Rational design of covalent heptazine framework photocatalysts with high oxidation ability through reaction-dependent...

Due to structural tunability, high surface area, abundant pore structures, and abundant active sites, covalent heptazine frameworks (CHFs) constructed from heptazine and other molecular blocks are especially prominent. Here, we proposed a reaction-dependent strategy for designing two dimensional CHFs including high-throughput precursors screening, structure generation, and performance evaluation. Assuming that oxamide-like precursors can undergo the same thermal polymerization reaction as producing C₆N₇, seven precursors were screened from more than 10⁹ molecules in the ZINC20 database in terms of molecular weight, number of substructures, shape index, and symmetry. Furthermore, CHF-L1 to CHF-L7 were constructed from urea and the seven precursors according to the topologically assembling scheme in thermal polymerization. The designed CHFs had band gaps ranging from 1.89 to 3.10 eV. Among them, CHF-L3 assembled structurally by urea and 1,2,4,5-tetrazine-3,6-dicarboxamide with the smallest bandgap and an oxidative potential bias of 1.38 V for oxygen evolution reaction was screened as the candidate with high oxidative ability. The negative formation energy based on the synthesis route indicated the synthetic feasibility of CHF-L3, and negative cohesive energy as well as the stable structure under ab initio molecular dynamics simulations confirmed the stability of CHF-L3. The present work is expected to provide a powerful design strategy for two-dimensional CHFs design and is broadly applicable to various computational covalent organic framework design systems and experimental studies.