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胶束纳米反应器实现了对功能化介孔SiO₂/WO₃复合材料负载的Pt纳米颗粒进行位点选择性修饰以改善CO传感性能。

Micellar Nanoreactors Enabled Site-Selective Decoration of Pt Nanoparticles Functionalized Mesoporous SiO /WO Composites for Improved CO Sensing.

作者信息

Ma Junhao, Xie Wenhe, Li Jichun, Yang Haitao, Wu Limin, Zou Yidong, Deng Yonghui

机构信息

Department of Chemistry, Department of Gastroenterology and Hepatology, State Key Laboratory of Molecular Engineering of Polymers, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, State Key Lab of Transducer Technology, Zhongshan Hospital, iChEM, Fudan University, Shanghai, 200433, P. R. China.

School of Materials Science and Engineering, Nanchang Hangkong University, Nanchang, 330063, P. R. China.

出版信息

Small. 2023 Aug;19(32):e2301011. doi: 10.1002/smll.202301011. Epub 2023 Apr 17.

Abstract

Site-selective and partial decoration of supported metal nanoparticles (NPs) with transition metal oxides (e.g., FeO ) 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 SiO /WO framework, and meanwhile FeO nanolayers are in situ partially deposited on the supported Pt NPs due to the strong metal-support interaction between FeO and Pt. The selective modification of Pt NPs with FeO makes the Pt NPs present an electron-deficient state, which promotes the mobility of CO and activates the oxidation of CO. Therefore, mesoporous SiO /WO -FeO /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).

摘要

用过渡金属氧化物(如FeO)对负载型金属纳米颗粒(NPs)进行位点选择性和部分修饰,可以显著提高其催化性能,并保持载体的功能。然而,通过传统的沉积方法将过渡金属氧化物选择性地沉积在嵌入支撑基质介孔中的金属NPs上具有挑战性。在此,提出了一种利用聚环氧乙烷-嵌段-聚苯乙烯(PEO-b-PS)胶束纳米反应器的受限原位位点选择性修饰策略来克服这一障碍。PEO-b-PS胶束的PEO壳层与水解的钨盐和二氧化硅前驱体相互作用,而疏水性有机铂配合物和二茂铁则被限制在疏水性PS核中。热处理导致介孔SiO /WO框架的形成,同时由于FeO与Pt之间强烈的金属-载体相互作用,FeO纳米层原位部分沉积在负载的Pt NPs上。用FeO对Pt NPs进行选择性修饰使Pt NPs呈现电子缺陷状态,这促进了CO的迁移并激活了CO的氧化。因此,介孔SiO /WO -FeO /Pt基气体传感器在低工作温度(66°C,相对湿度74%)下对CO气体表现出高灵敏度(在50 ppm CO中为31±2)、优异的选择性和快速响应时间(对25 ppm为响应时间3.6 s)。

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