Bimetallic MOF-Based Sensor for Highly Sensitive Detection of Ammonia Gases.

Abstract

The demand for the detection of ultralow concentrations of ammonia gas is growing. A bimetallic metal-organic framework (MOF) comprising Prussian blue analogs (PBAs) was used to achieve highly sensitive and stable detection of ammonia gas at room temperature in this study. First, PB was enriched by using ammonia for improved gas sensing properties. Second, a sensitive membrane with more vacancies was formed by partially replacing Fe3+ with Cu2+ through a cation-exchange strategy. Finally, a capacitive sensor was developed for ultralow-concentration ammonia detection using a Cu-Fe PBA sensitive membrane and interdigitated electrodes (IDEs). To investigate the adsorption efficiency of the designed composite sensitive film for ammonia, PBAs nanoparticles were deposited on a quartz microcrystal balance (QCM) via cyclic voltammetry and a hydrothermal method. Approximately 10 ppm of ammonia was adsorbed under 1 atm by the Cu-Fe PBA film prepared using a reaction time of 36 h, and the adsorption efficiency was measured to be 2.2 mmol g-1 using the QCM frequency response. The Cu-Fe PBAs were also tested using scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and Brunauer-Emmett-Teller theory. The introduction of Cu2+ ions significantly increased the specific surface area of Cu-Fe PBAs MOF, and the number of adsorption sites for ammonia also increased; however, its skeleton structure remained similar to that of PB. Then, the capacitive sensor based on Cu-Fe PBA sensitive membrane and IDE was fabricated and the gas sensing detection device was established for ammonia detection. Overall, the developed capacitive sensor exhibits a linear response of 75-1000 ppb and a detection limit of 3.8 ppb for ultralow ammonia concentrations, which makes it superior to traditional detection methods and thus allows excellent application prospects.