Gas sensors based on titanium dioxide (TiO₂) have attracted much public attention during the past decades due to their excellent potential for applications in environmental pollution remediation, transportation industries, personal safety, biology, and medicine. Numerous efforts have therefore been devoted to improving the sensing performance of TiO₂. In those effects, the construct of nanoheterostructures is a promising tactic in gas sensing modification, which shows superior sensing performance to that of the single component-based sensors. In this review, we briefly summarize and highlight the development of TiO₂-based heterostructure gas sensing materials with diverse models, including semiconductor/semiconductor nanoheterostructures, noble metal/semiconductor nanoheterostructures, carbon-group-materials/semiconductor nano- heterostructures, and organic/inorganic nanoheterostructures, which have been investigated for effective enhancement of gas sensing properties through the increase of sensitivity, selectivity, and stability, decrease of optimal work temperature and response/recovery time, and minimization of detectable levels.

Multilayers of Ti doped diamond-like carbon (Ti-DLC) coatings were deposited on aluminum alloys by filtered cathodic vacuum arc (FCVA) technology using C₂H₂ as a reactive gas. The effect of different Ti transition layer thicknesses on the structure, mechanical and adhesion properties of the coatings, was investigated by scanning electron microscopy (SEM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), nanoindentation and a scratch tester. The results showed that the Ti transition layer could improve interfacial transition between the coating and the substrate, which was beneficial in obtaining excellent adhesion of the coatings. The Ti transition layer thickness had no significant influence on the composition and structure of the coatings, whereas it affected the distortion of the sp²-C bond angle and length. Nanoindentation and scratch test results indicated that the mechanical and adhesion properties of the Ti-DLC coatings depended on the Ti transition layer thickness. The Ti transition layer proved favorable in decreasing the residual compressive stress of the coating. As the Ti transition layer thickness increased, the hardness value of the coating gradually decreased. However, its elastic modulus and adhesion exhibited an initial decrease followed by an increasing fluctuation. Among them, the Ti-DLC coating with a Ti transition layer thickness of 1.1 μm exhibited superior mechanical properties.

Hierarchical nanostructures with much increased surface-to-volume ratio have been of significant interest for prototypical gas sensors. Herein we report a novel resistive gas sensor based on TiO ₂ /V ₂ O ₅ branched nanoheterostructures fabricated by a facile one-step synthetic process, in which well-matched energy levels induced by the formation of effective heterojunctions between TiO ₂ and V ₂ O ₅ , a large Brunauer–Emmett–Teller surface area and complete electron depletion for the V ₂ O ₅ nanobranches induced by the branched-nanofiber structures are all beneficial to the change of resistance upon ethanol exposure. As a result, the ethanol sensing performance of this device shows a lower operating temperature, faster response/recovery behavior, better selectivity and about seven times higher sensitivity compared with pure TiO ₂ nanofibers. This study not only confirms the gas sensing mechanism for performing enhancement of branched nanoheterostructures, but also proposes a rational approach to the design of nanostructure-based chemical sensors with desirable performance.

Much greater surface-to-volume ratio of hierarchical nanostructures renders them attract considerable interest as prototypical gas sensors. In this work, a novel resistive gas sensor based on TiO₂/Ag_0.35V₂O₅ branched nanoheterostructures is fabricated by a facile one-step synthetic process and the ethanol sensing performance of this device is characterized systematically, which shows faster response/recovery behavior, better selectivity, and higher sensitivity of about 9 times as compared to the pure TiO₂ nanofibers. The enhanced sensitivity of the TiO₂/Ag_0.35V₂O₅ branched nanoheterostructures should be attributed to the extraordinary branched hierarchical structures and TiO₂/Ag_0.35V₂O₅ heterojunctions, which can eventually result in an obvious change of resistance upon ethanol exposure. This study not only indicates the gas sensing mechanism for performance enhancement of branched nanoheterostructures, but also proposes a rational approach to design nanostructure based chemical sensors with desirable performance.