新型层状氢氧化物的合成、插层组装与修饰
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摘要
层状化合物的插层组装一直备受人们关注,这是由于客体分子或离子的插入会给插层化合物带来一些普通结构难以媲美的化学物理性质。插层氢氧化物包括层状双金属氢氧化物和层状氢氧化物盐,它们是比较少见的阴离子型插层化合物,在多个领域内都有广泛的应用。本文围绕插层氢氧化物做了一些研究。我们合成了以层状金属氢氧化物盐为结构单元的微米管/棒,并详细研究了管/棒的形成机理;我们合成了一种新型含镉类水滑石材料,讨论了合成它的条件和影响因素,并对它的物理,化学性质进行了表征;我们以新型类水滑石为基础对其进行插层组装,得到了碘插层的类水滑石,这种罕见的中性小分子插层类水滑石具有比较特殊的插层结构,而且具有碘的可控吸附-释放性质;此外,将含镉类水滑石硫化而得到的硫化物纳米粒子复合物具有较好的光电压性质。
Intercalation compounds are a family of layered compounds with interlayer species including a variety of molecules and ions. These compounds are widely used in the areas of adsorption, ion exchange, catalyst, ion conductor, etc. so that the host-guest assemble of layered compounds are attracting more and more attention. We describe the synthesis, intercalation and modification of layered hydroxide salt (LHS) and layered double hydroxide (LDH) containing cadmium in this article.
     (1) We have synthesized layered hydroxide salt Cd_2(OH)3DS·nH_2O (DS=C_(12)H_(25)SO_4~-) with microtube/rod morphology. The microtubes/rods have a diameter of 1-2μm and a length of 5-10μm. The forming of tube/rod is driven by directional growth of rolling layers. The growth process of microtubes/rods under the experimental conditions employed follows a dissolution–recrystallization route.
     (2) We have synthesized cadmium/gallium containing layered double hydroxide Cd_2Ga(OH)_6NO_3·H_2O with high purity and high crystalinity. Being the same with hydrotalcite, the LDH has the typical rhomblehedral 3R polytype. We have studied the effect of varying reaction conditions and synthesis rute about the formation of the LDH products. Based on the research above, a possible Cd/Ga LDH formation mechanism is speculated. The intercalated NO_3~- can be substituted by a lot of anions such as CrO_4~(2-),MnO_4~-,Cl~-,I~-,etc. The anion exchanging property of Cd/Ga LDH is essential for its further use.
     (3) We have operated the intercalation and modification on the Cd/Ga LDH. According to our experiments, the cadmium-contianing LDH and ioding molecules have some special interactions between each other. We have found that iodine molecules and anions between the LDH layers form a two-dimentional net-like structure which serves as the charge balancing species. Because of the special interaction between Cd/Ga LDH and iodine, the LDH can absorb and release absorbed I2 in both liquid and gaseous phases in modified reaction conditions. Furthermore, we have synthesized CdS nanoparticles based on the Cd/Ga LDH. The nanocomposite shows excellent photovoltage property under visible light. Its potential in photocatalyst and polar cells has yet to be developed.
引文
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