CN102557147B - 一种微波法制备铁酸钐纳米粉体的方法 - Google Patents
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Abstract
一种微波法制备铁酸钐纳米粉体的方法，它涉及一种铁酸钐纳米材料的制备方法。本发明利用微波技术，以硝酸铁、硝酸钐、聚乙烯醇和尿素为原料，制备了晶粒平均厚度为30nm和带隙为1.94eV，并且具有优良可见光催化活性的铁酸钐纳米粉体。其步骤分为反应液的制备和微波条件下纳米粉体的制备两步。本发明提供了一种简单、可靠、快速高效、成本低的制备铁酸钐纳米粉体的方法。
Description
技术领域
本发明涉及铁酸盐纳米材料的制备，特别是涉及一种铁酸钐纳米粉体的制备方法。
背景技术
铁酸钐(SmFeO3)是铁酸盐系列的一种，属于钙钛矿型(ABO3)复合氧化物。正如文献(中国稀土学报，2007，25(3)：305-308)报道的一样，钙钛矿型复合氧化物是一种具有独特物理性质和化学性质的新型无机金属材料，由于这类化合物具有稳定的晶体结构、独特的电磁性能，以及优良的催化活性和气敏性能，因而在光学、电学、磁学、催化等领域具有广泛的用途。
目前，制备SmFeO3的方法主要有固相法、溶胶-凝胶法、声化学法、微乳液法和热分解法等方法。如文献(传感技术学报，2006，19(5)：2138-2141)报道以K3[Fe(CN)6]和Sm2O3为主要原料，采用热分解法于800℃制备得到了SmFeO3；文献(科技与经济，2006，(6)：104-105)以Sm2O3、Fe(NO3)3·9H2O和柠檬酸为主要原料，采用溶胶-凝胶法制备得到溶胶，将溶胶于102℃真空干燥17h得到干凝胶，再将干凝胶于750℃煅烧处理6h得到了纳米SmFeO3。目前制备SmFeO3粉体的方法中，基本上都要经高温(600℃～1000℃)热处理才能得到SmFeO3，而高温热处理易导致SmFeO3颗粒的团聚和长大，并且高温热处理会消耗更多的能源，存在制备较工艺复杂、耗时长和成本高等缺点，工业化应用前景堪忧。
微波是一种高频率的电磁波，具有加热速度快、穿透性强、热惯性小，所需设备简单、反应条件易于控制、易于工业化和节能高效等优点，在陶瓷材料和纳米材料合成等领域具有广泛的应用。目前，采用微波法直接制备SmFeO3纳米粉体还未见报道。
发明内容
本发明的目的在于克服现有技术的不足，提供一种微波法制备铁酸钐纳米粉体的方法。
本发明的目的是通过以下技术方案来实现的，具体步骤为：
(1)反应液的制备
在室温条件下，将硝酸钐溶于95％的乙醇中制得浓度为0.2mol/L的硝酸钐乙醇溶液；将硝酸铁溶于95％的乙醇中制得浓度为0.2mol/L的硝酸铁乙醇溶液。将聚乙烯醇溶解于55℃蒸馏水中制得质量浓度为5g/L的溶液。在搅拌条件下，将体积比为1∶3的硝酸钐乙醇溶液和聚乙烯醇溶液混合，然后将与硝酸钐乙醇溶液体积相同的硝酸铁乙醇溶液缓慢加入其中得到混合液，再将物质的量是硝酸钐1.4倍的尿素加入到混合液中。在55℃条件下搅拌30min得到反应液。
(2)微波条件下纳米粉体的制备
将70～100ml反应液放入微波炉中，在保持微波功率400W～4500W条件下反应28min至完全燃烧，冷却至室温取出，研磨得到SmFeO3纳米粉体产品。
与现有技术相比，本发明的积极效果是：采用微波法制备，具有工艺和设备简单，达到了快速高效、节能、易于工业化生产SmFeO3纳米粉体的目的。
附图说明
图1：实施例1所得SmFeO3产品的XRD图；
图2：实施例1所得SmFeO3产品的扫描电镜照片；
图3：实施例1所得SmFeO3产品的漫反射吸收谱；
图4：实施例1所得SmFeO3产品与参比商品二氧化钛P25可见光催化降解甲基橙(MO)的脱色率随光照时间的变化曲线。
具体实施方式
实施例1
在室温条件下，将0.004mol Sm(NO3)3溶于20ml 95％的乙醇中得到含Sm3+的乙醇溶液；将0.004mol Fe(NO3)3溶于20ml 95％的乙醇中得到含Fe3+的乙醇溶液。在搅拌条件下，将0.3g聚乙烯醇溶于60ml 55℃的蒸馏水中得到溶液，将20ml含Sm3+的乙醇溶液加入其中得到混合溶液。将20ml含Fe3+的乙醇溶液缓慢加入到上述混合溶液中，然后将0.0056mol的尿素加入到混合液中。保持混合液温度为50℃，继续搅拌30min得到反应液。将反应液放入微波炉中，调节微波炉的功率为450W，微波反应28min至其完全燃烧得到产物，冷却后将产物研磨得到产品。对得到的产品分别进行X射线衍射分析(XRD)、扫描电镜(SEM)和漫反射吸收谱(DRS)测试，结果分别如图1、图2和图3所示。
图1是采用XD-6型X射线衍射分析仪，粉末法分析测试产品的XRD图。从图1可知，所得产品的XRD图谱与标准的SmFeO3(JCPDS：74-1474)吻合，说明合成的产品是SmFeO3晶粒。
图2是采用日立S-4800型场发射扫描电子显微镜测试产品的SEM照片。从图2可知，SmFeO3产品以平均厚度为30nm的纳米薄片存在为主。
图3是采用Hitachi UV4100型光谱仪，以标准的BaSO4作参比，将SmFeO3粉末压片，然后进行测试得到的漫反射吸收谱。从图3可知，SmFeO3的吸收边波长λ为640nm，利用公式E(eV)＝1240/λ计算得到SmFeO3的带隙宽度为1.94eV。
为了表征SmFeO3纳米粉体的可见光催化活性，光催化实验在自制的光催化反应装置中进行：光源为150W金属卤化物灯，利用JB400滤光片获得波长大于400nm的可见光；将20mg SmFeO3纳米粉体加入到10ml 10mg/L的模拟污水甲基橙(MO)溶液中避光吸附平衡30min后，进行光催化降解实验；降解所需时间后取出离心分离去除粉体，以MO溶液最大吸收峰464nm处吸光度的标准曲线计算其脱色率，用学术界常用的商品二氧化钛P25作对比光催化实验，实验结果如图4所示。从图4可知，10mg/L的MO溶液在可见光照射下没有明显的分解，是稳定的；而SmFeO3对MO溶液的降解脱色率在60min前迅速增加，60min时已经达到86％，120min时已经完全降解，SmFeO3产品表现出了优良的可见光催化活性。而参比P25对MO溶液的降解脱色率从5min～120min虽然在缓慢增加，但120min时才达到28％，这表明SmFeO3产品的可见光催化活性远优于P25。
实施例2
在室温条件下，将0.003mol Sm(NO3)3溶于15ml 95％的乙醇中得到含Sm3+的乙醇溶液；将0.003mol Fe(NO3)3溶于15ml 95％的乙醇中得到含Fe3+的乙醇溶液。在搅拌条件下，将0.225g聚乙烯醇溶于45ml 55℃的蒸馏水中得到溶液，将15ml含Sm3+的乙醇溶液加入其中得到混合溶液。将15ml含Fe3+的乙醇溶液缓慢加入到上述混合溶液中，然后将0.0042mol的尿素加入到混合液中。保持混合液温度为55℃，继续搅拌30min得到反应液。将反应液放入微波炉中，调节微波炉的功率为400W，微波反应28min至其完全燃烧得到产物，冷却后将产物研磨得到产品。按照实施例1相同的光催化实验方法，可见光催化降解10mg/L的MO溶液60min时，MO脱色率达到88％，SmFeO3产品表现出了优良的可见光催化活性。
Claims (1)
1.一种微波法制备铁酸钐纳米粉体的方法，其特征在于包括以下步骤：在室温条件下，将0.004mol Sm(NO3)3溶于20ml95％的乙醇中得到含Sm3+的乙醇溶液；将0.004mol Fe(NO3)3溶于20ml95％的乙醇中得到含Fe3+的乙醇溶液；在搅拌条件下，将0.3g聚乙烯醇溶于60ml55℃的蒸馏水中，并将20ml含Sm3+的乙醇溶液加入其中得到混合溶液；向该混合溶液中缓慢加入20ml含Fe3+的乙醇溶液，然后再加入0.0056mol的尿素，在温度为50℃的条件下继续搅拌30min得到反应液；将该反应液放入到微波炉中，调节微波炉的功率为450W，微波反应28min至其完全燃烧得到产物，冷却后研磨得到铁酸钐纳米粉体；该铁酸钐纳米粉体以平均厚度30nm的纳米薄片为主，吸收边波长为640nm。
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