Tricyclicquinazoline-Based Porous Organic Polymers For Functional Application And Structure Activity Relationship

Porous Organic polymers(POPs)are a new type of porous materials composed of organic building blocks connected by covalent bonds.POPs materials with impressive large surface areas,well-defined pore sizes,robust physicochemical stability,and flexible synthetic strategy have provided a new platform toward future multifunctional implementation of porous materials.From the perspective of application of synthetic POPs materials,we recognize that the reasonable structural design proposes the valid avenue toward specific functional property.To provide flexible design guidance for future functional exploration of POPs materials,the content of this paper is mainly divided into the following two aspects:1.We designed and synthetized a tricycloquinazoline-based 3D conjugated microporous polymer(TQ-CMP)anchoring Mo S2 on its surface by in-situ growth.The semiconductor property of the rigid conjugate plane of TQ-CMP was greatly enhanced by the delocalization effect of electrons.The rich porosity inside TQ-CMP can limit the overgrowth of Mo S2 and avoid the aggregation of nanosheets.In the electrochemical hydrogen evolution reaction,the excellent catalytic activity and faster reaction kinetics of TQ-CMP@Mo S2 2:1 are epitomized by the achieved lower overpotential of 71 m V and Tafel slope of 52 m V dec^-1.2.By tuning the geometry of N-rich skeleton TQ unit,the isomers of 3D amorphous conjugated microporous polymer(TQ-CMP)and 2D laminar covalent quinazoline network(TQ-CQN)were synthesized.Based on the rich-nitrogen,high conjugation degree and strong physicochemical stability of tricycloquinazoline(TQ),the derived diversity microstructure and electrical conductivity related to the applications of gas adsorption and hydrogen evolution reaction(HER)are systematically discussed.TQ-CMP fabricated with internal crosslinking network revealed notable CO2 uptakes of 25.6 wt%and at 273 K and1 bar,which could be attributed to the higher BET surface area(781.0 m² g^-1)and dispersed pore size(1.1 nm to 13.1 nm)for guest molecules absorption.As the electrochemical catalysis of HER,the ordered?-?stacked layered structure of TQ-CQN was more conducive to HER activity,with overpotential of 80 m V and a Tafel slope of 40m V dec^-1.This work not only clarified the interaction of microstructure and conductivity of porous organic polymers for gas adsorption and HER,but also proved flexible design guidance for future functional exploration.