Micellar Nanoreactors Enabled Site‐Selective Decoration of Pt Nanoparticles Functionalized Mesoporous SiO₂/WO_3‐x Composites for Improved CO Sensing

Abstract Site‐selective and partial decoration of supported metal nanoparticles (NPs) with transition metal oxides (e.g., FeO_x) can remarkably improve its catalytic performance and maintain the functions of the carrier. However, it is challenging to selectively deposit transition metal oxides on the metal NPs embedded in the mesopores of supporting matrix through conventional deposition method. Herein, a restricted in situ site‐selective modification strategy utilizing poly(ethylene oxide)‐block‐polystyrene (PEO‐b‐PS) micellar nanoreactors is proposed to overcome such an obstacle. The PEO shell of PEO‐b‐PS micelles interacts with the hydrolyzed tungsten salts and silica precursors, while the hydrophobic organoplatinum complex and ferrocene are confined in the hydrophobic PS core. The thermal treatment leads to mesoporous SiO₂/WO_3‐x framework, and meanwhile FeO_x nanolayers are in situ partially deposited on the supported Pt NPs due to the strong metal‐support interaction between FeO_x and Pt. The selective modification of Pt NPs with FeO_x makes the Pt NPs present an electron‐deficient state, which promotes the mobility of CO and activates the oxidation of CO. Therefore, mesoporous SiO₂/WO_3‐x‐FeO_x/Pt based gas sensors show a high sensitivity (31 ± 2 in 50 ppm of CO), excellent selectivity, and fast response time (3.6 s to 25 ppm) to CO gas at low operating temperature (66 °C, 74% relative humidity).