Progress in the Synthesis of Inorganic Hollow Nanomaterials with Core-Shell-Corona Polymer Micelles as Templates
CHEN Youwei1,2,3, WANG Xiatian2,3, LI Qi1, ZHANG Weibo2,3, SHI Dan2,3, HUANG Jiao2,3, CHEN Danchao2,3,ZHOU Shenghu1
1 State key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China 2 Ningbo Academy of Science and Technology for Inspection and Quarantine, Ningbo 315012, China 3 Ningbo Entry-Exit Inspection and Quarantine Bureau Technical Center, Ningbo 315012, Chin
Abstract: Inorganic hollow nanomaterials have shown outstanding application potential in catalysis, lithium battery electrode materials, drug delivery and many other fields due to their low density, high surface volume ratio and low thermal expansion coefficient. At present, template method is the most widely used method in the preparation of this kind of materials. Hard template method was used in the early stage. Hard template gene-rally includes metal crystals, silica nanospheres and PS latex nanospheres. However, this method suffered from low product yield due to complex synthesis process and shell weakness upon template remove. In order to overcome these shortcomings, researchers have turned to soft template method. Common soft templates include emulsion droplets, surfactant micelles and block copolymer micelles. For emulsion and surfactant methods, the morphology and dispersity of the resulting hollow products are usually poor due to the deformability of soft templates. Block copolymer micelles can provide a relatively more rigid scaffold for hollow nanostructures that can afford better size and shape control.Amphiphilic molecules can self-assemble into ordered spherical and other shaped micelles with “core-corona” structure, which are mainly composed of single molecules, AB diblock, ABA triblock copolymers, etc. In these systems, the corona of the micelles acts as a reservoir of the inorganic precursors, and the core acts as a template of the hollow. In this approach, however, the template micelles become very unstable when the precursor is asorbed into the corona, leading to the formation of aggregates. To circumvent these problems, a three-component ABC triblock copolymer is newly developed. ABC triblock copolymer micelles can provide nanoassemblies with more diverse morphological and functional features than AB diblock and ABA triblock copolymers. The precursor of the inorganic material is selectively asorbed into the shell domain, leaving the corona free from the inorganic precursors that would destabilize the micelle. The core, meanwhile, is the template for the formation of the hollow void. At present, “core-shell-corona” polymer micelles formed by different ABC triblock copolymers, such as PS-PVP-PEO, PS-PVMP-PEO, PS-b-PAA-b-PEO, have successfully been used to prepare hollow silica nanospheres, metal oxide hollow nanospheres, hollow titanium oxide nanosp-heres, and hollow mesoporous silica nanostructures containing metal oxides in their cavities. In the preparation of these inorganic hollow structures, the core region of the polymer micelles mainly serves as a template for the formation of hollow void; the shell region mainly serves as the reaction region for the sol-gel reaction of the inorganic precursor; corona area acts to stabilize the micelles. This review reports the research progress in the preparation of inorganic hollow nanomaterials using “core-shell-corona” polymer micelles, with respect to the development of polymer micelle templates and the preparation methods of the inorganic hollow nanomaterials with different structures. The applications of inorganic hollow nanomaterials are also discussed, such as the electrode materials, catalysis and drug delivery.
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2020, Vol. 34 
