Porphyrinoid-Functionalized ZnO Nanoflowers for Visible Light-Enhanced and Selective Benzylamine Detection at Room Temperature

Functionalization of hybrid organic molecules as layers on ZnO nanoflowers (NFs) gives an excellent combination of sensing toward visible light and vapors of various volatile organic compounds (VOCs). In this work, hybrid organic molecules functionalized ZnO NFs were utilized for the photoinduced detection of benzylamine at room temperature. The ZnO NFs were synthesized via a facile solution route and functionalized with four different porphyrin-conjugated molecules namely (i) pyrene-porphyrin (PP), (ii) pyrene- porphyrinato zinc (ZnPP), (iii) triphenylamine- porphyrin (TP) and (iv) triphenylamine- porphyrinato zinc (ZnTP). The diameter of the flower-like structure was found to be ∼3.2 μm with the thickness of petals being ∼24.1 nm. The gas adsorption performance of the functionalized ZnO NFs on light activation at room temperature was studied by using a scanning Kelvin probe (SKP) system. The improved adsorption properties of the samples can be attributed to the heterojunctions and light activation. In particular, an enhanced response of ZnTP functionalized ZnO (ZnTPZ) toward benzylamine was observed. Further, static gas sensing experiments using ZnTPZ under various concentrations (1, 3, 5, 10, 15, and 25 ppm) of benzylamine vapors both in dark and visible light conditions have exhibited a linear increase in the response. The selectively enhanced response of ZnTPZ compared to that of pristine ZnO was thus confirmed at 1 ppm of benzylamine. The sensitivity and limit of detection of the ZnTPZ sensor were calculated to be 0.0292 ppm^-1 and 197 ppb, respectively. The coordination metal (Zn) has helped in effective charge transfer between benzylamine and ZnTPZ by providing additional active sites for interactions. Also, density functional theory calculations demonstrated the role of the hybrid organic molecules on the sensor surface in improving gas adsorption. Further, fresh cabbage was utilized for real sample analysis with the proposed sensor under visible light illumination conditions, and a linear response was obtained for low ppm evaluation at room temperature. Overall, the obtained results suggest the development of novel ZnTPZ-based light-activated gas sensors for low ppm benzylamine detection at room temperature. These kinds of sensors can be used to track the freshness of vegetables as they are transported from farms to commercial outlets.