This work presents a hydrothermal-based facile method for synthesizing ZnFe2O4, whose size can be controlled with the concentration of sodium acetate used as a fuel and its physical changes at nanoscales when exposed to two different gases. The structural, morphological, compositional, and electronic properties of the synthesized samples are also presented in this paper. The crystal structure of the synthesized samples was determined using an X-ray Diffractometer (XRD). The results revealed fluctuations in the size, lattice parameter, and strain in the nanoparticles with increasing the concentration of sodium acetate. Field-Emission Scanning Electron Microscopy (FESEM) was used to determine synthesized materials’ morphology and particle size. It revealed that the particles possessed approximately spherical morphology whose size decreased significantly with the increasing amount of sodium acetate. Transmission Electron Microscopy (TEM) was utilized to determine the structure, morphology, and elemental distributions in particles at the nanoscale, and it confirmed the findings of XRD and FESEM analyses. The high-resolution TEM (HRTEM) imaging analysis of the nanoparticles in our studied samples revealed that the particles predominantly possessed (001) type facets. X-ray photoelectron spectroscopy (XPS) and core-loss electron energy loss spectroscopy (EELS) showed an increasing fraction of Fe2+ with the decreasing size of the particles in samples. The Brunauer, Emmett, and Tellers (BET) analysis of samples revealed a higher surface area as the particle size decreases. In addition, the determined surface area and pore size values are compared with the literature, and it was found that the synthesized materials are promising for gas-sensing applications. The ab initio calculations of the Density of States (DOS) and Band structure of (001) surface terminating ZnFe2O4 were carried out using Quantum Espresso software to determine the bandgap of the synthesized samples. They were compared to their corresponding experimentally determined bandgap values and showed close agreement. Finally, in-situ TEM measurement was carried out on one of the four studied samples with robust properties using Ar and CO2 as reference and target gases, respectively. It is concluded from the presented study that the size reduction of the ZnFe2O4 nanoparticles (NPs) tunes the bandgap and provides more active sites due to a higher concentration of oxygen vacancies. The in-situ TEM showed us a nanoscale observation of the change in one of the crystal structure parameters. The d spacing of ZnFe2O4 NPs showed a noticeable fluctuation, reaching more than 5% upon exposure to CO2 and Ar gases.
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