Large-Scale Fabrication of Novel Hierarchical 3D CaMoO4 and SrMoO4 Mesocrystals via a Microemulsion-Mediated Route

Molybdates such as CaMoO4 and SrMoO4 have received much attention recently because of their interesting luminescence and structural properties. Herein, we report a microemulsion-mediated method as a novel technique to synthesize CaMoO4 and SrMoO4 mesocrystals with high hierarchy and with hollow structure. The “arms” of the flowerlike 3D mesocrystals are radial and are about 2−3 μm in length. They are constructed from nanoparticles with regular morphology and a size of about 150−300 nm. Study on the formation mechanism of the superstructures reveals that the oriented aggregation mechanism is responsible for the self-assembly. The mesocrystals of CaMoO4 and SrMoO4 are shown to be in a thermodynamically metastable state, which can be destroyed by further reaction time or temperature change.

[1]  Banfield,et al.  Imperfect oriented attachment: dislocation generation in defect-free nanocrystals , 1998, Science.

[2]  H. Yang,et al.  Self-construction of hollow SnO(2) octahedra based on two-dimensional aggregation of nanocrystallites. , 2004, Angewandte Chemie.

[3]  Takashi Kato,et al.  Self-organized calcium carbonate with regular surface-relief structures. , 2003, Angewandte Chemie.

[4]  George M Whitesides,et al.  Three-dimensional self-assembly of metallic rods with submicron diameters using magnetic interactions. , 2003, Journal of the American Chemical Society.

[5]  Zhang,et al.  Temperature dependence of the polarized Raman spectra of ZnWO4 single crystals. , 1992, Physical review. B, Condensed matter.

[6]  D. Kuang,et al.  Preparation of inorganic salts (CaCO3, BaCO3, CaSO4) nanowires in the Triton X-100/cyclohexane/water reverse micelles , 2002 .

[7]  M. Antonietti,et al.  Polymer-controlled crystallization of zinc oxide hexagonal nanorings and disks. , 2006, The journal of physical chemistry. B.

[8]  Peidong Yang,et al.  Synthesis and assembly of BaWO4 nanorods , 2001 .

[9]  M. Antonietti,et al.  Uniform Hexagonal Plates of Vaterite CaCO3 Mesocrystals Formed by Biomimetic Mineralization , 2006 .

[10]  D. Jiang,et al.  Hydrothermal synthesis of highly ordered micropompon of lanthanum molybdate nanoflakes , 2005 .

[11]  M. Antonietti,et al.  Polymer-Controlled Morphosynthesis and Mineralization of Metal Carbonate Superstructures (†). , 2003, The journal of physical chemistry. B.

[12]  Weigang Lu,et al.  Perfect orientation ordered in-situ one-dimensional self-assembly of Mn-doped PbSe nanocrystals. , 2004, Journal of the American Chemical Society.

[13]  L. Qi,et al.  Architectural Control of Hierarchical Nanobelt Superstructures in Catanionic Reverse Micelles , 2005 .

[14]  S. Mann,et al.  The Chemistry of Form. , 2000, Angewandte Chemie.

[15]  P. Yang,et al.  Langmuir-Blodgett nanorod assembly. , 2001, Journal of the American Chemical Society.

[16]  J. Banfield,et al.  Aggregation-based crystal growth and microstructure development in natural iron oxyhydroxide biomineralization products. , 2000, Science.

[17]  Zhiyong Tang,et al.  Simple Preparation Strategy and One-Dimensional Energy Transfer in CdTe Nanoparticle Chains , 2004 .

[18]  Qingsheng Wu,et al.  Abnormal Polymorph Conversion of Calcium Carbonate and Nano-Self-Assembly of Vaterite by a Supported Liquid Membrane System , 2004 .

[19]  Xun Fu,et al.  Fabrication of hollow spheres and thin films of nickel hydroxide and nickel oxide with hierarchical structures. , 2005, The journal of physical chemistry. B.

[20]  Qingsheng Wu,et al.  Simultaneous Synthesis of Dendritic Superstructural and Fractal Crystals of BaCrO4 by Vegetal Bi-templates , 2006 .

[21]  Thomas E Mallouk,et al.  Nanowires as building blocks for self-assembling logic and memory circuits. , 2002, Chemistry.

[22]  Q. Zhuang,et al.  Laser photochemical ablation of CdWO4 studied with the time‐of‐flight mass spectrometric technique , 1995 .

[23]  T. Ohta,et al.  Self-assembly of Co nanoplatelets into spheres: Synthesis and characterization , 2005 .

[24]  P. Yuan,et al.  Synthesis of crystalline SrMoO4 nanowires from polyoxometalates , 2005 .

[25]  Hua-gui Zheng,et al.  A Simple Aqueous Mineralization Process to Synthesize Tetragonal Molybdate Microcrystallites , 2006 .

[26]  Daqin Chen,et al.  Evolution of single crystalline dendrites from nanoparticles through oriented attachment. , 2005, The journal of physical chemistry. B.

[27]  Shuhong Yu,et al.  Morphology control of stolzite microcrystals with high hierarchy in solution. , 2004, Angewandte Chemie.

[28]  M. Antonietti,et al.  Promises and problems of mesoscale materials chemistry or why meso? , 2004, Chemistry.

[29]  Stephen Mann,et al.  Higher-order organization by mesoscale self-assembly and transformation of hybrid nanostructures. , 2003, Angewandte Chemie.

[30]  M. Pileni,et al.  Nanocrystal Self-Assemblies: Fabrication and Collective Properties , 2001 .

[31]  Xiaogang Peng,et al.  Mechanisms of the Shape Evolution of CdSe Nanocrystals , 2001 .

[32]  Markus Antonietti,et al.  Mesocrystals: inorganic superstructures made by highly parallel crystallization and controlled alignment. , 2005, Angewandte Chemie.

[33]  Shuhong Yu,et al.  Selective synthesis and characterization of single-crystal silver molybdate/tungstate nanowires by a hydrothermal process. , 2004, Chemistry.

[34]  L. Qi,et al.  Morphosynthesis of rhombododecahedral silver cages by self-assembly coupled with precursor crystal templating. , 2005, Angewandte Chemie.

[35]  T. Oi,et al.  Scintillation study of ZnWO4 single crystals , 1980 .

[36]  G. Blasse,et al.  The Luminescence of Calcium Molybdate , 1979 .

[37]  Jong-Won Yoon,et al.  Microwave-assisted synthesis of CaMoO4 nano-powders by a citrate complex method and its photoluminescence property , 2005 .

[38]  G. Whitesides,et al.  Self-Assembly at All Scales , 2002, Science.

[39]  Qingsheng Wu,et al.  Controlled synthesis of different morphologies of BaWO4 crystals through biomembrane/organic-addition supramolecule templates , 2005 .

[40]  Hongwei Liao,et al.  Hydrothermal Preparation and Characterization of Luminescent CdWO4 Nanorods. , 2000 .

[41]  B. Liu,et al.  Mesoscale organization of CuO nanoribbons: formation of "dandelions". , 2004, Journal of the American Chemical Society.