Molecular Recognition with Covalent-Organic-Framework Nanofilms at Terahertz Band

Abstract

Development of rapid molecular detection technologies is critical for the safer and smarter urban agriculture, medicine, and pro-environment. The emergent terahertz (THz) spectroscopy has the distinct advantages of being non-destructive and label-free and able to trace intermolecular and intramolecular vibrations, yet it suffers from the low performance of sensing materials available and their high fabrication cost. Here, we introduce a reticular material -- two dimensional (2D) covalent organic frameworks (COFs) and prepare their nanofilms as the lossy layer for THz absorbers. The COF film can be directly deposited on the dielectric layer of THz absorbers via an in-situ wet-chemistry growth. It possesses designable hierarchical structures, high specific areas of 736-971 m2/g, and precise nanopores of 1.6-2.1 nm, depending on its 2D COF constituents. The resulting THz absorber has been tested for pesticide detection. It presents a limit of detection at 2.2 ng and a selective response of 2.7-7.8 times that of interferents such as saccharides, antibiotics, and dyes, satisfying the need for practical application. Such flexible filmy sensor can measure the pesticide residue on the surface of apple for practical application. The THz sensor also demonstrates high stability over 1000 cycles of bending. Use of reticular nanofilm as the responsive layer may permit the future development of high-performance THz absorbers and other sensors for rapid molecular recognition.

Keywords: Terahertz, covalent organic framework, molecular recognition, nanofilm, hierarchical structure