Insights into Selective Sensitivity of In2O3-CuO Heterojunction Nanocrystals to CH4 over CO and H2: Experiments and First-Principles Calculations

Metal oxide semiconductor gas sensors have demonstrated exceptional potential in gas detection due to their high sensitivity, rapid response time, and impressive selectivity for identifying various sorts of gases. However, selectively distinguishing CH4 from those of CO and H2 remains a significant challenge. This difficulty primarily stems from the weakly reducing nature of CH4, which results in a low adsorption response and makes it prone to interference from stronger reducing gases in the surroundings. Herein, we synthesized In2O3-xCuO nanocomposites using a hydrothermal method to explore their gas sensing properties toward CH4, CO, and H2. Characterization tests confirmed the successful preparation of In2O3-xCuO nanocomposites with different In:Cu molar ratios and the formation of a p-n heterojunction. The gas sensing test results indicated that the In2O3-2.1CuO nanocomposites calcined at 500 °C and measured at 350 °C displayed a p-type response for CH4 and an n-type response for CO and H2, allowing for accurate differentiation of CH4 from CO and H2. Moreover, the In2O3-2.1CuO sensor also showed excellent stability and reproducibility across all three gases. First-principles calculations revealed distinct changes in the electronic structure of the In2O3-CuO heterojunction upon adsorption of CH4, CO, and H2, a finding that aligns with empirical evidence. The gas selectivity mechanism was effectively explained by variations in the energy band gap, driven by electrical behavior during the adsorption process. This work suggests a promising approach for developing selective gas sensors capable of detecting weakly reducing gases.