The detection of hydrogen gas is crucial for both industrial fields, as a green energy carrier, and biomedical applications, where it is a biomarker for diagnosis. TiO₂ nanomaterials are stable and sensitive to hydrogen gas, but their gas response can be negatively affected by external factors such as humidity. Therefore, a strategy is required to mitigate these influences. The utilization of organic–inorganic hybrid gas sensors, specifically metal oxide gas sensors coated with ultra-thin copolymer films, is a relatively novel approach in this field. In this study, we examined the performance and long-term stability of novel TiO₂-based sensors that were coated with poly(trivinyltrimethylcyclotrisiloxane-co-tetrafluoroethylene) (P(V3D3-co-TFE)) co-polymers. The P(V3D3-co-TFE)/TiO₂ hybrid sensors exhibit high reliability even for more than 427 days. They exhibit excellent hydrogen selectivity, particularly in environments with high humidity. An optimum operating temperature of 300 °C to 350 °C was determined. The highest recorded response to H₂ was approximately 153% during the initial set of measurements at a relative humidity of 10%. The developed organic–inorganic hybrid structures open wide opportunities for gas sensor tuning and customization, paving the way for innovative applications in industry and biomedical fields, such as exhaled breath analysis, etc.

A novel two-in-one sensor for both carbon dioxide and hydrogen detection has been obtained based on a hybrid heterostructure. It consists of a 30 nm thick TiO₂ nanocrystalline film grown by atomic layer deposition (ALD), thermally annealed at 610 °C, and subsequently coated with bimetallic AgAu nanoparticles and covered with a PV4D4 nanolayer, which was thermally treated at 430 °C. Two types of gas response behaviors have been registered, as n-type for hydrogen gas and p-type semiconductor behavior for carbon dioxide gas detection. The highest response for carbon dioxide has been registered at an operating temperature of 150 °C with a value of 130%, while the highest response for hydrogen gas was registered at 350 °C with a value of 230%, although it also attained a relatively good gas selectivity at 150 °C. It is considered that a thermal annealing temperature of 610 °C is better for the properties of TiO₂ nanofilms, since it enhances gas sensor sensitivity too. Polymer coating on top is also believed to contribute to a higher influence on selectivity of the sensor structure. Accordingly, to our previous research where PV4D4 has been annealed at 450 °C, in this research paper, a lower temperature of 430 °C for annealing has been used, and thus another ratio of cyclocages and cyclorings has been obtained. Knowing that the polymer acts like a sieve atop the sensor structure, in this study it offers increased selectivity and sensitivity towards carbon dioxide gas detection, as well as maintaining a relatively increased selectivity for hydrogen gas detection, which works as expected with Ag and Au bimetallic nanoparticles on the surface of the sensing structure. The results obtained are highly important for biomedical and environmental applications, as well as for further development of the sensor industry, considering the high potential of two-in-one sensors. A carbon dioxide detector could be used for assessing respiratory markers in patients and monitoring the quality of the environment, while hydrogen could be used for both monitoring lactose intolerance and concentrations in cases of therapeutic gas, as well as monitoring the safe handling of various concentrations.

Considering the various applications where detection is required—whether for industrial or medical purposes—providing cost-efficient, stable, and highly selective solutions remains challenging. Different industries require hydrogen detectors, because this gas has the potential to serve as a clean and versatile energy carrier; therefore, precise monitoring and feedback in such systems are of enormous importance. Simultaneously, the medical field is developing new therapeutic methods using hydrogen as a medical gas, while also utilizing it as a biomarker in exhaled breath for various gastric diseases. In this paper, a ZnO-based gas sensor, doped with Ag nanoparticles produced via the Solution Chemical Synthesis (SCS) method, was coated with a thin polymer film of poly(1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane) PV4D4 via initiated Chemical Vapor Deposition (iCVD). The results are promising: at a relatively high operating temperature of 350 °C, the sensor showed its highest registered response to H₂ gas (up to 23%). Compared to other gases studied at the same temperature, the sensor also showed potential for detecting 2-propanol, n-butanol, and ethanol, albeit with lower responses. Based on the dynamic response analysis, the fastest reaction time was also recorded at the highest operating temperature, thus showing versatile possibilities for using the specified detector.