【作者】 许家胜；

【导师】 薛冬峰；

【作者基本信息】 大连理工大学 ， 化学工艺， 2009， 博士

【摘要】 铜化合物微纳米材料是一类重要的功能材料,因具有许多特殊的性质和广阔的应用前景而倍受关注。本论文以六种铜化合物（氧化亚铜、碱式磷酸铜、碱式碳酸铜、碱式钼酸铜、硫氰酸亚铜和钼酸铜铵）为研究对象,探索溶液相化学合成复杂结构微纳米材料的新方法。对铜化合物微纳米材料生长机理和结晶形态进行深入研究,获得了一些对铜化合物微纳米材料生长规律的初步认识,在一定程度上实现了对六种铜化合物微纳米结构的控制合成。EDTA还原法制备氧化亚铜（Cu₂O）微晶,其结晶形态展示了立方晶系中的五种枝晶生长方式。该合成体系中,EDTA具有鳌合作用、还原作用和选择性吸附作用。通过改变实验条件,可以对氧化亚铜结晶形态进行有效控制。采用水热法合成了六种结晶形态的碱式磷酸铜（Cu₂（OH）PO₄）。单晶、孪晶以及各种新颖的碱式磷酸铜复杂结构可以通过改变实验条件来控制合成。碱式磷酸铜晶体具有沿着c轴方向生长的趋势,并具有旋转孪晶生长的习性,这是能够形成不同结晶形态碱式磷酸铜的内因。水热条件下制备出新颖球形等级结构的碱式碳酸铜（Cu₂（OH）₂CO₃）和毛刺状空心等级结构的碱式钼酸铜（Cu₃（OH）₂（MoO₄）₂）微晶材料。碱式碳酸铜球形等级结构是由大量平行于球表面的二维薄片构成,其形成过程是逐层生长机理,在一定范围内,球的直径随着反应时间的增加而逐渐增大。碱式钼酸铜空心等级结构的形成过程中,奥氏熟化起到关键作用。对碱式碳酸铜和碱式钼酸铜样品分别进行热处理,可以得到相应的氧化铜和钼酸铜等级结构材料。采用室温液相法在铜基片上制备出硫氰酸亚铜（β-CuSCN）阵列和钼酸铜铵（（NH₄）₂Cu（MoO₄）₂）纳米片,该方法利用铜片作为反应物和基底,使制备工艺大大简化。硫氰酸亚铜阵列中,每一个基元的结晶形态是倒立锥体,且均匀分部在铜片表面。硫氰酸亚铜晶体具有沿着c轴方向生长的习性,这是能够形成硫氰酸亚铜阵列的内因。钼酸铜铵纳米片近似垂直于铜片表面生长,片与片之间相互啮合形成纳米沟槽形态。该合成体系中,甲酰胺不仅促进了铜片氧化,而且选择性吸附在晶体表面改变了晶体生长的微观环境,从而影响了硫氰酸亚铜和钼酸铜铵的结晶形态。更多还原

【Abstract】 As one kind of inorganic functional materials,copper-based micro/nanomaterials present some novel properties and wide applications.In this dissertation,copper compounds （i.e.,cuprous oxide,copper hydroxyphosphate,malachite,lindgrenite,cuprous thiocyanate, and ammonium copper molybdate） were investigated.The aim is to explore the synthesis of complex micro/nanostructure copper compounds by solution routes.Their growth mechanisms and crystal shapes were investigated.Cuprous oxide（Cu₂O） was selected in this study to elucidate the shape evolution in the cubic crystal system.A wide range of novel cuprous oxide microcrystals（based on the five branching growth patterns） has been prepared through an EDTA reduction route by employing EDTA molecule as chelating reagent,reductant,and sorbent.The morphology of these microcrystals has a strong dependence on the reaction conditions,which implies vast possibilities of designing new crystal morphologies.Copper hydroxyphosphate（Cu₂（OH）PO₄） with complex architectures has been successfully synthesized through a hydrothermal route. Single-crystals,twinned-crystals,and various novel architectures of copper hydroxyphosphate were constructed through a careful control of synthetic parameters.Copper hydroxyphosphate crystals tend to grow along the c-axis and have a rotation twinned growth habit,which is essential for the formation of various complex architectures.Malachite（Cu₂（OH）₂CO₃） with a hierarchical sphere-like architecture has been successfully synthesized via a hydrothermal route in the absence of any external inorganic additives or organic structure-directing templates.The hierarchical malachite particles are comprised of numerous two-dimensional micro-platelets paralleling to the sphere surface. The growth of the hierarchical architecture is believed to be a layer-by-layer growth process. Copper oxide with the similar morphology can be easily obtained from the as-prepared malachite.Lindgrenite（Cu₃（OH）₂（MoO₄）₂） with a hollow and prickly sphere-like architecture has been synthesized via the same hydrothermal route.The hierarchical lindgrenite particles are hollow and prickly spheres,which are comprised of numerous small crystal strips that are aligned perpendicularly to the spherical surface.Ostwald ripening in solution is responsible for the hollow structure.Furthermore,Cu₃Mo₂O₉ with the similar size and morphology can be easily obtained by a thermal treatment of the as-prepared lindgrenite in air atmosphere. A novel strategy has been designed to form upended taper-shaped cuprous thiocyanate （β-CuSCN） arrays and curved ammonium copper molybdate（（NH₄）₂Cu（MoO₄）₂） nanoflakes on a copper substrate using a solution-phase method at room temperature.This method consists in a liquid-solid reaction between a solution of thiocyanate ammonium and the copper substrate itself in the assistance of fonnamide.Novel cuprous thiocyanate arrays are approximately perpendicular to copper substrate surfaces.Every single crystal shows an upended taper-like morphology.Cuprous thiocyanate crystals tend to grow along the c-axis, which is essential for the formation of cuprous thiocyanate arrays on a copper substrate.The lamellar ammonium copper molybdate are approximately perpendicular to the copper substrate surface and are intermeshed with each other to form nanogroove structures. Formamide molecules can not only promote the oxidation of copper substrate and the formation of copper-complex,but also act as NH₄⁺ source in the final products.Furthermore, the selective adsorption of formamide molecules on different crystallographic planes of ammonium copper molybdate plays the major role in determining the curved morphology.更多还原