Size-Controlled Au Nanoparticles Incorporating Mesoporous ZnO for Sensitive Ethanol Sensing

Zinc oxide (ZnO) as a commonly used semiconductor material has aroused extensive research attention in various fields, such as field-effect transistors, solar cells, luminescent devices, and sensors, because of its excellent light-electrical features and large exciton bonding energy. Herein, ultrasmall Au nanoparticles with tunable size decorated mesoporous ZnO nanospheres were synthesized via facile formaldehyde-assisted metal-ligand cross-linking strategy, where these active Au species could be transferred into Au nanoparticles in the frameworks by various reduction strategies. Typically, mesoporous ZnO-Au with a photoreduction technique showed superior ethanol sensing performance (ca. 159 for 50 ppm at 200 °C) because of its high surface area, dual-mesoporous structure, and interface effect (electron effect, surface catalytic/adsorption). Moreover, the mesoporous ZnO-Au composites by photoreduction show much better performance than those via H₂ reduction and NaBH₄ reduction, which is ascribed to the providential size of Au nanoparticles (ca. 6.6 nm) and abundant oxygen defects in the composites. In particular, the selectivity and sensitivity of mesoporous ZnO-Au far exceeds those of materials loaded with other noble metals (Pt, Pd, and Ag). The sensing mechanism of mesoporous ZnO-Au for ethanol is attributed to classical surface adsorption/catalytic reaction, where strong sensitization effect (electron and chemical) and the spillover effect of Au nanoparticles in the catalytic reaction cause superior ethanol sensing performances. In situ FTIR and GC-MS measurement revealed that the catalytic oxidation of ethanol follows the process of dehydrogenation and deep oxidation, that is, dehydrogenation to acetaldehyde, and then further oxidation to carbon dioxide and water.