Synthesis of Zr-coordinated amide porphyrin-based two-dimensional covalent organic framework at liquid-liquid interface for electrochemical sensing of tetracycline.

Highly-conductive two-dimensional covalent organic framework (COF) displays prominent applications in various fields of science and technology. This paper reports the design and liquid-liquid interface synthesis of a novel Zr-coordinated amide porphyrin-based 2D COF (Zr-amide-Por-based 2D COF). The COF adopts a graphene-like multilayer structure with the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) band gap of 1.6 eV. The ordered multilayer structure of the amide COF was confirmed through a series of characterization techniques, including scanning electron microscopy, high-resolution transmission electron microscopy, atomic force microscopy, Fourier-transform infrared spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. In particular, the inherent-ordered structure of Zr-amide-Por-based 2D COF with Zr as the catalytically active center confers several distinct advantages to the material, such as high conductivity and high electrocatalysis performance. A molecularly imprinted tetracycline electrochemiluminescence sensor was constructed based on the Zr-amide-Por-based 2D COF, and gate control effect was used as a signal-generation mechanism. Under optimal conditions, the sensor showed a good linear relationship with tetracycline in the concentration range of 5-60 pM, with a detection limit of 2.3 pM. Because the sensor is rapid, cost-efficient, highly sensitive, and specific, it can be considered as a viable platform for veterinary drug residue monitoring.