CN115254123B - 一种新型镍磁性复合光催化剂SnO2/NiFe2O4的制备方法 - Google Patents
一种新型镍磁性复合光催化剂SnO2/NiFe2O4的制备方法 Download PDFInfo
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- 229910006404 SnO 2 Inorganic materials 0.000 title claims abstract description 74
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 45
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- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
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- 238000000227 grinding Methods 0.000 claims abstract description 16
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
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- 230000001699 photocatalysis Effects 0.000 abstract description 14
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 abstract description 8
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- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
一种新型镍磁性复合光催化剂SnO2/NiFe2O4的制备方法，其属于无机催化材料领域。本发明先通过水热法制备了纯相NiFe2O4和纯相SnO2，然后通过研磨制备出镍磁性复合光催化剂SnO2/NiFe2O4。本发明方法制备工艺简单，使用设备少且生产成本低。制备的SnO2/NiFe2O4光催化活性高，在模拟太阳光照射下，制备的0.1g镍磁性复合二氧化锡光催化剂降解100mL浓度为5mg/L的罗丹明B溶液，120min降解率达到97.3％，高于相同条件下SnO2的降解率(67.4％)。复合磁性光催化剂在相同降解条件下循环使用4次后对罗丹明B溶液的降解率仍达95.5％，本发明制备出的产品可广泛用于光催化降解有机污染物的领域中。
Description
技术领域
本发明涉及一种新型镍磁性复合光催化剂SnO2/NiFe2O4的制备方法，属于无机催化材料技术领域。
背景技术
随着人们对水体污染和能源危机的重视，利用清洁和丰富的太阳能受到了广泛的关注。二氧化锡(SnO2)由于其稳定性高、不易被腐蚀、无二次污染且价格低廉的特点，受到学者关注。但是，SnO2是典型的n型半导体，禁带宽度较大(约为3.6eV)，不能被可见光激发，只能对高能量的紫外光产生响应，因此SnO2对光能的利用率较低。同时，SnO2内部的光生电子-空穴对易复合，这些因素都抑制了SnO2的光催化性能，制约了其在实际生产中的应用。另外，现阶段制备的SnO2多为粉末状，反应后悬浮于体系中，难以回收，这制约了SnO2的光催化剂开发与利用。将光催化剂与磁性材料结合构筑磁性光催化剂，能为半导体光催化材料的循环回收和重复使用提供参考。镍铁氧体(NiFe2O4)具备特殊的反尖晶石结构，是当下研究最为广泛的软磁性铁氧体之一。NiFe2O4属于软磁材料，为p型半导体，可对可见光响应，同时其具有高稳定性、高磁导率和独特的微波吸收性能，是一种理想的SnO2赋磁改性剂。
目前通过对SnO2掺杂不同元素和复合不同化合物来提高其光催化活性的研究较多，其中SnO2负载铁氧体等半导体能提高在可见光区的光响应，提升光催化活性，同时磁性也使得光催化剂更易于回收利用。因此SnO2与铁氧体的复合开始受到了研究者的青睐。如“Materials Letters”2017年第199卷第135-138页“A spray pyrolysis synthesis ofMnFe2O4/SnO2 yolk/shell composites for magnetically recyclable photocatalyst”一文，公开的方法是：在先制备MnFe2O4的情况下，用乙二醇作为介质，通过超声波喷雾器，利用喷雾热解法制备了MnFe2O4/SnO2复合光催化剂。该方法的主要缺点是：(1)采用乙二醇溶液分散体系、超声喷雾(Ar气体)、800℃热解法，且使用了有机溶剂为介质，制备工艺复杂、设备要求高。(2)制备的MnFe2O4/SnO2复合光催化剂平均粒径为432nm，粒径较大，不利于光催化降解过程中催化剂本身与有机污染物充分接触和反应。(3)复合催化剂仅在紫外光照射下对甲基橙(MO)溶液有降解作用。
又如“Materials Science in Semiconductor Processing”2020年第107卷“SnO2quantum dots decorated NiFe2O4 nanoplates:0D/2D heterojunction forenhanced visible-light-driven photocatalysis”一文，公开的方法是：先用焙烧法和沉淀法制备出纯相NiFe2O4和SnO2，再采取溶剂(乙醇)热法制备出NiFe2O4/SnO2复合光催化材料。该方法的主要缺点是：(1)制备工艺复杂，复合催化剂制备采用了焙烧法、沉淀法和溶剂热法三种方法；(2)制备的复合光催化剂，实际上是用SnO2去改性NiFe2O4以提高NiFe2O4的光催化活性。
将镍铁氧体(NiFe2O4)负载到SnO2上，可改善SnO2光生电子-空穴对复合快的问题。NiFe2O4与SnO2间可形成Z型异质结结构，提升光生电子在半导体间的迁移速率，促进电荷有效分离，有效降低光生载流子的复合速率，提高SnO2的光催化活性，且便于磁性回收。同时，可以改善SnO2在可见光区光响应差的问题，提高对可见光的利用率，进而提高其光催化活性。复合材料是通过水热法和简单的物理研磨法制备成功，生产工艺简单、效率高、成本低、产品性能稳定。
发明内容
本发明的目的是针对纯SnO2在可见光下降解效率低和粉末催化剂难以回收的问题，提出采用NiFe2O4对SnO2进行改性以提高其光催化活性，即提出了一种SnO2/NiFe2O4复合镍磁性光催化剂的制备方法，该制备工艺方法简单，生产成本低，周期短，催化活性高，且经过4次回收后的复合光催化剂对罗丹明B溶液的降解率仍达到95.5％，光催化性能稳定。本发明SnO2/NiFe2O4复合磁性光催化剂的制备方法如下：
(1)NiFe2O4的制备
按照Ni:Fe＝2:1的摩尔比，分别以NiCl2·6H2O和FeCl3·6H2O为镍源与铁源，将其溶解于50mL蒸馏水中，超声15min得到溶液A；将2mo/L的NaOH溶液逐滴加入溶液A中，调节pH＝12，得到悬浊液B，继续搅拌30min后，将悬浊液B转移到100mL的聚四氟乙烯内衬不锈钢反应釜并放入烘箱，180℃下反应18h，反应釜自然冷却至室温后，过滤，滤饼分别用蒸馏水和无水乙醇洗涤3次，80℃下干燥24h，研磨得到棕色粉末NiFe2O4；
(2)SnO2的制备
称取1.2271g的SnCl4·5H2O溶于25mL蒸馏水中，磁力搅拌30min得到澄清透明溶液；将2mo/L的NaOH溶液逐滴加入透明溶液中，调节溶液的pH为11.0，继续搅拌30min后向混合溶液中加入35mL无水乙醇，得到乳白色SnO2前驱体溶液；将前驱体溶液继续搅拌30min后转移到100mL聚四氟乙烯内衬反应釜中，200℃下反应24h后冷却至室温，过滤，滤饼分别用蒸馏水和无水乙醇离心洗涤3次，在80℃下烘干24h，研磨得白色SnO2；
(3)镍磁性复合光催化剂SnO2/NiFe2O4的制备
按照NiFe2O4:SnO2质量1-10:100比例，称取NiFe2O4和SnO2置于研钵中，研磨10min后，即得到镍磁性复合光催化剂SnO2/NiFe2O4。
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SnO2/NiFe2O4复合光催化剂在具有较高的光催化活性，在模拟太阳光(300W氙灯)照射下，制备的0.1g复合镍磁性复合光催化剂SnO2/NiFe2O4分散于100mL浓度为5mg/L的罗丹明B溶液中，120min后降解率达到了97.3％，而相同条件下SnO2的降解率仅为67.4％。
(2)本发明方法制备的SnO2/NiFe2O4复合磁性光催化剂磁回收，循环使用4次后的复合光催化剂对罗丹明B的降解率仍高达95.5％。
(3)本发明采用水热法与研磨法制备，制备操作简单，所需设备少，能耗低。
附图说明
图1为SnO2、NiFe2O4和SnO2/NiFe2O4的X射线衍射图谱。
图2为SnO2/NiFe2O4的X-射线光电子能谱图。
图3为SnO2和SnO2/NiFe2O4对罗丹明B溶液的光催化降解曲线图。
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
一种新型镍磁性复合二氧化锡光催化剂SnO2/NiFe2O4的制备方法，具体步骤如下：
(1)NiFe2O4的制备
按照Ni:Fe＝2:1的摩尔比，分别以NiCl2·6H2O和FeCl3·6H2O为镍源与铁源，将其溶解于50mL蒸馏水中，超声15min得到溶液A；将2mo/L的NaOH溶液逐滴加入溶液A中，调节pH＝12，得到悬浊液B，继续搅拌30min后，将悬浊液B转移到100mL的聚四氟乙烯内衬不锈钢反应釜并放入烘箱，180℃下反应18h，反应釜自然冷却至室温后，过滤，滤饼分别用蒸馏水和无水乙醇洗涤3次，80℃下干燥24h，研磨得到棕色粉末NiFe2O4；
(2)SnO2的制备
称取1.2271g的SnCl4·5H2O溶于25mL蒸馏水中，磁力搅拌30min得到澄清透明溶液；将2mo/L的NaOH溶液逐滴加入透明溶液中，调节溶液的pH为11.0，继续搅拌30min后向混合溶液中加入35mL无水乙醇，得到乳白色SnO2前驱体溶液；将前驱体溶液继续搅拌30min后转移到100mL聚四氟乙烯内衬反应釜中，200℃下反应24h后冷却至室温，过滤，滤饼分别用蒸馏水和无水乙醇离心洗涤3次，在80℃下烘干24h，研磨得白色SnO2。
(3)镍磁性复合光催化剂SnO2/NiFe2O4的制备
按照NiFe2O4:SnO2质量1:100比例，称取NiFe2O4和SnO2置于研钵中，研磨10min后，即得到镍磁性复合光催化剂SnO2/NiFe2O4(SN-1)。
实施例2
一种新型镍磁性复合二氧化锡光催化剂SnO2/NiFe2O4的制备方法，具体步骤如下：
(1)同实施例1中(1)。
(2)同实施例2中(2)
(3)镍磁性复合光催化剂SnO2/NiFe2O4的制备
按照NiFe2O4:SnO2质量3:100比例，称取NiFe2O4和SnO2置于研钵中，研磨10min后，即得到镍磁性复合光催化剂SnO2/NiFe2O4(SN-3)。
实施例3
一种新型镍磁性复合二氧化锡光催化剂SnO2/NiFe2O4的制备方法，具体步骤如下：
(1)同实施例1中(1)。
(2)同实施例2中(2)。
(3)镍磁性复合光催化剂SnO2/NiFe2O4的制备
按照NiFe2O4:SnO2质量5:100比例，称取NiFe2O4和SnO2置于研钵中，研磨10min后，即得到镍磁性复合光催化剂SnO2/NiFe2O4。
(3)SnO2/NiFe2O4光催化剂的制备
按照NiFe2O4与SnO2复合比例为5:100，称取NiFe2O4和SnO2置于研钵中，研磨10min后，即得到镍磁性复合光催化剂SnO2/NiFe2O4(SN-5)。
实施例4
一种新型镍磁性复合二氧化锡光催化剂SnO2/NiFe2O4的制备方法，具体步骤如下：
(1)同实施例1中(1)。
(2)同实施例2中(2)。
(3)镍磁性复合光催化剂SnO2/NiFe2O4的制备
按照NiFe2O4:SnO2质量10:100比例，称取NiFe2O4和SnO2置于研钵中，研磨10min后，即得到镍磁性复合光催化剂SnO2/NiFe2O4(SN-10)。
实验结果
实施例2制备的SnO2/NiFe2O4(SN-3)复合磁性光催化剂催化降解活性最佳。
NiFe2O4的XRD图如图1所示，纯相NiFe2O4在2θ＝18.42°、30.30°、35.69°、43.38°、53.83°、57.38°和63.02°处出现特征衍射峰，分别对应(111)、(220)、(311)、(400)、(422)、(511)和(440)晶面，与JCPDS No.86-2267标准卡片匹配成功，没有出现杂峰，说明通过水热法成功制备出尖晶石型铁氧体NiFe2O4；SnO2样品在2θ衍射角等于26.6°、33.9°、37.9°、51.8°、54.7°、57.8°和65.9°处出现衍射峰，对应(110)、(101)、(200)、(211)、(002)和(301)晶面，与标准PDF卡片(JCPDS NO.99-0024)相吻合，并且没有发现杂峰存在，表明制备所得SnO2为纯相的稳定四方相结构。
SN-3的XRD图谱特征峰与纯相SnO2基本对应，能在2θ为26.6°、33.9°、37.9°、51.8°和54.7°处发现对应四方晶系二氧化锡的特征衍射峰(JCPDS No.99-0024)，分别对应(110)、(101)、(200)、(211)和(220)晶面，衍射峰位置未发生偏移，说明NiFe2O4的加入没有明显改变SnO2的结构，在SN-3样品图谱中未出现NiFe2O4对应的特征衍射峰，这是由于样品中NFO含量较少所致。SN-3的X射线光电子能谱(XPS)图如图2所示。可以看出，SN-3样品中含有Sn、Fe、O和Ni四种元素，表明复合物中存在NiFe2O4。
磁性复合二氧化锡SnO2/NiFe2O4光催化剂降解罗丹明B的实验结果如图3所示。由图3可知，SnO2和SN-3在光照120min对罗丹明B的降解率分别为67.4％和97.3％，NiFe2O4(NFO)没有光催化活性，表明NiFe2O4改性后SnO2的光催化活性得到明显改善。VSM测试显示，SN-3饱和磁化强度为1.06emu/g，可实现磁分离。降解实验结束后，经过4次磁回收的SN-3复合光催化剂对罗丹明B的降解率仍达到95.5％，性能稳定。
Claims (1)
1.一种新型镍磁性复合光催化剂SnO2/NiFe2O4的制备方法，包括以下步骤：
(1)NiFe2O4的制备
按照Ni:Fe＝1:2的摩尔比，分别以NiCl2·6H2O和FeCl3·6H2O为镍源与铁源，将其溶解于50mL蒸馏水中，超声15min得到溶液A；将2mo/L的NaOH溶液逐滴加入溶液A中，调节pH＝12，得到悬浊液B，继续搅拌30min后，将悬浊液B转移到100mL的聚四氟乙烯内衬不锈钢反应釜并放入烘箱，180℃下反应18h，反应釜自然冷却至室温后，过滤，滤饼分别用蒸馏水和无水乙醇洗涤3次，80℃下干燥24h，研磨得到棕色粉末NiFe2O4；
(2)SnO2的制备
称取1.2271g的SnCl4·5H2O溶于25mL蒸馏水中，磁力搅拌30min得到澄清透明溶液；将2mo/L的NaOH溶液逐滴加入透明溶液中，调节溶液的pH为11.0，继续搅拌30min后向混合溶液中加入35mL无水乙醇，得到乳白色SnO2前驱体溶液；将前驱体溶液继续搅拌30min后转移到100mL聚四氟乙烯内衬反应釜中，200℃下反应24h后冷却至室温，过滤，滤饼分别用蒸馏水和无水乙醇离心洗涤3次，在80℃下烘干24h，研磨得白色SnO2；
(3)镍磁性复合光催化剂SnO2/NiFe2O4的制备
按照NiFe2O4:SnO2质量1-10:100比例，称取NiFe2O4和SnO2置于研钵中，研磨10min后，即得到镍磁性复合光催化剂SnO2/NiFe2O4。
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