CN111974407A - 一种制备磁性三氧化钨复合光催化剂的方法 - Google Patents
一种制备磁性三氧化钨复合光催化剂的方法 Download PDFInfo
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Abstract
一种磁性三氧化钨复合光催化剂WO3/SrFe12O19的制备方法，属于无机纳米光催化材料领域。本发明先采用水热法制备了磁性基体SrFe12O19，再采用水热‑焙烧法制备了磁性复合光催化剂WO3/SrFe12O19。本发明方法制备工艺简单，能耗少，易于控制，生产成本低。制备的WO3/SrFe12O19复合磁性光催化剂磁性能稳定，结晶度良好。在模拟太阳光氙灯的照射下，当5mM的H2O2存在时，0.1g制备的复合磁性光催化剂，降解100mL浓度为10mg/L的罗丹明B溶液，80min时对罗丹明B的降解率达到98.4％，重复使用3次后对罗丹明B降解率保持在86.6％以上。本发明制备的产品使用过程绿色环保，对工业化有机染料废水的处理具有突出的优势。
Description
技术领域
本发明涉及一种磁性三氧化钨复合光催化剂WO3/SrFe12O19的制备方法，属于无机纳米光催化材料技术领域。
背景技术
纳米材料的光催化领域作为一种涵盖多学科交叉的新兴研究领域，已成为工业废水治理和洁净能源生产技术的热点研究方向。其中，以三氧化钨(WO3)为代表的过渡金属氧化物，具有优异的光电、热电、湿敏和气敏等特性。特别是纳米结构的WO3在催化、光开关、显示器智能窗口和光记录设备等领域有着广泛的应用前景。同时，WO3作为一种窄带隙半导体材料，禁带宽度约为2.4eV-2.8eV，并表现出在价带边缘电位上光催化氧化能力增强的特性。此外，它具有在酸性溶液中的稳定性、低毒性、性价比高等优势，被认为是一种高效可见光驱的半导体光催化剂。
就目前相关文献报道，对于WO3的改性及其复合物的研究成果较多，如“Preparation of hierarchical micro/nanostructured Bi2S3-WO3 composites forenhanced photocatalytic performance”(Journal of Alloys and Compounds,2016,685:812-819)一文(对比文件1)，该文先采用水热-焙烧法制备出WO3，再采用水热法复合得到纳米结构的Bi2S3-WO3。该方法存在的主要问题是：(1)制备WO3时是将Pb(Ac)2·H2O和Na2WO4分别溶解于乙二醇溶液中，水热反应12h(160℃)形成前驱体PbWO4，然后将PbWO4浸入HNO3溶液中48h以洗脱Pb2+，最后使H2WO4在500℃下焙烧2h制得，该过程制备周期较长，前驱体在有机溶剂乙二醇中反应生成，特别是所用试剂含有醋酸铅(Pb(Ac)2·H2O)具有毒性，成本较高，且会产生含有一类重金属污染物的高浓度有机废水，不适合推广；(2)制备的WO3光催化活性不高，120min对罗丹明B的降解率仅为25％，复合物Bi2S3-WO3的降解率为90.7％；(3)复合材料的回收成本较高，且易造成催化剂回收不彻底而引发二次污染。
为了使光催化剂做到节能环保，将其赋磁以便于分离使用是十分必要的。目前，磁性基体主要是以软磁性的四氧化三铁(Fe3O4)为主，如“Fe3O4/WO3 Hierarchical Core-Shell Structure:High-Performance and Recyclable Visible-Light Photocatalysis”(CHEMISTRY-A EUROPEAN JOURNAL,2011,17(18):5145-5154)一文(对比文件2)，以水热法先制备Fe3O4，再采用水热-焙烧法得到复合磁性光催化剂Fe3O4/WO3。该方法存在的问题是：(1)制备Fe3O4和WO3的过程中均涉及到有机溶剂乙二醇，致使成本较高，且反应时间较长，使得能耗较大，对于大规模的工业化生产并不适用；(2)制得的复合磁性光催化材料的矫顽力较小(160Oe)，磁化后易失去磁性，磁稳定性能不佳；(3)复合磁性光催化剂仅对低浓度的污染物具有一定的处理效果，0.1g的Fe3O4/WO3降解100mL浓度为4mg/L的罗丹明B，在1.5h时的降解率为93％左右。
锶铁氧体(SrFe12O19)作为一种硬磁性材料，是一种可见光驱的n型半导体光催化剂，禁带宽度较小，仅为1.5eV，与上述传统的金属软磁材料Fe3O4相比，矫顽力较高、抗退磁能力较强。因此，本发明以SrFe12O19为磁性基体，制备复合磁性光催化剂，以此提高WO3的光催化活性并赋予磁性能，便于分离和循环利用。
发明内容
本发明解决的技术问题是提供了一种WO3/SrFe12O19复合磁性光催化剂的制备方法，其核心在于合成磁学性能优异且稳定的复合磁性光催化剂，在提高WO3光催化活性的同时，有效解决传统方法回收不彻底对环境造成的二次污染的问题。本发明制备工艺简便，易于控制，生产效率高且成本低，对工业化有机染料废水的处理具有突出的优势，同时也拓展了WO3及其复合材料光催化剂的应用。
本发明WO3/SrFe12O19复合磁性光催化剂的制备方法如下：
(1)SrFe12O19的制备
分别称取0.7465g的SrCl2·6H2O和6.0545g的FeCl3·6H2O，用35mL去离子水超声溶解，得到混合溶液A；称取8.736g的NaOH，用20mL去离子水超声溶解，得到溶液B；在恒温20℃水浴和磁力搅拌下，将溶液B缓慢滴加到混合溶液A中，持续搅拌15min，待溶液充分混合，得到SrFe12O19前驱体C；将前驱体C倒入100mL水热釜中，200℃下反应24h取出，自然冷却至室温，抽滤，滤饼用去离子水洗涤至滤液呈中性后，置于80℃烘箱中干燥24h，研磨得到SrFe12O19。
(2)WO3/SrFe12O19的制备
分别称取1g的Na2WO4·2H2O和1.2g的柠檬酸C6H8O7·H2O，加入到60mL去离子水中，超声15min并机械搅拌15min使其充分混合，得到溶液D；按照理论生成SrFe12O19在复合物中的质量百分数3wt％～7wt％，称取已制备好的SrFe12O19粉末加入到溶液D中，持续机械搅拌30min，用2mol/L的稀HCl调节混合溶液的pH为1，继续搅拌1h，得到悬浊液E；将悬浊液E装入100mL的水热釜中，120℃下反应24h取出，冷却至室温，过滤，滤饼用去离子水洗涤后置于80℃烘箱中干燥12h，将烘干样研磨后装入50mL的陶瓷坩埚，置于马弗炉中，在400℃下焙烧4h，即得到WO3/SrFe12O19。
本发明采用上述技术方案，主要有以下效果：
(1)本发明方法制备的磁性复合光催化剂WO3/SrFe12O19具有较高的光催化活性，在H2O2(5mM)的共同参与下，0.1g制备的最优复合磁性光催化剂降解100mL浓度为10mg/L的罗丹明B溶液，80min时降解率达98.4％(明显优于对比文件2制备的Fe3O4/WO3复合磁性光催化剂)，且本发明用于降解目标染料罗丹明B的浓度更高，所用时间更短。
(2)本发明方法制备的磁性复合光催化剂WO3/SrFe12O19可在外加磁场作用下进行回收，3次回收重复使用对罗丹明B降解率仍达到86.6％。
(3)本发明方法制备的磁性复合光催化剂WO3/SrFe12O19，比表面积为11.9m2/g，其制备方法简便，成本低，安全环保。
附图说明
图1为SrFe12O19、WO3和WO3/SrFe12O19的X射线衍射图谱；
图2为WO3/SrFe12O19的场发射扫描电镜SEM图；
图3为SrFe12O19、WO3和WO3/SrFe12O19的红外光谱图；
图4为SrFe12O19和WO3/SrFe12O19的磁滞回线图。
具体实施方式
下面结合具体实施方式，进一步说明本发明。
实施例1
一种磁性复合光催化剂WO3/SrFe12O19的制备方法，具体步骤如下：
(1)SrFe12O19的制备
分别称取0.7465g的SrCl2·6H2O和6.0545g的FeCl3·6H2O，用35mL去离子水超声溶解，得到混合溶液A；称取8.736g的NaOH，用20mL去离子水超声溶解，得到溶液B；在恒温20℃水浴和磁力搅拌下，将溶液B缓慢滴加到混合溶液A中，持续搅拌15min，待溶液充分混合，得到SrFe12O19前驱体C；将前驱体C倒入100mL水热釜中，200℃下反应24h取出，自然冷却至室温，抽滤，滤饼用去离子水洗涤至滤液呈中性后，置于80℃烘箱中干燥24h，研磨得到SrFe12O19。
(2)WO3/SrFe12O19的制备
分别称取1g的Na2WO4·2H2O和1.2g的C6H8O7·H2O，加入到60mL去离子水中，超声15min并机械搅拌15min使其充分混合，得到溶液D；按照理论生成SrFe12O19在复合物中的质量百分数3wt％，称取已制备好的SrFe12O19粉末加入到溶液D中，持续机械搅拌30min，用2mol/L的稀HCl调节混合溶液的pH为1，继续搅拌1h，得到悬浊液E；将悬浊液E装入100mL的水热釜中，120℃下反应24h取出，冷却至室温，过滤，滤饼用去离子水洗涤后置于80℃烘箱中干燥12h，将烘干样研磨后装入50mL的陶瓷坩埚，置于马弗炉中，在400℃下焙烧4h，即得到WO3/SrFe12O19。
实施例2
一种磁性复合光催化剂WO3/SrFe12O19的制备方法，具体步骤如下：
(1)同实施例1的步骤(1)。
(2)WO3/SrFe12O19的制备
分别称取1g的Na2WO4·2H2O和1.2g的C6H8O7·H2O，加入到60mL去离子水中，超声15min并机械搅拌15min使其充分混合，得到溶液D；按照理论生成SrFe12O19在复合物中的质量百分数5wt％，称取已制备好的SrFe12O19粉末加入到溶液D中，持续机械搅拌30min，用2mol/L的稀HCl调节混合溶液的pH为1，继续搅拌1h，得到悬浊液E；将悬浊液E装入100mL的水热釜中，120℃下反应24h取出，冷却至室温，过滤，滤饼用去离子水洗涤后置于80℃烘箱中干燥12h，将烘干样研磨后装入50mL的陶瓷坩埚，置于马弗炉中，在400℃下焙烧4h，即得到WO3/SrFe12O19。
实施例3
一种磁性复合光催化剂WO3/SrFe12O19的制备方法，具体步骤如下：
(1)同实施例1的步骤(1)。
(2)WO3/SrFe12O19的制备
分别称取1g的Na2WO4·2H2O和1.2g的C6H8O7·H2O，加入到60mL去离子水中，超声15min并机械搅拌15min使其充分混合，得到溶液D；按照理论生成SrFe12O19在复合物中的质量百分数7wt％，称取已制备好的SrFe12O19粉末加入到溶液D中，持续机械搅拌30min，用2mol/L的稀HCl调节混合溶液的pH为1，继续搅拌1h，得到悬浊液E；将悬浊液E装入100mL的水热釜中，120℃下反应24h取出，冷却至室温，过滤，滤饼用去离子水洗涤后置于80℃烘箱中干燥12h，将烘干样研磨后装入50mL的陶瓷坩埚，置于马弗炉中，在400℃下焙烧4h，即得到WO3/SrFe12O19。
实验结果
实施例2制备的磁性复合光催化剂WO3/SrFe12O19的催化降解活性最佳。为了方便对比，制备了WO3样品。WO3制备方法为实施例2步骤(2)中不加入SrFe12O19。
本发明所制备的SrFe12O19、WO3和WO3/SrFe12O19的XRD表征如图1中所示。图1(a)为SrFe12O19的X射线衍射图，2-Theta位于23.19°，30.39°，31.02°，32.36°、34.22°、37.18°、40.43°、42.53°、55.18°和63.12°处的特征峰，分别归属于M型的六方晶系SrFe12O19(JCPDS卡片No.33-1340)的(006)、(110)、(008)、(107)、(114)、(203)、(205)、(206)、(217)和(220)晶面；图1(c)为WO3的X射线衍射图，2-Theta位于23.11°、23.58°、24.34°和34.12°处的衍射峰，分别对应标准卡片中单斜相WO3(JCPDS卡片No.43-1035)的(002)、(020)、(200)和(202)晶面；图1(b)是采用本发明方法所制备的磁性复合光催化剂WO3/SrFe12O19的X射线衍射图，特征衍射峰与上述SrFe12O19和WO3的特征峰一一对应，其各峰形都较为明显，说明产物结晶完整，谱图中既存在SrFe12O19的衍射峰，也有WO3的衍射峰，表明WO3/SrFe12O19复合磁性光催化是由单斜相三氧化钨和M型锶铁氧体所构成的，具有其相关的特性，结构稳定。
本发明所制备的SrFe12O19、WO3和WO3/SrFe12O19的扫描电镜图如图2所示，可以看出，采用水热-焙烧法制备的WO3是由60nm-65nm厚的纵横交错状纳米片组装而成的纳米微球，直径约为2.5μm-2.8μm；SrFe12O19呈现形貌完整的正六边形，无杂质生成，该形貌与XRD检测结果所对应的M型锶铁氧体的形貌特征相符；在放大倍数为200nm可视条件下，WO3/SrFe12O19选区中可明显辨识出磁性基体SrFe12O19，即六角纳米片分布在WO3微球中与球形颗粒具有良好的界面接触，复合样品同时满足三氧化钨和锶铁氧体的形貌特征，证明按照本发明方法已成功制备得到了WO3/SrFe12O19复合磁性光催化剂。
本发明方法所制备的SrFe12O19、WO3和WO3/SrFe12O19的红外光谱如图3所示，在特征区中，波数为1617.5cm-1处的吸收峰是被测样品表面的复合氧化物吸附水的羟基O-H弯曲振动所形成的吸收振动峰，在2921.7cm-1左右处的吸收峰为C-H键的伸缩振动所引起的；其中，指纹区所显示的特征吸收峰1410.6cm-1和1343.7cm-1处的微弱吸收带，分别归属于单斜相WO3的W-OH和W＝O键，说明样品表面存在微小的水合作用；在500cm-1-1000cm-1区间的吸收峰为O-W-O的伸缩振动；位于541cm-1和580cm-1(Fe3+-O2-振动)处的吸收峰归属于SrFe12O19的特征吸收峰，但由于此范围内的吸收带与WO3(610cm-1左右)的部分特征峰重叠，因此，复合样品WO3/SrFe12O19在该峰位上向低波数方向略有偏移，这也可以说明WO3与SrFe12O19复合后，二者之间确实存在一种电子的供受体关系，从而表现为特征键位上的移动。由于WO3/SrFe12O19复合磁性光催化剂拥有SrFe12O19和WO3明显的特征峰，且上述表征结果与文献相符并与XRD表征结果相对应，证明本发明WO3/SrFe12O19复合磁性光催化剂的制备方法切实有效。
光催化实验显示，本发明方法制备的一种WO3/SrFe12O19复合磁性光催化剂，在模拟太阳光氙灯的照射下，0.1g制备的最优复合磁性光催化剂与H2O2(5mM)的共同作用，降解100mL浓度为10mg/L的罗丹明B溶液，80min时降解率达98.4％，说明采用本发明制备的WO3/SrFe12O19复合磁性光催化剂具有较高的光催化活性，对模拟太阳光有较强的利用转换和吸收作用，能够加快生成电子-空穴对，使得反应生成大量的具有强氧化性的·OH自由基，快速降解染料分子，且3次重复利用后，对罗丹明B的降解率保持在86.6％以上。
SrFe12O19和WO3/SrFe12O19的磁性能参数测试结果如图4所示，SrFe12O19饱和磁化强度为61.5emu/g、矫顽力为746.3Oe；WO3/SrFe12O19饱和磁化强度为3.4emu/g、矫顽力为951.1Oe；以本发明方法制备的磁性复合光催化剂WO3/SrFe12O19拥有较强的磁学性能优势，其矫顽力有明显的提升，具有更高的抗退磁能力和磁稳定性，有利于光催化剂的回收利用。
以上实施例描述了本发明的制备方法、主要特征及优点。本发明不受上述实施例的限制，在不脱离本发明原理、方法的范围下，本发明将持续改进，这些均落入本发明保护的范围内。
Claims (2)
1.一种磁性三氧化钨复合光催化剂WO3/SrFe12O19的制备方法，其特征包括以下步骤：
(1)SrFe12O19的制备
分别称取0.7465g的SrCl2·6H2O和6.0545g的FeCl3·6H2O，用35mL去离子水超声溶解，得到混合溶液A；称取8.736g的NaOH，用20mL去离子水超声溶解，得到溶液B；在恒温20℃水浴和磁力搅拌下，将溶液B缓慢滴加到混合溶液A中，持续搅拌15min，待溶液充分混合，得到SrFe12O19前驱体C；将前驱体C倒入100mL水热釜中，200℃下反应24h取出，自然冷却至室温，抽滤，滤饼用去离子水洗涤至滤液呈中性后，置于80℃烘箱中干燥24h，研磨得到SrFe12O19。
(2)WO3/SrFe12O19的制备
分别称取1g的Na2WO4·2H2O和1.2g的柠檬酸C6H8O7·H2O，加入到60mL去离子水中，超声15min并机械搅拌15min使其充分混合，得到溶液D；按照理论生成SrFe12O19在复合物中的质量百分数3wt％～7wt％，称取已制备好的SrFe12O19粉末加入到溶液D中，持续机械搅拌30min，用2mol/L的稀HCl调节混合溶液的pH为1，继续搅拌1h，得到悬浊液E；将悬浊液E装入100mL的水热釜中，120℃下反应24h取出，冷却至室温，过滤，滤饼用去离子水洗涤后置于80℃烘箱中干燥12h，将烘干样研磨后装入50mL的陶瓷坩埚，置于马弗炉中，在400℃下焙烧4h，即得到WO3/SrFe12O19。
2.根据权利要求1所述的WO3/SrFe12O19复合磁性光催化剂的制备方法，其特征在于以水热-焙烧两步法制备，实现了活性组分WO3与磁性基体SrFe12O19的有效复合。
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| CN114939416A (zh) * | 2022-07-01 | 2022-08-26 | 重庆大学 | 一种可见光响应的复合磁性二氧化锡光催化剂的制备方法 |
| CN114950463A (zh) * | 2022-07-01 | 2022-08-30 | 重庆大学 | 一种新型磁性复合光催化剂MoO3/SrFe12O19的制备方法 |
| CN114939416B (zh) * | 2022-07-01 | 2023-08-22 | 重庆大学 | 一种可见光响应的复合磁性二氧化锡光催化剂的制备方法 |
| CN114950463B (zh) * | 2022-07-01 | 2023-09-08 | 重庆大学 | 一种新型磁性复合光催化剂MoO3/SrFe12O19的制备方法 |
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