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Molecular Design of Two-Dimensional Covalent Heptazine Frameworks for Photocatalytic Overall Water Splitting under
Haiyun Wang1, Hao Cheng1, Haifeng Lv1
1School of Chemistry and Materials Sciences, CAS Key Lab of Materials for Energy Conversion, Synergetic Innovation of Quantum Information & Quantum Technology, and CAS Center for Excellence in Nanoscience, University of Science and Technology of China, Hefei, Anhui 230026, China.
Abstract:
Photocatalytic water splitting sustainably offers clean hydrogen energy, but it is challenging to produce low-cost photocatalysts that split water stoichiometrically into H2 and O2 without sacrificial agents under visible light. Here, we designed 17 two-dimensional (2D) covalent heptazine frameworks (CHFs) by topologically assembling heptazine and benzene-containing molecular units that provide active sites for hydrogen and oxygen evolution reactions, respectively. Among them, 12 CHFs have band gap values of <3.0 eV with band margins straddling the chemical reaction potential of H2/H+ and O2/H2O. In particular, a 2D H@DBTD CHF based on heptazine and 4,7-diphenyl-2,1,3-benzothiadiazole is a potential photocatalyst with a band gap of 2.47 eV for overall water splitting, which was confirmed with the calculated Gibbs free energy, non-adiabatic molecular dynamics, and preliminary experiment. This study presents an experimentally feasible molecular design of 2D CHFs as metal-free photocatalysts for overall water splitting under visible light.
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