Abstract
We have demonstrated a solution-based synthesis of novel waxberry-like hierarchical ZnO microparticles in the presence casein micelles under mild conditions. The microstructures of the sub-micrometer-sized hierarchical microparticles were characterized, and the synthesis conditions were optimized. The formation mechanism of the hierarchical microparticle was analyzed through control experiments. The hierarchical ZnO microparticles are found to be super-assemblies of 30–70 nm ZnO nanoparticles, which are thought to be based on casein micelle induction followed by Ostwald ripening. In the same manner, copper-based hierarchical microparticles with a similar morphology have also been successfully synthesized. By controlling the synthetic time or temperature, solid or hollow microparticles can be fabricated. The narrowly distributed ZnO microparticles have a high specific surface area, exhibiting great potential application in fields such as photocatalytic and energy conversion. Our findings may meanwhile open a new bottom-up strategy in order to construct structurally sophisticated nanomaterials.
Notes
Unpublished results: the viscosity of 10 wt % casein solution at shear rates ranging from 1 to 100 s−1 and the intrinsic viscosity ([η]) of casein in the presence of additional Zn(NO3)2 have been found to be lower than those in the presence of NaCl with identical ionic strength. These observations were attributed to the shrinkage of the casein micelles via intramicellar “cross linking” induced by positively charged multivalent zinc complexes like [Zn(NH3)4]2+. The [η] of casein micelles in ammonia aqueous solution has been found to decrease with rising temperature, where these changes take place very slowly within hours.
Moreover, electrospray ionization-mass spectroscopic (ESI-MS) measurement of the thermally treated casein micelle solution displayed molecular weight in the range from 230 to 1300 Da, indicating disruption and decomposition of casein under the hydrothermal synthesis condition.
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Acknowledgments
We thank Prof. Dr. B. A. Wolf and Prof. Dr. W. Tremel for valuable comments and discussions. The sponsoring of X. Xiong’s stay in Germany by the DAAD-K.C.Wong is gratefully acknowledged. This work was financially funded by the National Natural Science Foundation of China (No. 51273166) and the National Basic Research Program of China (2010CB732203).
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Xiong, X., Duan, J., Wang, Y. et al. Novel hierarchical microparticles super-assembled from nanoparticles with the induction of casein micelles. J Nanopart Res 15, 1870 (2013). https://doi.org/10.1007/s11051-013-1870-4
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DOI: https://doi.org/10.1007/s11051-013-1870-4