On March 1, Nature Communications published online the latest findings of Prof. Wang Cheng’s team from the College of Chemistry and Molecular Sciences, Wuhan University (WHU). The research synthesized a series of 2D porphyrin-based covalent organic frameworks with the incorporation of different transition metals and realized tuning photocatalytic hydrogen evolution.

The paper is entitled Rational Design of Isostructural 2D Porphyrin-based Covalent Organic Frameworks for Tunable Photocatalytic Hydrogen Evolution. Dr. Chen Rufan (WHU), Dr. Wang Yang (Technical Institute of Physics and Chemistry) and doctoral candidate Ma Yuan (University of Science and Technology Beijing) are co-first authors of the paper, and Prof. Wang Cheng, Associate Researcher Li Xubin and Academician Wu Lizhu (Technical Institute of Physics and Chemistry) are co-corresponding authors.

Covalent organic frameworks (COFs), which find promising applications in a number of fields, are a sort of crystalline porous organic polymer composed of organic bases connected via covalent bonds. Owing to their unique layered stacking structure, growing attention is paid by researchers to COFs’ application in photocatalytic hydrogen generation. However, how to tune COFs’ structures rationally to promote hydrogen evolution rate remains to be explored. Therefore, there is a need to construct isostructural 2D COFs with tunable optoelectronic properties, to better consider their photocatalytic performances and demonstrate their structure-property-activity relationship from a molecular level.

During the study, Wang’s team designed and synthesized a series of isostructural  porphyrin-based COFs (MPor-DETH-COF, M = H2, Co2+, Ni2+, Zn2+) and cooperated with Academician Wu Lizhu and Associate Researcher Li Xubin’s team to examine the COFs’ photocatalytic performances. The results showed that all four isostructural porphyrin-based COFs, with high crystallinity and large surface area, feature very different photocatalytic performances. Detailed experiments on the mechanism revealed that the four COFs have different capacity of excited-state charge separation and the variation of their separations correspond with the results from photocatalytic hydrogen experiments (ZnPor-DETH-COF > NiPor-DETH-COF > H2Por-DETH-COF > CoPor-DETH-COF). Prof. Qiao Lijie’s team from the University of Science and Technology Beijing has offered a theoretical justification on the results.

This research received financial support from the National Natural Science Foundation of China, the Fundamental Research Funds for the Central Universities and the National Key R&D Research Program.

Link to the paper: https://doi.org/10.1038/s41467-021-21527-3

Rewritten by Zhang Ruoxi

Edited by Geng Jinwei