CN114042459B - 一种类树状软磁性Sr2FeMoO6高效可见光催化剂的制备方法 - Google Patents
一种类树状软磁性Sr2FeMoO6高效可见光催化剂的制备方法 Download PDFInfo
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Abstract
本发明属于功能材料领域，具体是涉及一种改进的溶胶‑凝胶法制备类树状软磁性Sr2FeMoO6高效可见光催化剂的方法。首先将硝酸锶、钼酸铵和硝酸铁水溶液混合，再将柠檬酸和乙二胺四乙酸依次加入混合溶液中，调节体系pH值，在一定水浴温度下经强烈搅拌形成澄清透明溶胶和凝胶；最后经过陈化、干燥、预分解、加氢煅烧，得到一种类树状软磁性Sr2FeMoO6高效可见光催化剂。本发明的制备方法工艺简单易控，无污染，对设备要求低。制备的类树状Sr2FeMoO6光催化剂在可见光作用下能够有效降解亚甲基蓝，具有极佳的光催化活性。同时，由于该材料具有软磁性材料特点，回收方便，可以重复使用。
Description
技术领域
本发明属于功能材料领域，具体是涉及一种改进的溶胶-凝胶法制备类树状软磁性Sr2FeMoO6高效可见光催化剂的方法。
背景技术
双钙钛矿型氧化物材料的命名由钙钛矿型氧化物ABO3而来，当两种不同阳离子占据ABO3中的B位，氧离子位于两种阳离子之间，且阳离子以NaCl型结构有序排列，就形成了双钙钛矿型结构氧化物，通式可写为A2BB'O6。Sr2FeMoO6属于一种典型的双钙钛矿型结构氧化物。Sr2FeMoO6由于具有室温下的高磁阻效应、高居里温度和低矫顽力等优点，可作为在室温下随机存储及传感器领域的磁电阻材料应用，因而受到广泛关注。同时由于其具有半金属性质和存在大量的氧空穴，其也具有固体氧化物燃料电池和催化剂的应用潜力。
目前对于双钙钛矿型复合氧化物在电磁学的研究较多，将双钙钛矿型氧化物作为催化材料的报道尚不多见，2004年，国外首次报道了利用柠檬酸分解法合成了双钙钛矿Sr2FeMoO6并作为甲烷高温燃烧催化剂，此后针对双钙钛矿型氧化物催化甲烷燃烧方面，许多研究者做了深入的研究。化工学报(胡瑞生，2008，59(6):1418-1424)采用葡萄糖溶胶-凝胶法制备出Sr2FeMoO6粉体，研究了制备工艺对催化剂的结构、磁性能和甲烷燃烧催化活性的影响。但将双层钙钛矿型氧化物应用于光催化的研究还甚少。
目前合成Sr2FeMoO6及其掺杂材料的方法有很多，常见的有高温固相法、溶胶-凝胶法、电泳沉积法、化学沉淀法等，其中最典型的方法就是高温固相法。研究发现，不同的制备工艺对晶体的结构、形貌和物理特性都有重要影响。稀有金属(崔玉建，2008,32(6):735-738)用固相反应法和柠檬酸溶胶-凝胶自燃法在还原气氛下焙烧后得到了双钙钛矿Sr2FeMoO6，研究表明，溶胶-凝胶法制备的样品烧结温度较低，粒度较小、粒径分布更均匀，且饱和磁化强度较高。人工晶体学报(盖文超，2015，44(10):2767-2770)采用溶胶-凝胶柠檬酸燃烧法成功制备出Sr2FeMoO6－δ粉体，研究了制备工艺对材料的结构和形貌的影响。功能材料(胡艳春，2016,47(1):01169-01171)采用高温固相反应法在还原气氛下焙烧后得到了双钙钛矿Sr2FeMoO6，研究了烧结时间对晶体结构和物相的影响，研究结果表明，结果表明随着烧结时间的增加，晶粒越来越大，空洞逐渐减少，晶界越来越清晰，晶粒尺寸越来越均匀。功能材料(王玉平，2016,47(7):07130-07134)用高温固相法和柠檬酸溶胶-凝胶法在还原气氛下焙烧后得到了双钙钛矿Sr2FeMoO6，研究表明，在等同条件下，溶胶-凝胶法制备的样品Fe/Mo的有序度更高、结晶性更好。石油化工(郑建东，2013，42(12):1331-1335)采用共沉淀方法合成了一系列双钙钛矿型材料，并发现其催化降解性能也很好。中国专利CN107413351B采用EDTA螯合剂溶胶-凝胶法制备出了柳叶状双层钙钛矿型Sr2FeMoO6光催化剂，能够有效降解亚甲基蓝，具有较佳的光催化活性。
目前，柠檬酸和乙二胺四乙酸都是一种较优良的螯合剂被广泛用于制备各种氧化物材料，本研究采用改进的柠檬酸-乙二胺四乙酸溶胶凝胶法，将柠檬酸作为螯合剂、乙二胺四乙酸作为软模板剂用于制备特殊形貌的双钙钛矿型结构的类树状软磁性Sr2FeMoO6，且用做光催化剂使用还未见报道。
众所周知，光催化剂的催化效率受催化剂的结构、形貌和尺寸的影响较大。因此，利用特殊制备工艺制备具有特殊形貌的Sr2FeMoO6，以期获得更多的载体催化中心，从而提高催化剂的催化性能，具有特别的意义。
发明内容
本发明要解决的技术问题为克服高温固相法具有的颗粒大，颗粒粒径分布不均匀的缺点，采用改进的柠檬酸-乙二胺四乙酸溶胶-凝胶法制备出一种类树状软磁性高效可见光催化剂Sr2FeMoO6，该方法具有工艺简单，易控，无污染，对设备要求低等优点。按照本发明制得的类树状Sr2FeMoO6光催化剂在可见光作用下具有高效的光催化活性，且由于Sr2FeMoO6光催化剂具有软磁性材料的特点，易于回收再利用。
本发明所采用的技术方案为：一种类树状软磁性Sr2FeMoO6高效可见光催化剂的制备方法，采用改进的溶胶-凝胶法，具体步骤如下：
①、前驱液A是将硝酸锶(Sr(NO3)2)水溶液和四水钼酸铵((NH4)6Mo7O24.4H2O)水溶液混合，形成前驱液A；
②、接着在强烈搅拌下，将硝酸铁(Fe(NO3)3)水溶液缓慢加入前驱液A中混合形成乳液状溶液B；
③、称取一定量柠檬酸(CA)，溶解于水溶液中记为C；
④、称将一定量乙二胺四乙酸(EDTA)记为D；
⑤、在强烈搅拌下，将溶液C缓慢滴加入乳液状溶液B中形成混合溶液，再加入D，调节体系pH值至5～9，形成澄清透明的Sr2FeMoO6溶胶；
⑥、将Sr2FeMoO6溶胶经水浴搅拌、陈化形成澄清透明的凝胶；
⑦、将Sr2FeMoO6凝胶干燥、预分解、加氢煅烧从而形成类树状软磁性Sr2FeMoO6高效可见光催化剂；
制备的Sr2FeMoO6具有较好的类树状结构，它由一个主树干和四周排列整齐的叶片组成，其饱和磁化强度较大，矫顽力极小，具有软磁性材料特点。
优选地，步骤①的前驱液A中Sr和Mo之间的摩尔比为2∶1。
优选地，步骤②的乳液状溶液B中Sr与Fe之间的摩尔比为2∶1。
优选地，步骤③的溶液C中CA和Sr的摩尔比为1.5～4∶1。
优选地，步骤④的D中EDTA和Sr的摩尔比为1～3∶1。
优选地，步骤⑤中使用氨水和硝酸调节体系pH值。
优选地，步骤⑥中将Sr2FeMoO6溶胶在60～90℃水浴锅中搅拌3～8h，接着于10～25℃下陈化16～48h，形成澄清透明的凝胶。
优选地，步骤⑦中将Sr2FeMoO6凝胶于烘箱中180℃干燥3h，再于马弗炉中500～800℃预分解3.5h，最后在含3～6％体积百分比的H2/N2气氛下煅烧3～9h，从而形成类树状软磁性Sr2FeMoO6高效可见光催化剂。
本发明的类树状软磁性Sr2FeMoO6高效可见光催化剂的制备方法，相对于现有技术的有益效果表现在：
本发明采用改进的柠檬酸-乙二胺四乙酸溶胶-凝胶法制备出了类树状软磁性Sr2FeMoO6高效可见光催化剂，该制备工艺简单易控，无污染，对设备要求低。本发明制备出的类树状软磁性Sr2FeMoO6光催化剂在可见光作用下能够有效降解亚甲基蓝，具有极佳的可见光催化活性。同时，由于Sr2FeMoO6光催化剂本身具有软磁性材料的特点，可以采用简单的磁回收的方法予以回收再利用，从而解决了光催化剂在悬浮体系中难回收的问题，可以重复使用。
附图说明
图1是本发明实施1制备的双钙钛矿型Sr2FeMoO6光催化剂的XRD图。
图2是本发明实施1制备的双钙钛矿型Sr2FeMoO6光催化剂的XPS图(插图为室温下O-1s电子谱图及多峰拟合曲线)。
图3、图4是本发明1实施制备的Sr2FeMoO6可见光催化剂的SEM图。
图5是本发明实施1制备的Sr2FeMoO6可见光催化剂的磁性能图。
图6是本发明实施1制备的Sr2FeMoO6光催化剂在可见光作用下降解亚甲基蓝溶液的光催化降解图。
具体实施方式
下面结合附图对本发明的优选方式作进一步详细的描述。
实施例1
步骤①、分别取0.01mol的Sr(NO3)2和0.000714mol的(NH4)6Mo7O24.4H2O溶解于20mL的水中，混合配成轻微浑浊状的前驱液A。
步骤②、取5mL的1mol/L Fe(NO3)3水溶液在强烈搅拌下，缓慢加入前驱液A中，先形成澄清透明的溶液，后逐渐变成乳液状混合液B。
步骤③、称取0.015mol的柠檬酸，溶解于15mL水溶液中，得到柠檬酸水溶液C。
步骤④、称取0.015mol的乙二胺四乙酸，记为D。
步骤⑤、在强烈搅拌下，将柠檬酸水溶液C缓慢加入混合溶液B中，再加入D，用氨水或硝酸调至pH为7，形成澄清透明的Sr2FeMoO6溶胶。
步骤⑥、将获得的Sr2FeMoO6溶胶在70℃水浴锅中搅拌5h，接着于20℃下陈化24h，形成澄清透明的凝胶，然后于烘箱中180℃干燥3h，于马弗炉中700℃煅烧3.5h进行预分解，再在5％H2/N2气氛下煅烧5h，形成类树状软磁性Sr2FeMoO6光催化剂。
从附图1的XRD图可以看出，所制备的样品为纯的双钙钛矿型Sr2FeMoO6光催化剂，没有观察到其它杂质峰的存在；谱图中各个谱峰尖锐，说明样品晶化程度良好。
从附图2的XPS图可以看出，所制备的Sr2FeMoO6样品中Sr 3d、Fe 2p、Mo 3d、O 1s和C 1s都在谱图中出现，最重要的是存在着大量的表面吸附氧(O 531.50eV)，约占总氧含量的60％，这对于光催化剂的光催化活性非常有利。
从附图3和4的SEM图可以看出，所制备的Sr2FeMoO6具有较好的类树状结构，它由一个主树干和四周排列整齐的叶片组成。
从附图5的磁性能图可以看出，所制备的Sr2FeMoO6光催化剂饱和磁化强度较大，矫顽力极小，具有软磁性材料特点。
从附图6的光催化降解图可以看出，所制备的Sr2FeMoO6光催化剂以亚甲基蓝为模拟污染物，在可见光作用下，经过35分钟，光催化降解率达到98.9％，表明光催化剂具有极佳的光催化活性。
因此，从XRD图、SEM图、磁性能图和可见光催化降解图的分析结果中可以看出，通过改进的柠檬酸-乙二胺四乙酸溶胶-凝胶法这种简单易控的方法，能方便的制备出类树状双钙钛矿型Sr2FeMoO6光催化剂，且具有软磁性材料特点和极佳的可见光催化活性。通过对比即可发现，其性能明显优于柳叶状的Sr2FeMoO6光催化剂(中国专利CN 107413351B公开方法制备)。这种性能差异得益于本发明将柠檬酸作为螯合剂、乙二胺四乙酸作为软模板剂，通过这种改进的柠檬酸-乙二胺四乙酸溶胶-凝胶法，从而制备出类树状这一特殊形貌的双钙钛矿型结构软磁性Sr2FeMoO6光催化剂。
实施例2
步骤①、分别取0.01mol的Sr(NO3)2和0.000714mol的(NH4)6Mo7O24.4H2O溶解于20mL的水中，混合配成轻微浑浊状的前驱液A。
步骤②、取5mL的1mol/L Fe(NO3)3水溶液在强烈搅拌下，缓慢加入前驱液A中，先形成澄清透明的溶液，后逐渐变成乳液状混合液B。
步骤③、称取0.02mol的柠檬酸，溶解于20mL水溶液中，得到柠檬酸水溶液C。
步骤④、称取0.015mol的乙二胺四乙酸，记为D。
步骤⑤、在强烈搅拌下，将柠檬酸水溶液C缓慢加入混合溶液B中，再加入D，用氨水或硝酸调至pH为8，形成澄清透明的Sr2FeMoO6溶胶。
步骤⑥、将获得的Sr2FeMoO6溶胶在65℃水浴锅中搅拌4.5h，接着于15℃下陈化36h，形成澄清透明的凝胶，然后于烘箱中180℃干燥3h，于马弗炉中600℃煅烧3.5h进行预分解，再在5.5％H2/N2气氛下煅烧6h，形成类树状软磁性Sr2FeMoO6光催化剂。
实施例3
步骤①、分别取0.01mol的Sr(NO3)2和0.000714mol的(NH4)6Mo7O24.4H2O溶解于20mL的水中，混合配成轻微浑浊状的前驱液A。
步骤②、取5mL的1mol/L Fe(NO3)3水溶液在强烈搅拌下，缓慢加入前驱液A中，先形成澄清透明的溶液，后逐渐变成乳液状混合液B。
步骤③、称取0.025mol的柠檬酸，溶解于25mL水溶液中，得到柠檬酸水溶液C。
步骤④、称取0.02mol的乙二胺四乙酸，记为D。
步骤⑤、在强烈搅拌下，将柠檬酸水溶液C缓慢加入混合溶液B中，再加入D，用氨水或硝酸调至pH为6，形成澄清透明的Sr2FeMoO6溶胶。
步骤⑥、将获得的Sr2FeMoO6溶胶在80℃水浴锅中搅拌3h，接着于25℃下陈化48h，形成澄清透明的凝胶，然后于烘箱中180℃干燥3h，于马弗炉中800℃煅烧3.5h进行预分解，再在6％H2/N2气氛下煅烧4h，形成类树状软磁性Sr2FeMoO6光催化剂。
上述各实施例只是为了说明本发明的技术构思及特点，其目的是在于让本领域内的普通技术人员能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围。凡是根据本发明内容的实质所作出的等效的变化或修饰，都应涵盖在本发明的保护范围内。
Claims (1)
1.一种类树状软磁性Sr2FeMoO6高效可见光催化剂在可见光催化降解有机染料中的应用，其特征在于，所述类树状软磁性Sr2FeMoO6高效可见光催化剂采用改进的溶胶-凝胶法制备，制备的Sr2FeMoO6具有较好的类树状结构，它由一个主树干和四周排列整齐的叶片组成，其饱和磁化强度较大，矫顽力极小，具有软磁性材料特点，制备方法具体步骤如下：
①、前驱液A是将硝酸锶水溶液和四水钼酸铵水溶液混合，形成前驱液A，前驱液A中Sr和Mo之间的摩尔比为2∶1；
②、接着在强烈搅拌下，将硝酸铁水溶液缓慢加入前驱液A中混合形成乳液状溶液B，乳液状溶液B中Sr与Fe之间的摩尔比为2∶1；
③、称取一定量柠檬酸CA，溶解于水溶液中记为C，溶液C中CA和Sr的摩尔比为1.5～4∶1；
④、称取一定量乙二胺四乙酸EDTA记为D，D中EDTA和Sr的摩尔比为1～3∶1；
⑤、在强烈搅拌下，将溶液C缓慢滴加入乳液状溶液B中形成混合溶液，再加入D，使用氨水和硝酸调节体系pH值至5～9，形成澄清透明的Sr2FeMoO6溶胶；
⑥、将Sr2FeMoO6溶胶在60～90℃水浴锅中搅拌3～8 h，接着于10～25℃下陈化16～48h，形成澄清透明的凝胶；
⑦、将Sr2FeMoO6凝胶于烘箱中180℃干燥3 h，再于马弗炉中500～800℃预分解3.5 h，最后在含3～6%体积百分比的H2/N2气氛下煅烧3～9 h，从而形成类树状软磁性Sr2FeMoO6高效可见光催化剂。
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