【作者】 赵林；

【导师】 邢彦军； 李戎；

【作者基本信息】 东华大学 ， 纺织化学与染整工程， 2017， 硕士

【摘要】 磷酸锆铜作为一种磷酸复盐,有关其合成与应用的报道较少,报道的磷酸锆铜的合成方法主要采用水热法,即采用阳离子交换理论在高温高压的条件下使二价铜离子与磷酸锆中的氢离子发生离子交换反应,生成磷酸锆铜,该方法步骤繁琐,反应时间长,同时制备的磷酸锆铜形貌难以控制。微波辅助合成法作为新兴的纳米材料合成方法,能制备结构完好、形态均一的纳米材料,微波的非热效应也能够影响产物晶型的形成,同时又高效节能、绿色环保。目前尚未有报道采用微波辅助法制备磷酸锆铜。本论文采用微波辅助合成法在低温开放条件下对特殊形貌磷酸锆铜的一步合成法进行了一系列研究,探索一种简便、快速的磷酸锆铜合成方法。本论文采用氧氯化锆、氟化铵、氯化铜、磷酸二氢钠为原料,在低温（<100℃）开放体系下,通过微波辅助加热,在较短的时间内制备出具有特殊形貌的磷酸锆铜颗粒。研究了反应液p H、反应物浓度、反应温度、反应物比例,以及络合剂等因素对合成磷酸锆铜晶体的影响。实验结果表明,以上因素均会对磷酸锆铜的合成产生影响。当反应条件为[Zr⁴⁺]=0.005mol·L-1,[Cu²⁺]/[Zr⁴⁺]=1,[F^-]/[Zr⁴⁺]=6,[PO₄^3-]/[Zr⁴⁺]=20,pH=4.8,在90℃微波反应30min条件下,可制备出由纳米片插层组成的类线团状的磷酸锆铜。测试了类线团状磷酸锆铜的热性能,磷酸锆铜的热失重分为三个阶段,分别在55⁷5℃、75¹22℃与122²60℃三个阶段依次失去1个、2个、1个结晶水,在经过800℃煅烧后发生相变。此外,本论文还测试了其微波吸波性能,磷酸锆铜具有一定的电磁波吸收性能,但对电磁波的吸收能力表现一般,在2-18GHz范围的反射损失均在-10d B左右,反射损失在高频带15.6GHz处达到最小值-10.74d B。为了探究磷酸锆铜的光催化性能,本论文通过在可见光照射下催化降解阳离子染料罗丹明B对磷酸锆铜的光催化活性及其在非均相类芬顿反应中的催化活性进行研究。实验以磷酸锆铜为光催化剂,使用HCl和NaOH溶液调节反应体系p H,吸附平衡后加入一定量H₂O₂,在室温下（10¹5℃）进行光催化反应。研究结果表明,类线团状的磷酸锆铜具有一定的光催化活性,反应体系加入H₂O₂构成非均相类芬顿体系,对染料的脱色率大幅提高,远大于只加入磷酸锆铜或只加入H₂O₂二者催化效果的简单加和;在紫外-可见光照射下,不同形貌的磷酸锆铜表现出不同的催化性能,其中类线团状>火焰状>片状;染料的脱色率随着H₂O₂的投加量增加而增大;磷酸锆铜的用量对染料的最终脱色率影响不大,但染料的初始降解速率随着磷酸锆铜投加量的增加而增大;磷酸锆铜在p H5.0⁹.0范围内表现出较好的催化性能;磷酸锆铜具有优异的重复使用性,重复使用5次后,染料的脱色率仍可达到63%。本论文还测试了ZPCu-H₂O₂体系在水浴加热条件下对罗丹明B的降解性能。实验以磷酸锆铜为催化剂,催化H₂O₂在加热条件下降解罗丹明B。结果表明,在罗丹明B的初始浓度为5.0×10-5mol·L-1,磷酸锆铜用量0.03g,H₂O₂（30%）用量为0.5m L,水浴50℃加热10min条件下,染料脱色率可达97.1%,而不加入磷酸锆铜与H₂O₂的条件下,染料的脱色率仅为6.1%。该体系对染料的降解性能随着温度的升高、催化剂用量的增加以及染料初始浓度的降低而提高;磷酸锆铜作在重复5次使用后染料的脱色率仍可达到85%,具有良好的重复使用性。本课题采用微波辅助合成法一步制备出具有特殊形貌的磷酸锆铜,操作简单、反应时间短且绿色节能,并讨论了磷酸锆铜的光催化性能及其在非均相类芬顿体系中的催化性能。本课题开创了一种新的磷酸锆铜合成方法,与传统水热法相比,大大地缩短了反应时间,提高了合成效率并拓展了磷酸锆铜的应用领域。更多还原

【Abstract】 The synthesis and application of zirconium copper phosphate（ZPCu）,a kind of phosphate complex salt,is seldom reported.The reported zirconium copper phosphate is always prepared by Cu²⁺/H+ ion exchange using hydrothermal method.However,the morphology is difficult to be controled which is usually performed under high temperature,high pressure and long reaction time.Microwave-assisted heating method is a new green synthetic method for nano-material with narrow distribution of particle size,good dispersibility and special morphology.The microwave non-thermal effect can also affect the formation of crystal shape.However,there is no report about the preparation of zirconium copper phosphate using microwave-assisted heating method.In this paper,the preparation of zirconium copper phosphate was one-step prepared by a microwave-assisted heating method under low temperature（<100℃）and normal pressure.A special morphology zirconium copper phosphate was prepared by microwave-assisted heating method using ZrOCl₂,NH₄F,CuCl₂ and NaH₂PO₄ as raw materials and water as solvent.The influence of p H values,reactant concentrations,microwave heating temperature and time,n（Cu）:n（Zr）and n（F）:n（Zr）on the formation and morphology of ZPCu were studied.The result shows that the morphology and crystallinity were significant influenced by the mentioned condition.ZPCu assembled coil-like with uniform size can be prepared under reaction condition:[Zr⁴⁺]=0.005mol·L-1,[Cu²⁺]/[Zr⁴⁺]=1,[F^-]/[Zr⁴⁺]=6,[PO₄^3-]/[Zr⁴⁺]=20,pH=4.8,90℃ and 30 min.There are three stages in thermal weight loss process of ZPCu,they are 55⁷5℃,75¹22℃and 122²60℃,respectively loss one,two and one crystal water.Phase transition of ZPCu would be occurred after calcinated at 800℃.In addition,microwave absorbing property of ZPCu was also investigated.The result shows that ZPCu behaves a little absorbing property,the reflectivity is below-10 d B at the frequency range from 2GHz to 18 GHz,and the lowest reflectivity is-10.74 d B at 15.6GHz.Photocatalytic properties and behavior in heterogeneous Fenton-like system of ZPCu under illumination were evaluated by degrading model pollutant rhodamine B（Rh B）.ZPCu as a photocatalyst in the experiment,using HCl and Na OH adjusts p H,then,adding a certain volume of H₂O₂ after absorption and desorption equilibrium.This experiment reacts under illumination and room temperature（10¹5℃）.The results revealed that ZPCu exhibited a little photocatalytic activity under ultraviolet and visible light,the catalytic efficiency enhanced obviously with addition of H₂O₂.The degradation rate of the dye enhanced with the increasing dosage of ZPCu and H₂O₂.ZPCus with different morphologies have different photocatalytic properties,the order photocatalytic activity of ZPCu at the presence of H₂O₂ is: coil-like > flame-like > flaky.The system showed the best photocatalytic activity at p H values between 5.0 to 9.0.In this paper,the degradation performance of ZPCu-H₂O₂ system under heating was studied.ZPCu as a photocatalyst in the experiment,catalyzed H₂O₂ to degrade Rh B solution under heating.The result shows that Rh B 5.0×10-5mol·L-1,the dosage of ZPCu 0.03 g,30%H₂O₂ 0.5m L,the reaction system was heated at 50℃ for 10 min,the decolorization of Rh B could reach 97.1%.Degradation property of this system increased with increasing temperature and the dosage of ZPCu and decreasing the initial concentration of dye.ZPCu exhibited excellent stability and effectiveness after 5 consecutive runs in terms of degradation of Rh B.The degradation rate still reached 85% after 5 runs.In conclusion,a simple,efficient and eco-friendly synthetic method for ZPCu was obtained in this paper.Compared with traditional hydrothermal method,the microwave-assisted synthetic method of ZPCu shorted the reaction time and improve efficiency.The photocatalytic properties and behavior in heterogeneous Fenton-like system of ZPCu were discussed,it would wide the application fields ZPCu.更多还原