Mixed-Valence Cobalt(II/III) Metal-Organic Framework for Ammonia Sensing with Naked-Eye Color Switching.

Abstract

The construction of colorimetric sensing materials with high selectivity, low detection limits, and great stability provides a significant way for facile device implementation of an ammonia (NH3) sensor. Herein, with excellent alkaline stability and exposed N sites in molecule as well as with naked-eye color switching nature generated from changeable cobalt (Co) valence, a three-dimensional mixed-valence cobalt(II/III) metal-organic framework (FJU-56) with tris-(4-tetrazolyl-phenyl)amine (H3L) ligand was synthesized for colorimetric sensing toward ammonia. The activated FJU-56 demonstrates a limit of detection of 1.38 ppm for ammonia sensing, with high selectivity in ammonia and water competitive adsorption, and shows outstanding stability and reversibility in the cyclic test. The NH3 or water molecules binding to the exposed N sites with the hydrogen-bond are observed by single-crystal X-ray diffraction, determining that the attachment of guest molecules to the FJU-56 framework changes the valence of Co ions with a naked-eye color switching response, which provides an ocular demonstration for ammonia capture and a valuable insight into ammonia sensing.