Enhancement of Low-Temperature Gas-Sensing Performance Using Substoichiometric WO_3- Modified with CuO

To verify the effect of oxygen vacancy on gas sensitivity, we have systematically investigated the gas-sensing performance of copper oxide/substoichiometric tungsten oxide (CuO/WO_3-) nanocomposite sensors. Oxygen deficiency in WO_3- facilitates the reaction of hydrogen sulfide (H₂S) gas with chemisorbed oxygen species (i.e., O₂^-, O^-, and O^2-) at low temperature. The oxygen/sulphur exchange reaction between CuO and H₂S in the sensing process can achieve room temperature operation of gas sensors. After the WO_3- nanorods were modified by a low content of CuO nanoparticles (Cu:W = 1:20), the sensors present an n-type sensing behavior. Their best working temperatures drop from 289 °C (or 386 °C) to 99 °C (or 70 °C) at which the responses are improved by 14 to 163 times for different x values. Among them, CuO(L)/W₅O₁₄ shows the highest sensitivity of 1575.7 to 10 ppm H₂S at 99 °C and 171.5 to 10 ppm H₂S at room temperature. Once WO_3- were loaded with a high concentration of CuO nanoparticles (Cu:W = 1:2), they exhibit a p-type behavior, and the optimal working temperatures reduce suddenly to room temperature at which CuO(H)/W₁₈O₄₉ displays the most sensitive response of 7.2 even toward trace amounts of H₂S as low as 100 ppb. In addition, p-type CuO weakens the metal-like characteristics of W₁₈O₄₉ and such weakening effect enhances with an increase in the CuO content. Therefore, the sensing performance of the CuO/W₁₈O₄₉ composite is the best among the four CuO/WO_3- sensors. The two designs for low and high Cu/W molar ratios all achieve enhanced room-temperature H₂S gas response, with a fast recovery time of ∼60 s under heating pulse, as well as an excellent selectivity, which makes the sensors a promising candidate for practical applications. Moreover, the micro-Raman spectra confirmed CuS formation and the thermal effect on the decomposition of CuS in the sensing process was studied.