triazine-based conjugated microporous polymers were synthesized. The structures were controllably adjusted to explore the structure–photocatalytic activity relationship. T-CMP-1 containing more triazine units exhibited a hydrogen evolution rate of 3214.3 μmol h–1 g–1, much higher than that of T-CMP-2 (242.1 μmol h–1 g–1). The increasing contents of triazine units bring better hydrogen evolution efficiency.

Finding the Sweet Spot of Photocatalysis─A Case Study Using Bipyridine-Based CTFs

“…A series of periodic copolymers with the desired quantity and positioning of the dopant in the material were adjusted by the stoichiometric ratio of diamidine and dialdehyde in a 2:1 ratio for in situ polycondensation of the triazine linkage (Figure a). This polycondensation approach, recently reported by Cooper, Tan, and co-workers, provides superior control compared with the well-established ionothermal CTF synthesis, paving the way to master the desired building block sequence in the bipyridine-containing CTF family by applying the principle of orthogonal chemistry. , However, so far, only a few CTFs obtained by polycondensation are reported, mostly limited to functionalized aromatic aldehydes and nonfunctionalized terephthalamidine or [1,1′-biphenyl]-4,4′-bis­(carboximidamide). − Here, we employed bipyridine and biphenyl aromatic cores as n-doping and nondoping moieties, respectively (Figure ). Since the aromatic dialdehydes are commercially available, the synthesis of CTFs started with preparing 5,5′-diamidine-2,2′-bipyridine dihalide and 4,4′-biphenyldiamidine dihalide, adapting the previously established procedure …”

“…26,27 However, so far, only few CTFs obtained by polycondensation are reported, mostly limited to functionalized aromatic aldehydes and non-functionalised terephthalamidine or [1,1'-biphenyl]-4,4'-bis(carboximidamide). [28][29][30][31][32] Here, we employed bipyridine and biphenyl aromatic cores as n-doping and non-doping moieties, respectively (Figure 1). Since the aromatic dialdehydes are commercially available, the synthesis of CTFs started with preparing 5,5'-diamidine-2,2'-bipyridine dihalide and 4,4'-biphenyldiamidine dihalide, adapting the previously established procedure.…”

Polymer Photoelectrodes for Solar Fuel Production: Progress and Challenges

“…The progress of OPV, the limitations of inorganic metal oxides, and the urgent need for sustainable fuels have triggered the reconsideration of a wide range of materials for solar-driven catalysis, including polymer photoelectrodes. Recently, the fabrication of polymer photocathodes using CN x , covalent organic frameworks (COFs), metal–organic frameworks (MOFs), conjugated triazine frameworks (CTFs), and graphene have been explored for solar fuel synthesis. Notably, tuning the optical and catalytic properties by altering the synthesis conditions dramatically enhanced the PEC performances .…”

Porous organic polymers for drug delivery: hierarchical pore structures, variable morphologies, and biological properties

“…24 Based on the differences in their synthetic methods and structures, POPs can be divided into covalent organic frameworks (COFs), 25,26 hypercrosslinked polymers (HCPs), 27,28 polymers of intrinsic microporosity (PIMs), 29,30 porous aromatic frameworks (PAFs), 31,32 and conjugated microporous polymers (CMPs). 33,34 HCPs, PIMs, PAFs, and CMPs are amorphous, whereas COFs are highly crystalline.…”