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

Covalent triazine frameworks (CTFs) are a class of porous organic polymers that continuously attract growing interest because of their outstanding chemical and physical properties. However, the control of extended porous organic framework structures at the molecular scale for a precise adjustment of their properties has hardly been achieved so far. Here, we present a series of bipyridine-based CTFs synthesized through polycondensation, in which the sequence of specific building blocks is well controlled. The reported synthetic strategy allows us to tailor the physicochemical features of the CTF materials, including the nitrogen content, the apparent specific surface area, and optoelectronic properties. Based on a comprehensive analytical investigation, we demonstrate a direct correlation of the CTF bipyridine content with the material features such as the specific surface area, band gap, charge separation, and surface wettability with water. The entirety of these parameters dictates the catalytic activity as demonstrated for the photocatalytic hydrogen evolution reaction (HER). The material with the optimal balance between optoelectronic properties and highest hydrophilicity enables HER production rates of up to 7.2 mmol/(h.g) under visible light irradiation and in the presence of a platinum cocatalyst.

Automated summary

In this study, a series of bipyridine-based CTFs were synthesized with a well-controlled sequence of specific building blocks, allowing for the tailoring of physicochemical features. A direct correlation between the bipyridine content and material properties was demonstrated, and an optimal balance was found for photocatalytic hydrogen evolution reaction. Under visible light irradiation and in the presence of a platinum cocatalyst, the material exhibited high HER production rates.