Urchin-like ZnO microspheres synthesized by thermal decomposition of hydrozincite as a copper catalyst promoter for the Rochow reaction

Urchin-like ZnO microspheres were successfully prepared by thermal decomposition of hydrozincite synthesized via homogeneous precipitation of zinc nitrate and urea in the presence of a nonionic surfactant polyethylene glycol. The synthesis conditions, such as reaction temperature and time, precursor concentration, and the amount of surfactant added, as well as the catalytic properties of urchin-like ZnO microspheres as promoters for a commercial copper catalyst in dimethyldichlorosilane synthesis were investigated. In addition, the formation mechanism of urchin-like microspheres from hydrozincite to ZnO was proposed. The ZnO samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, thermogravimetric analysis, and N2 adsorption. It was found that zinc nitrate concentration and the amount of surfactant are the key factors that lead to the formation of urchin-like ZnO microspheres. These ZnO samples had BET surface areas of 16–30 m2 g−1 and an average diameter of 3–8 μm. Compared with commercial Zn microspheres and ZnO nanoparticles, urchin-like ZnO microspheres showed a better performance in dimethyldichlorosilane synthesis via the Rochow reaction due to their larger surface area, which created more interfacial contacts with the copper catalyst and active Cu3Si species. The work is helpful for developing novel catalyst promoters and understanding the role of the promoter in the Rochow reaction.

[1]  Alexander D. Gordon,et al.  Effects of Multiple Promotion of the Direct Synthesis Contact Mass with P, Zn, and Sn on the Synthesis of Methylchlorosilanes , 2009 .

[2]  J. Rathouský,et al.  Electrodeposited Mesoporous ZnO Thin Films as Efficient Photocatalysts for the Degradation of Dye Pollutants , 2007 .

[3]  Tierui Zhang,et al.  Site-specific nucleation and growth kinetics in hierarchical nanosyntheses of branched ZnO crystallites. , 2006, Journal of the American Chemical Society.

[4]  Di Gao,et al.  Preferential Growth of Long ZnO Nanowire Array and Its Application in Dye-Sensitized Solar Cells , 2010 .

[5]  D. Rethwisch,et al.  Role of metallic promoters in the direct synthesis of methylchlorosilanes , 1991 .

[6]  Alexander D. Gordon,et al.  Effects of individual promoters on the Direct Synthesis of methylchlorosilanes , 2009 .

[7]  Xuefeng Guo,et al.  Microsphere organization of nanorods directed by PEG linear polymer. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[8]  R. Schlögl,et al.  Knowledge-based development of a nitrate-free synthesis route for Cu/ZnO methanol synthesis catalysts via formate precursors. , 2011, Chemical communications.

[9]  N. Lewis,et al.  Active site formation in the direct process for methylchlorosilanes , 1986 .

[10]  Jinfu Wang,et al.  Effect of CuCl particle size on the reduction reaction by silicon in preparation of contact mass used for methylchlorosilane synthesis , 2006 .

[11]  L. Lewis,et al.  Effect of low aluminum silicon on the direct process , 2003 .

[12]  Kuei-Hsien Chen,et al.  Catalytic performance of plate-type Cu/Fe nanocomposites on ZnO nanorods for oxidative steam reforming of methanol. , 2011, Chemical communications.

[13]  C. M. Li,et al.  Randomly oriented ZnO nanorods as advanced substrate for high-performance protein microarrays. , 2010, ACS applied materials & interfaces.

[14]  Chunjuan Tang,et al.  Controllable Preferential-Etching Synthesis and Photocatalytic Activity of Porous ZnO Nanotubes , 2008 .

[15]  W. Park,et al.  Sonochemical Preparation of Shape-Selective ZnO Nanostructures , 2008 .

[16]  M. C. Neves,et al.  Synthetic hollow zinc oxide microparticles , 2001 .

[17]  Hanning Xiao,et al.  Investigation of PEG adsorption on the surface of zinc oxide nanoparticles , 2004 .

[18]  Jiajian Gao,et al.  Facile Synthesis of Mesoporous Cu2O Microspheres with Improved Catalytic Property for Dimethyldichlorosilane Synthesis , 2012 .

[19]  Zhong Lin Wang,et al.  Mesoporous polyhedral cages and shells formed by textured self-assembly of ZnO nanocrystals. , 2003, Journal of the American Chemical Society.

[20]  Hao Wang,et al.  Facile fabrication of porous ZnO microspheres by thermal treatment of ZnS microspheres. , 2010, Journal of hazardous materials.

[21]  Zhifeng Liu,et al.  Assembly of ordered ZnO porous thin films by cooperative assembly method using polystyrene spheres and ultrafine ZnO particles , 2006 .

[22]  Jiajian Gao,et al.  Flower-like CuO microspheres with enhanced catalytic performance for dimethyldichlorosilane synthesis , 2012 .

[23]  Zorica Crnjak Orel,et al.  Correlation between Morphology and Defect Luminescence in Precipitated ZnO Nanorod Powders , 2009 .

[24]  Yueping Fang,et al.  Electrochemical route to the preparation of highly dispersed composites of ZnO/carbon nanotubes with significantly enhanced electrochemiluminescence from ZnO , 2008 .

[25]  Gaoke Zhang,et al.  Facile Synthesis of Monodisperse Porous ZnO Spheres by a Soluble Starch-Assisted Method and Their Photocatalytic Activity , 2011 .

[26]  W. Banholzer,et al.  Characterization of reactive areas in the direct process for the production of methylchlorosilanes , 1988 .

[27]  Costas P. Grigoropoulos,et al.  ZnO nanowire network transistor fabrication on a polymer substrate by low-temperature, all-inorganic nanoparticle solution process , 2008 .

[28]  Y. Xiong,et al.  Selected-control synthesis of ZnO nanowires and nanorods via a PEG-assisted route. , 2003, Inorganic chemistry.

[29]  Jinwoo Cheon,et al.  Anisotropic Shape Control of Colloidal Inorganic Nanocrystals , 2003 .

[30]  W. J. Ward,et al.  The Use of a Fixed-Bed Reactor to Evaluate the Interactions of Catalysts and Promoters in the Methyl Chlorosilane Reaction and to Determine the Effect of Cu in the Form of the Eta Phase on This Reaction , 2002 .

[31]  L. Lewis,et al.  Mechanism of the methylchlorosilane reaction: Improved lab reactor design and kinetic data , 2003 .

[32]  Qingliang Liao,et al.  Synthesis and Characterization of Sb-Doped ZnO Nanobelts with Single-Side Zigzag Boundaries , 2008 .

[33]  Wei-min Liu,et al.  PEG-mediated synthesis of ZnO nanostructures at room temperature , 2007 .

[34]  E. G. Rochow.  The Direct Synthesis of Organosilicon Compounds , 1945 .

[35]  C. M. Li,et al.  Tailoring Zinc Oxide Nanowires for High Performance Amperometric Glucose Sensor , 2007 .

[36]  D. Lan,et al.  From hexagonally arrayed nanorods to ordered porous film through controlling the morphology of ZnO crystals , 2008 .

[37]  D. Seyferth.  Dimethyldichlorosilane and the Direct Synthesis of Methylchlorosilanes. The Key to the Silicones Industry , 2001 .

[38]  K. Sing.  Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity (Recommendations 1984) , 1985 .

[39]  Kijung Yong,et al.  Mechanism Study of ZnO Nanorod-Bundle Sensors for H2S Gas Sensing , 2011 .

[40]  Jian Shen,et al.  A novel tetragonal pyramid-shaped porous ZnO nanostructure and its application in the biosensing of horseradish peroxidase , 2008 .

[41]  J. Carnahan,et al.  A study of copper oxide catalysts used in the methylchorosilane reaction and determination of the fate of oxygen , 2002 .

[42]  Xuefeng Guo,et al.  Mechanistic investigations of PEG-directed assembly of one-dimensional ZnO nanostructures. , 2006, The journal of physical chemistry. B.

[43]  Chenglin Yan,et al.  Morphosynthesis of hierarchical hydrozincite with tunable surface architectures and hollow zinc oxide. , 2006, The journal of physical chemistry. B.

[44]  Lei Liao,et al.  Carbon-decorated ZnO nanowire array: A novel platform for direct electrochemistry of enzymes and biosensing applications , 2009 .

[45]  B. Reeja‐Jayan,et al.  Structural Characterization and Luminescence of Porous Single Crystalline ZnO Nanodisks with Sponge-like Morphology , 2008 .

[46]  E. McFarland,et al.  Combinatorial Electrochemical Synthesis and Screening of Mesoporous ZnO for Photocatalysis , 2004 .

[47]  Timothy C. Frank,et al.  Catalytic formation of silanes on copper-silicon alloys , 1985 .

[48]  J. Falconer,et al.  Interaction of Copper Catalysts and Si(100) for the Direct Synthesis of Methylchlorosilanes , 1994 .