摘要
本论文选择具有工业催化应用背景的经典Keggin型多金属氧酸盐(POM)为基质，利用一种简便的无模板水溶液合成法，制备出四种Keggin型POM微米管：金属阳离子Zn~(2+)和Cd~(2+)调变的Keggin型POM微米管；生物活性分子掺杂的Keggin型POM微米管；Mo/V取代的Keggin型POM微米管；Keggin型杂多蓝微米管。探讨了Keggin型POM微米管的合成条件，生长机理，化学性质和物理性质。
1、过渡金属阳离子具有丰富多彩的物理化学性质，将其引入POM微米管中，替换部分K+和Na+离子，从而可以将过渡金属的性质引入到POM微米管中。基于这一反应原理，我们制备了Zn~(2+)和Cd~(2+)离子调变的Zn-SiW_(12)和Cd-SiW_(12)微米管。将得到的Zn-SiW_(12)和Cd-SiW_(12)微米管用8-羟基喹啉(Q)乙醇溶液处理后，测定了其荧光发射光谱，显示出ZnQ_2和CdQ_2的荧光特性。
2、在对POM微米管生长机理的研究中我们发现，在适当的条件下可以将有机组分掺杂于Keggin型多酸微米管，从而将掺杂剂的性质引入到POM微米管中。我们在微米管生长过程中掺杂了抗坏血酸(AA)和L-半胱氨酸(Lcys)，AA和Lcys的含量在一定范围内可以进行调控。得到的AA-SiW_(12)和Lcys-SiW_(12)微米管对氨气具有敏感变色性质。
3、Keggin型杂多钨硅酸盐中的W原子可以被Mo和V原子等过渡金属原子所取代，取代后的POM的电化学性质和电催化性质将会明显不同于全钨系列的POM。我们利用单缺位杂多钨硅酸盐在酸性介质中不稳定并且在有Mo和V存在时容易生成Mo和V取代的POM的化学性质，以单缺位杂多钨硅酸盐为原料制备出Mo和V取代的Keggin型SiW_(11)Mo和SiW_(11)V微米管，研究了所制备的微米管的氧化还原性。
4、氧化态的多金属氧酸盐具有接受电子的能力而生成还原态的杂多蓝(HPB)。我们利用这一性质制备了SiW_(12)-HPB和SiMoVW_(11)微米管。所制备的微米管作为电子给体，可以将氧化还原电势匹配的金属阳离子(如贵金属阳离子)原位还原成金属纳米粒子而负载于管体上。应用此方法合成的金属纳米粒子尺寸分布较为一致且分散均匀。固载金属纳米粒子的微米管可以作为催化剂，对于一些有机反应，如烯烃环氧化和氢化、醇的氧化等有着很好的选择性和转化率。
本论文中所制备的微米管材料不仅结合了POM的优良物理化学性能而且还发挥了中空结构的特点，在光电信息材料、催化剂、分子吸收剂、微反应器、生物传感器和气体传感器等方面显示出潜在的应用前景。
In this thesis, the classical Keggin-type polyoxometalate (POM) with potentialapplications in industrial catalysis is selected as a substrate, four kinds of POMmicrotubes have been synthesized through a simple free-template aqueous synthesismethod, i.e., Zn~(2+)and Cd~(2+)cation-tuned Keggin-type POM microtubes, bioactivemolecule-doped Keggin-type POM microtubes, Mo/V-substituted Keggin-type POMmicrotubes, and Keggin-type heteropoly blue microtubes. Synthesis conditions,growth mechanism, chemical and physical properties of the POM microtubes arediscussed.
1. Transition metal cations with abundant physical and chemical properties canbe introduced into the POM microtubes through replacing part of K+or Na+ions inthe microtubes, so that the POM microtubes are endowed with the properties oftransition metals. Based on this principle, Zn~(2+)and Cd~(2+)cation-tuned POM (Zn-SiW_(12)and Cd-SiW_(12)) microtubes are prepared. Fluorescence emission spectra of theobtained microtubes dealt with an ethanol solution of8-hydroxyquinoline (Q) aremeasured, which display fluorescence of ZnO2and CdQ_2.
2. During the study on mechanism for the formation of the POM microtubes, wefound that some organic components can be doped into the POM microtubes undersuitable conditions. Thus, the POM microtubes may possess the properties of thedopant. We have doped ascorbic acid (AA) and L-cysteine (Lcys) into POMmicrotubes during the growth process of the microtubes. The content of the dopantscan be controlled to some extent. The obtained AA-SiW_(12)and Lcys-SiW_(12)microtubesshow sensitivity to ammonia gas.
3. The W atom in the Keggin-type tungstosilicate can be substituted by Mo, Vand the other transition metals, and the substituted POM will have differentelectrochemical and electrocatalytic properties from the full-W series. Themono-vacant Keggin-type tungstosilicate is unstable in an acidic medium, and readilyforms Mo and V-substituted POMs in the presence of Mo and V. According to thisreactivity, we have prepared the Mo and V-substituted POM (SiW_(11)Mo and SiW_(11)V)microtubes and investigated their redox properties.
4. The POM in oxidation state can accept electrons and form heteropoly blue(HPB). Accordingly, the SiW_(12)-HPB and SiMoVW_(11)microtubes are prepared. The obtained microtubes can be used as electron donor to in situ reduce the noble metalcations with matchable redox potential to metal nanoparticles (NPs), thus NPs aredeposited on the microtubes. The size of the obtained NPs is consistent, and the NPsare evenly spreaded. The NP-immobilized microtubes can be used as excellentcatalysts for some organic reactions, such as the epoxidation of alkene and theoxidation of alcohol.
The as-prepared POM tubular materials display potential applicationsin photoelectrical materials, catalysts, molecular absorbers, microreactors, biologicaland chemical sensors, due to combination of the perfect physicochemical properties ofPOMs and the mesoscopic hollow structure of microtubes.
引文
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