Room-temperature NO2 gas sensors based on rGO@ZnO1-xcomposites: Experiments and molecular dynamics simulation

Recently, room-temperature gas sensors have become very attractive due to the fact that they can be operated without heating, and thus simplifying the sensor design, reducing the fabrication cost, decreasing the power consumption and increasing the long-term stability. In this study, we propose a facile one-step hydrothermal method to prepare a composite of reduced graphene (rGO)/oxygen-deficient zinc oxide (ZnO1-x ), which exhibits obvious room-temperature gas sensing response. X-ray diffraction, Raman and X-ray photoelectron spectroscopy demonstrate that the rGO@ZnO1-x composite is successfully synthesized and large numbers of dual donor defects, oxygen vacancy and zinc interstitial, are introduced into the composite. Field-emission scanning electron microscopy and transmission electron microscopy results reveal that many nanoscale p-n junctions are in-situ formed between ZnO nanosheets and rGO sheets. UV-vis spectra show that the light absorption of the rGO@ ZnO1-x composite is red-shifted and extended to the whole visible light region in comparison. The fraction of rGO in the composites plays an important role in the sensing performance. 2.0% is the optimal proportion to obtain the best sensing properties in terms of sensitivity, response and recovery times. The rGO@ZnO1-x composite exhibits significant responses to ppb-level NO2 with white LED light stimulation at room temperature. The enhanced sensing properties can be attributed to three factors: light activation, synergistic effects between rGO and ZnO1-x, and high concentration in donor defects. Molecular Dynamics (MD) is used to quantitively simulate the adsorption process, and the results show that the incorporation of rGO decreases the adsorption energy of NO2. It means that more NO2 species would adsorb on the rGO@ZnO1-x composites, which greatly improves the sensitivity. A new gas sensing mechanism based on the MD calculated results and Langmuir adsorption model is used to explain the reason that the rGO@ZnO1-x composites have a much faster response and recovery process. In addition, the rGO@ZnO1- x sensor shows a weaker response to other interference gases.