Synthesis of poly(methacrylic acid)-manganese oxide dihydroxide/silica core-shell and the corresponding hollow microspheres

Shuxuan Sun; Bin Liu; Xiaomeng Fu; Meijun Zhou; Wei Liu; Guomin Bian; Yonglin Qi; Xinlin Yang

doi:10.1016/j.jcis.2014.09.051

Synthesis of poly(methacrylic acid)-manganese oxide dihydroxide/silica core-shell and the corresponding hollow microspheres

J Colloid Interface Sci. 2015 Jan 15:438:269-276. doi: 10.1016/j.jcis.2014.09.051. Epub 2014 Oct 8.

Authors

Shuxuan Sun¹, Bin Liu¹, Xiaomeng Fu¹, Meijun Zhou¹, Wei Liu², Guomin Bian³, Yonglin Qi³, Xinlin Yang⁴

Affiliations

¹ Key Laboratory of Functional Polymer Materials, Ministry of Education, Institute of Polymer Chemistry, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University, Tianjin 300071, PR China.
² State Key Laboratory of Hollow Fiber Membrane Materials and Processes, School of Environmental and Chemical Engineering, Tianjin Polytechnic University, Tianjin 300387, PR China. Electronic address: liuhuiwen217@yahoo.com.
³ Dynea Ltd. Co., Gaoyao City, Guangdong 526105, PR China.
⁴ Key Laboratory of Functional Polymer Materials, Ministry of Education, Institute of Polymer Chemistry, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University, Tianjin 300071, PR China. Electronic address: xlyang88@nankai.edu.cn.

PMID: 25454451
DOI: 10.1016/j.jcis.2014.09.051

Abstract

Poly(methacrylic acid)-MnO(OH)2/SiO2 core-shell microspheres were prepared by sol-gel hydrolysis of tetraethylorthosilicate (TEOS) in the presence of poly(methacrylic acid)-Mn(II) (PMAA-Mn(2+)) as template with ammonium hydroxide anion as catalyst and n-octadecyltrimethoxysilane (C18TMS) as pore-directing reagent. The PMAA-Mn(2+) core was prepared by incubation of Mn(2+) cations with PMAA microspheres via the coordination between carboxylate anion group on PMAA microsphere and Mn(2+) cations. During this process, the Mn(II) species were formed as white Mn(OH)2 precipitates at first, which were subsequently oxidized into brown MnO(OH)2 in air. The Mn2O3/mesoporous silica (Mn2O3/m-SiO2) double-shelled hollow microspheres (DSHMs) were prepared through calcination of the PMAA-MnO(OH)2/SiO2 core-shell microspheres at 600 °C for the selective removal of PMAA template and pore-directing organic component from C18TMS, during which the crystalline structure of DSHM was developed into Braunite-1Q via the reaction between Mn2O3 inner-shell and silica outer-shell by annealing the DSHMs under higher temperatures of 800 and 900 °C. The Mn2O3 hollow microspheres (HMs) were prepared through the selective removal of the silica layer from the DSHMs by sodium hydroxide aqueous solution, which exhibited structure integrity and good ethanol dispersity due to the presence of mesoporous structure.

Keywords: Core–shell microspheres; Double-shelled hollow microspheres; Hollow Mn(2)O(3) microspheres; Mn(2)O(3)/m-SiO(2) microspheres; Polymer/inorganic microspheres.