Structurally Diverse Covalent Triazine-Based Framework Materials for Photocatalytic Hydrogen Evolution from Water

A structurally
diverse family of 39 covalent triazine-based framework materials (CTFs) are synthesized by Suzuki–Miyaura
polycondensation and tested as hydrogen evolution photocatalysts using
a high-throughput workflow. The two best-performing CTFs are based
on benzonitrile and dibenzo­[b,d]­thiophene
sulfone linkers, respectively, with catalytic activities that are
among the highest for this material class. The activities of the different
CTFs are rationalized in terms of four variables: the predicted electron
affinity, the predicted ionization potential, the optical gap, and
the dispersibility of the CTFs particles in solution, as measured
by optical transmittance. The electron affinity and dispersibility
in solution are found to be the best predictors of photocatalytic
hydrogen evolution activity.

本研究通过铃木-宫浦缩聚反应合成了39种结构多样的共价三嗪基框架材料（covalent triazine-based framework materials，CTFs）系列，并采用高通量工作流程将其作为产氢光催化剂开展测试。性能最优的两种CTFs分别以苯甲腈和二苯并[b,d]噻吩砜作为连接基元，其催化活性处于该类材料的顶尖水平。不同CTFs的催化活性可通过四个变量进行合理化阐释：预测电子亲和能、预测电离势、光学带隙，以及通过透光率表征的CTFs颗粒在溶液中的分散性。研究发现，电子亲和能与溶液分散性是预测该类材料光催化产氢活性的最优指标。