ABSTRACT
Two-dimensional covalent organic frameworks (2D COFs) are promising for gas sensing owing to the large surface area, abundant active sites, and their semiconducting nature. However, 2D COFs are usually produced in the form of insoluble micro-crystallites. Their poor contacts between grain boundaries severely suppress the conductivity, which are too low for chemresistive gas sensing. Here, we demonstrate that halide perovskites can be employed as electric glues to bond 2D COF crystallites to improve their conductivity by two orders of magnitude, activating them to detect NO2 with high selectivity and sensitivity. Resonant microcantilever, grand canonical Monte Carlo, density functional theory and sum-frequency generation analyses prove that 2D COFs can enrich and transfer electrons to NO2 molecules, leading to increased device conductivity. This work provides a facile approach for improving the conductivity of polycrystalline 2D COF films and may expand their applications in semiconductor devices, such as sensors, resistors, memristors and field-emission transistors.
ABSTRACT
In recent years, the performance research of perovskite materials is not only concentrated in the field of solar cells or optics, but the field of gas sensing has gradually entered the public view. However, the detection of nitric oxide (NO) by lead-free halide perovskites has not yet been reported. Herein, we use Cs2PtI6 to realize the first example of a halide perovskite applied to NO sensing. Due to favoring Pt-N binding, the material has some excellent properties such as a NO detection limit as low as 100 parts-per-billion (ppb), ultrahigh selectivity to NO, and can work at room temperature for more than 2 months. In situ sum frequency generation (SFG) spectra and crystal orbital Hamilton population (COHP) analysis reveal that the strong bonding interaction between Pt 5s and N 2s ensure the high adsorption energy, and Pt 5d electron back donation to N 2px, N 2pz antibonding causes the conductive change of the sensors. In addition, its flexible wearable technology shows the application potential of the device and promotes the further development of perovskite materials.
Subject(s)
Calcium Compounds , Nitric Oxide , Oxides , TitaniumABSTRACT
Organic electrical gas sensors have been developed for many decades because of their high sensitivity and selectivity. However, their industrialization is severely hindered by their intrinsic humidity susceptibility and poor recovery. Conventional organic sensory materials can only operate at room temperature owing to their weak intermolecular interactions. Herein, we demonstrate using a croconate polymer (poly-4,4'-biphenylcroconate) that the "ion-in-conjugation" concept enables organic gas sensors to operate at 100 °C and 70 % relative humidity with almost complete recovery. The fabricated sensor had a parts-per-billion (ppb) detection limit for NO2 and showed the highest sensitivity (2526â ppm-1 at 40â ppb) of all reported NO2 chemiresistive sensors. Furthermore, charge transfer increased with temperature. Theoretical calculations and in situ FTIR spectra confirmed the ion-in-conjugation-inspired hydrogen bond as key for excellent sensitivity. A NO2 alarm system was assembled to demonstrate the feasibility of this sensor.
