The standing porous nanoplate-built ZnO hollow microspheres with micro/nanostructure are fabricated based on a modified hydrothermal strategy, using citrate as structural director, and subsequent annealing treatment. The hollow spheres are composed of the vertically standing and cross-linked single crystalline porous nanoplates with the exposed surface of nonpolar (10\(\bar 1\)0) planes. Experiments have revealed the structural evolution: the formation of amorphous spheres in the initial reaction stage, followed by surface crystallization and nanoplate outward growth accompanied by inward dissolution of the amorphous spheres. Citrate in the precursor solution plays a dominant role in the formation of such porous ZnO hollow spheres. A model is presented, based on citrate-induced amorphous sphere formation and kinetically controlled dissolution and crystal growth. The model describes the formation of the hollow spheres, thermodynamically and kinetically.
This is a preview of subscription content, access via your institution.
Buy single article
Instant access to the full article PDF.
Tax calculation will be finalised during checkout.
Subscribe to journal
Immediate online access to all issues from 2019. Subscription will auto renew annually.
Tax calculation will be finalised during checkout.
Y. Zhao and L. Jiang: Hollow micro/nanomaterials with multilevel interior structures. Adv. Mater. 21, 3621 (2009).
T.Y. Ma, X.J. Zhang, and Z.Y. Yuan: Hierarchical meso/macroporous aluminum phosphonate hybrid materials as multifunctional adsorbents. J. Phys. Chem. C 113, 12854 (2009).
F. Lu, W. Cai, and Y.G. Zhang: ZnO hierarchical micro/nanoarchitectures: Solvothermal synthesis and structurally enhanced photocatalytic performance. Adv. Funct. Mater. 18, 1047 (2008).
H.G. Zhang, Q.S. Zhu, Y. Zhang, Y. Wang, L. Zhao, and B. Yu: One-pot synthesis and hierarchical assembly of hollow Cu2O microspheres with nanocrystals-composed porous multishell and their gas-sensing properties. Adv. Funct. Mater. 17, 2766 (2007).
B. Meyer, H. Rabaab, and D. Marx: Water adsorption on ZnO(1010): From single molecules to partially dissociated monolayers. Phys. Chem. Chem. Phys. 8, 1513 (2006).
Y. Kikuchi, Q.R. Qian, M. Machida, and H. Tatsumoto: Effect of ZnO loading to activated carbon on Pb(II) adsorption from aqueous solution. Carbon 44, 195 (2006).
X.B. Wang, W.P. Cai, Y.X. Lin, G.Z. Wang, and C.H. Liang: Mass production of micro/nanostructured porous ZnO plates and their strong structurally enhanced and selective adsorption performance for environmental remediation. J. Mater. Chem. 20, 8582 (2010).
W.W. Lu, S.Y. Gao, and J.J. Wang: One-pot synthesis of Ag/ZnO self-assembled 3D hollow microspheres with enhanced photocatalytic performance. J. Phys. Chem. C 112, 16792 (2008).
Y.C. Lu, L.L. Wang, D.J. Wang, T.F. Xie, L.P. Chen, and Y.H. Lin: A comparative study on plate-like and flower-like ZnO nanocrystals surface photovoltage property and photocatalytic activity. Mater. Chem. Phys. 129, 281 (2011).
M. Chen, Z.H. Wang, D.M. Han, F.B. Gu, and G.S. Guo: High-sensitivity NO2 gas sensors based on flower-like and tube-like ZnO nanomaterials. Sens. Actuators, B 157, 565 (2011).
E. Kowsari: Sonochemically assisted synthesis and application of hollow spheres, hollow prism, and coralline-like ZnO nanophotocatalyst. J. Nanopart. Res. 13, 3363 (2011).
Y.Y. Zhang, W.Y. Fu, Y.M. Sui, H.B. Yang, J. Cao, M.H. Li, Y.X. Li, X.M. Zhou, Y. Leng, W.Y. Zhao, H. Chen, L. Zhang, Q. Jing, and H. Zhao: Twinned tabour-like ZnO: Surfactant-, template-free synthesis and gas sensing behaviors. Appl. Surf. Sci. 257, 5784 (2011).
F. Caruso, R.A. Caruso, and H. Mohwald: Nanoengineering of inorganic and hybrid hollow spheres by colloidal templating. Science 282, 1111 (1998).
Y.G. Sun, B.T. Mayers, and Y.N. Xia: Template-engaged replacement reaction: A one-step approach to the large-scale synthesis of metal nanostructures with hollow interiors. Nano Lett. 2, 481 (2002).
P.R. Selvakannan and M. Sastry: Hollow gold and platinum nanoparticles by a transmetallation reaction in an organic solution. Chem. Commun. 41, 1684 (2005).
Y.D. Yin, R.M. Rioux, C.K. Erdonmez, S. Hughes, G.A. Somorjai, and A.P. Alivisatos: Formation of hollow nanocrystals through the nanoscale Kirkendall effect. Science 304, 711 (2004).
H.L. Xu and W.Z. Wang: Template synthesis of multishelled Cu2O hollow spheres with a single-crystalline shell wall. Angew. Chem. Int. Ed. 46, 1489 (2007).
W. Ostwald: On the assumed isomerism of red and yellow mercury oxide and the surface-tension of solid bodies. Z. Phys. Chem. 34, 495 (1900).
Y.X. Du and Q.X. Yuan: Catalyst-free synthesis of honeycomb-like and straight ZnO nanowires. J. Alloy. Comp. 494, 468 (2010).
C. Li, Z.S. Yu, S.M. Fang, H.X. Wang, Y.H. Gui, J.Q. Xu, and R.F. Chen: Fabrication and gas sensing property of honeycomb-like ZnO. Chin. Chem. Lett. 19, 599 (2008).
Z.H. Jing and J.H. Zhan: Fabrication and gas-sensing properties of porous ZnO nanoplates. Adv. Mater. 20, 4547 (2008).
X.Y. Zeng, J.L. Yuan, and L.D. Zhang: Synthesis and photoluminescent properties of rare earth doped ZnO hierarchical microspheres. J. Phys. Chem. C 112, 3503 (2008).
J. Zhang, S.R. Wang, M.J. Xu, Y. Wang, B.L. Zhu, S.M. Zhang, W.P. Huang, and S.H. Wu: Hierarchically porous ZnO architectures for gas sensor application. Cryst. Growth Des. 9, 3532 (2009).
S. Brunauer, L.S. Deming, W.E. Deming, and E. Teller: On a theory of the van der Waals adsorption of gases. J. Am. Chem. Soc. 62, 1723 (1940).
S. Brunauer, P.H. Emmett, and E. Teller: Adsorption of gases in multimolecular layers. J. Am. Chem. Soc. 60, 309 (1938).
J.D. Verhoeven: Fundamentals of Physical Metallurgy, Ch. 8 (John Wiley & Sons, NY, 1975).
Z.R. Tian, J.A. Voigt, J. Liu, B. Mckenziei, M.J. Mcdermott, M.A. Rodriguez, H. Konishi, and H.F. Xu: Complex and oriented ZnO nanostructures. Nat. Mater. 2, 821 (2003).
C.L. Kuo, T.J. Kuo, and M.H. Huang: Hydrothermal synthesis of ZnO microspheres and hexagonal microrods with sheetlike and platelike nanostructures. J. Phys. Chem. B 109, 20115 (2005).
J.D. Verhoeven: Fundamentals of Physical Metallurgy, Ch. 11, 12 (John Wiley & Sons, NY, 1975).
Q. Hao, L.Q. Xu, G.D. Li, and Y.T. Qian: Hydrothermal synthesis of microscaled Cu@C polyhedral composites and their sensitivity to convergent electron beam. Langmuir 25, 6363 (2009).
W. Zhao, X.Y. Song, G.Z. Chen, and S.X. Sun: One-step template-free synthesis of ZnWO4 hollow clusters. J. Mater. Sci. 44, 3082 (2009).
X. Li, C.J. Tang, M. Ai, L. Dong, and Z. Xu: Controllable synthesis of pure-phase rare-earth orthoferrites hollow spheres with a porous shell and their catalytic performance for the CO+NO reaction. Chem. Mater. 22, 4879 (2010).
Y.M. Sui, W.Y. Fu, H.B. Yang, Y. Zeng, Y.Y. Zhang, Q. Zhao, Y.G. Li, X.M. Zhou, Y. Leng, M.H. Li, and G.T. Zou: Low-temperature synthesis of Cu2O crystals: Shape evolution and growth mechanism. Cryst. Growth Des. 10, 99 (2010).
This work was financially supported by the China Postdoctoral Science Foundation (Grant No. 2011M501407) and Natural Science Foundation of China (Grant No. 21001002).
About this article
Cite this article
Wang, X., Cai, W., Wang, G. et al. Standing porous ZnO nanoplate-built hollow microspheres and kinetically controlled dissolution/crystal growth mechanism. Journal of Materials Research 27, 951–958 (2012). https://doi.org/10.1557/jmr.2012.15