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.
Keywords: Au nanoparticles; catalytic oxidation; gas sensor; mesoporous zinc oxide; semiconductor.