Amphiphilic Block Copolymers Directed Interface Coassembly to Construct Multifunctional Microspheres with Magnetic Core and Monolayer Mesoporous Aluminosilicate Shell

Yu Zhang; Qin Yue; Lei Yu; Xuanyu Yang; Xiu-Feng Hou; Dongyuan Zhao; Xiaowei Cheng; Yonghui Deng

doi:10.1002/adma.201800345

Amphiphilic Block Copolymers Directed Interface Coassembly to Construct Multifunctional Microspheres with Magnetic Core and Monolayer Mesoporous Aluminosilicate Shell

Adv Mater. 2018 Jun;30(26):e1800345. doi: 10.1002/adma.201800345. Epub 2018 May 11.

Authors

Yu Zhang¹, Qin Yue², Lei Yu¹, Xuanyu Yang¹, Xiu-Feng Hou¹, Dongyuan Zhao¹, Xiaowei Cheng¹, Yonghui Deng^{1

3}

Affiliations

¹ Department of Chemistry, State Key Laboratory of Molecular Engineering of Polymers, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, iChEM, Fudan University, Shanghai, 200433, China.
² Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu, 610051, China.
³ State Key Laboratory of Transducer Technology, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, Shanghai, 200050, China.

PMID: 29749031
DOI: 10.1002/adma.201800345

Abstract

Core-shell magnetic porous microspheres have wide applications in drug delivery, catalysis and bioseparation, and so on. However, it is great challenge to controllably synthesize magnetic porous microspheres with uniform well-aligned accessible large mesopores (>10 nm) which are highly desired for applications involving immobilization or adsorption of large guest molecules or nanoobjects. In this study, a facile and general amphiphilic block copolymer directed interfacial coassembly strategy is developed to synthesize core-shell magnetic mesoporous microspheres with a monolayer of mesoporous shell of different composition (FDUcs-17D), such as core-shell magnetic mesoporous aluminosilicate (CS-MMAS), silica (CS-MMS), and zirconia-silica (CS-MMZS), open and large pores by employing polystyrene-block-poly (4-vinylpyridine) (PS-b-P4VP) as an interface structure directing agent and aluminum acetylacetonate (Al(acac)₃ ), zirconium acetylacetonate, and tetraethyl orthosilicate as shell precursors. The obtained CS-MMAS microspheres possess magnetic core, perpendicular mesopores (20-32 nm) in the shell, high surface area (244.7 m² g^-1 ), and abundant acid sites (0.44 mmol g^-1 ), and as a result, they exhibit superior performance in removal of organophosphorus pesticides (fenthion) with a fast adsorption dynamics and high adsorption capacity. CS-MMAS microspheres loaded with Au nanoparticles (≈3.5 nm) behavior as a highly active heterogeneous nanocatalyst for N-alkylation reaction for producing N-phenylbenzylamine with a selectivity and yields of over 90% and good magnetic recyclability.

Keywords: adsorption; aluminosilicate; amphiphilic block copolymers; catalysis; core-shell; mesoporous materials; surface acidity.