Constructing tightly integrated conductive metal-organic framework/covalent triazine framework heterostructure by coordination bonds for photocatalytic hydrogen evolution

Abstract

The construction of tightly integrated heterostructures with metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) has been confirmed to be an effective way for improved hydrogen evolution. However, the reported tightly integrated MOF/COF hybrids were usually limited to the covalent connection of COFs with aldehyde groups and NH₂-MOF via Schiff base reaction, restricting the development of MOF/COF hybrids. Herein, a covalent triazine framework (CTF-1), a subtype of crystalline COFs, was integrated with a conductive two-dimensional (2D) MOF (Ni-CAT-1) by a novel coordinating connection mode for significantly enhanced visible-light-driven hydrogen evolution. The terminal amidine groups in the CTF-1 layers offer dual N sites for the coordination of metal ions, which provides the potential of coordinating connection between CTF-1 and Ni-CAT-1. The conductive 2D Ni-CAT-1 in Ni-CAT-1/CTF-1 hybrids effectively facilitates the separation of photogenerated carriers of CTF-1 component, and the resultant hybrid materials show significantly enhanced photocatalytic hydrogen evolution activity. In particular, the Ni-CAT-1/CTF-1 (1:19) sample exhibits the maximum hydrogen evolution rate of 8.03 mmol g^-1h^-1, which is about four times higher than that of the parent CTF-1 (1.96 mmol g^-1h^-1). The enhanced photocatalytic activity of Ni-CAT-1/CTF-1 is mainly attributed to the incorporation of conductive MOF which leads to the formation of a Z-Scheme heterostructure, promoting the electron transfer in hybrid materials. The coordinating combination mode of Ni-CAT-1 and CTF-1 in this work provides a novel strategy for constructing tightly integrated MOF/COF hybrid materials.

Keywords: Charge separation; Conductive MOF; Covalent triazine frameworks; Photocatalytic hydrogen evolution; Z-Scheme heterostructure.