This review summarizes the recent research efforts and developments in nanomaterials for sensing volatile organic compounds (VOCs). The discussion focuses on key materials such as metal oxides (e.g., ZnO, SnO₂, TiO₂ WO₃), conductive polymers (e.g., polypyrrole, polythiophene, poly(3,4-ethylenedioxythiophene)), and carbon-based materials (e.g., graphene, graphene oxide, carbon nanotubes), and their mutual combination due to their representativeness in VOCs sensing. Moreover, it delves into the main characteristics and tuning of these materials to achieve enhanced functionality (sensitivity, selectivity, speed of response, and stability). The usual synthesis methods and their advantages towards their integration with microsystems for practical applications are also remarked on. The literature survey shows the most successful systems include structured morphologies, particularly hierarchical structures at the nanometric scale, with intentionally introduced tunable “decorative impurities” or well-defined interfaces forming bilayer structures. These groups of modified or functionalized structures, in which metal oxides are still the main protagonists either as host or guest elements, have proved improvements in VOCs sensing. The work also identifies the need to explore new hybrid material combinations, as well as the convenience of incorporating other transducing principles further than resistive that allow the exploitation of mixed output concepts (e.g., electric, optic, mechanic).

Zinc oxide rod structures are synthetized and subsequently modified with Au, Fe₂O₃, or Cu₂O to form nanoscale interfaces at the rod surface. X-ray photoelectron spectroscopy corroborates the presence of Fe in the form of oxide—Fe₂O₃; Cu in the form of two oxides—CuO and Cu₂O, with the major presence of Cu₂O; and Au in three oxidation states—Au³⁺, Au⁺, and Au⁰, with the content of metallic Au being the highest among the other states. These structures are tested towards nitrogen dioxide, ethanol, acetone, carbon monoxide, and toluene, finding a remarkable increase in the response and sensitivity of the Au-modified ZnO films, especially towards nitrogen dioxide and ethanol. The results for the Au-modified ZnO films report about 47 times higher response to 10 ppm of nitrogen dioxide as compared to the non-modified structures with a sensitivity of 39.96% ppm⁻¹ and a limit of detection of 26 ppb to this gas. These results are attributed to the cumulative effects of several factors, such as the presence of oxygen vacancies, the gas-sensing mechanism influenced by the nano-interfaces formed between ZnO and Au, and the catalytic nature of the Au nanoparticles.

This work presents the effect of magnesium (Mg) doping on the sensing properties of tin dioxide (SnO₂) thin films. Mg-doped SnO₂ films were prepared via a spray pyrolysis method using three doping concentrations (0.8 at.%, 1.2 at.%, and 1.6 at.%) and the sensing responses were obtained at a comparatively low operating temperature (160 °C) compared to other gas sensitive materials in the literature. The morphological, structural and chemical composition analysis of the doped films show local lattice disorders and a proportional decrease in the average crystallite size as the Mg-doping level increases. These results also indicate an excess of Mg (in the samples prepared with 1.6 at.% of magnesium) which causes the formation of a secondary magnesium oxide phase. The films are tested towards three volatile organic compounds (VOCs), including ethanol, acetone, and toluene. The gas sensing tests show an enhancement of the sensing properties to these vapors as the Mg-doping level rises. This improvement is particularly observed for ethanol and, thus, the gas sensing analysis is focused on this analyte. Results to 80 ppm of ethanol, for instance, show that the response of the 1.6 at.% Mg-doped SnO₂ film is four times higher and 90 s faster than that of the 0.8 at.% Mg-doped SnO₂ film. This enhancement is attributed to the Mg-incorporation into the SnO₂ cell and to the formation of MgO within the film. These two factors maximize the electrical resistance change in the gas adsorption stage, and thus, raise ethanol sensitivity.

Gas sensitive cerium oxide-tungsten oxide core-shell nanowires are synthesized and integrated directly into micromachined platforms via aerosol assisted chemical vapor deposition. Tests to various volatile organic compounds (acetone, ethanol, and toluene) involved in early disease diagnosis demonstrate enhanced sensitivity to acetone for the core-shell structures in contrast to the non-modified materials (i.e., only tungsten oxide or cerium oxide). This is attributed to the high density of oxygen vacancy defects at the shell, as well as the formation of heterojunctions at the core-shell interface, which provide the modified nanowires with ‘extra’ chemical and electronic sensitization as compared to the non-modified materials.