CN108273511B - 一种用于吸附和降解偶氮染料的光催化剂及其制备方法 - Google Patents
一种用于吸附和降解偶氮染料的光催化剂及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种用于吸附和降解偶氮染料的光催化剂，该光催化剂为固载在光纤上的含磁性材料的Cr掺杂ZnO；光催化剂的制备方法步骤：S1、制备含磁性材料的Cr掺杂ZnO：将可溶性的锌盐、铬盐、铁盐溶于乙醇中得到溶液A，将NaOH的乙醇溶液加入到溶液A中，搅拌，加热反应后，离心分离，干燥沉淀物，得到Cr‑ZnO/γ‑Fe2O3；S2、光纤包埋Cr‑ZnO/γ‑Fe2O3，包括：S21、去除光纤表面的外包层，裸露出光纤芯体；S22、采用溶胶凝胶法在光纤芯体表面包埋Cr‑ZnO/γ‑Fe2O3，即得到光催化剂。本发明将光催化剂包埋在光纤表面，克服了普通的多孔性载体孔内的光催化剂得不到光照，造成光催化剂浪费的缺陷，提高了光催化剂的有效利用率。
Description
技术领域
本发明属于光催化技术领域，具体涉及一种用于吸附和降解偶氮染料的光催化剂及其制备方法。
背景技术
偶氮类染料的化学性质相对稳定，故其废水成分比较复杂，难以彻底降解。未经过处理的废水直接排放到河流、湖泊中会造成水体严重污染，导致水生环境急剧恶化。传统的处理方法如混凝沉淀法、吸附法、膜分离法、气浮法等这些技术属于非破坏性的物理处理技术，只是对染料进行相间转移，并没有真正对染料进行脱色和矿化，并且会二次污染。其中混凝剂、吸附剂等再生问题一直得不到合理解决。而化学、生化等处理技术虽是破坏性的，但除净度低，废水中的有毒物含量仍远远高于国家废水排放标准。因此，寻找一种新型的处理偶氮染料的方法势在必行。
近年来，作为光催化剂的半导体材料被成功地用于有机处理水污染物。半导体光催化技术能够在常温常压下彻底分解水中的有机污染物，且无二次污染，是降解水中有机污染物的新型绿色技术，有望在环境污染治理领域取得重大突破。常用的半导体光催化材料有TiO2、Cu2O、Fe2O3、Ag3PO4、ZnO等。ZnO作为重要的半导体光催化剂，是一种直接宽带隙(3.37eV)半导体材料，激子束缚能为60meV，易被激发，具有较高的催化活性。在光催化反应降解有机污染物的研究当中，因其光催化活性高、化学稳定性好、无毒无污染、廉价等优良的性能已被广泛研究作为半导体光催化剂消除有机污染物的有效方法。
ZnO中掺杂过渡金属是提高其催化性能的很有效的方法。通过用过渡金属掺杂ZnO纳米颗粒就可以实现离子通过形成电子陷阱显示电子和空穴之间的电荷分离增强，并且还减小了材料的带隙。在三价掺杂金属中，Cr是一种离子半径约等于Zn2+的过渡金属，因此它可以很容易地取代ZnO晶格中的Zn2+位置，同时，掺杂Cr的ZnO还可在Cr位置化学吸附氧。到目前为止，也报道了很多种掺杂Cr的ZnO的沉积技术，如磁控溅射，溶胶-凝胶，脉冲激光沉积和溶剂热法等。其中，溶剂热法以制备过程简单、绿色、产物的组成和形貌易控制等特点而备受关注。并且，在溶剂热反应过程中，通过控制反应温度、时间和介质条件就可以获得形貌独特、性能优异的纳米材料。但是该种方法制备出的Cr-ZnO所需时间较长，产物量较少，而且还存在处理废水后，光催化剂与废水的分离难的问题，以及光催化剂的有效利用率不高，用量大，光催化剂浪费量大，不仅造成经济成本高，且大量资源浪费。
发明内容
本发明的一个目的是解决ZnO光催化剂在偶氮染料废水处理中存在的固液分离难，不能充分与光接触反应，催化剂利用率低等技术问题。
本发明还有一个目的是提供一种制备上述的用于吸附和降解偶氮染料的光催化剂的方法，其制备工艺简单，消耗时间少，产量高。
为了实现上述的这些目的和其它优点，本发明提供了一种用于吸附和降解偶氮染料的光催化剂，该光催化剂为固载在光纤上的含磁性材料的Cr掺杂ZnO。具体的是，所述磁性材料为γ-Fe2O3，所述光纤为去除外包层的光纤芯体，得到的光催化剂是固载在光纤上的含磁性材料的Cr-ZnO/γ-Fe2O3。
一种制备上述的用于吸附和降解偶氮染料的光催化剂的制备方法，包括如下步骤：
S1、制备含磁性材料的Cr掺杂ZnO：
将可溶性的锌盐、铬盐、铁盐溶于乙醇中得到溶液A，将NaOH的乙醇溶液加入到溶液A中，搅拌，加热反应后，离心分离，干燥沉淀物，得到含有γ-Fe2O3的Cr掺杂ZnO，即Cr-ZnO/γ-Fe2O3；
S2、光纤包埋Cr-ZnO/γ-Fe2O3，包括步骤：
S21、去除光纤表面的外包层，裸露出光纤芯体；
S22、采用溶胶凝胶法在光纤芯体表面包埋Cr-ZnO/γ-Fe2O3，即得到光催化剂。
优选的是，所述步骤S21具体为：将含有外包层的光纤置于丙酮溶液中浸泡腐蚀10-20min，然后用外力去除光纤表面的外包层裸露出光纤芯体，将光纤芯体浸泡在氢氧化钠溶液中约10min，再用清水清洗，擦干待用。
优选的是，所述步骤S22具体为：将偶联剂与四乙氧基硅烷混合均匀，再依次加入乙醇、水和0.1mol/L的盐酸，超声分散处理，得到溶胶凝胶；在溶胶凝胶中加入步骤S1制备的Cr-ZnO/γ-Fe2O3，超声分散均匀；然后将混有Cr-ZnO/γ-Fe2O3的溶胶凝胶涂覆在光纤芯体表面，或者将光纤芯体浸入溶胶凝胶中通过提拉法将Cr-ZnO/γ-Fe2O3包埋在光纤芯体表面，每次涂覆后或者每次提拉出光纤芯体后，在60℃下干燥，重复涂覆或提拉3-5次后，将包埋Cr-ZnO/γ-Fe2O3的光纤在室温下老化，即得到光催化剂。
优选的是，所述偶联剂为三氟丙基三甲氧基硅烷、丙基三甲氧基硅烷或3-氨基丙基三乙氧基硅烷中的一种。
优选的是，所述步骤S22具体为：取7.5ml偶联剂与3.5ml四乙氧基硅烷混合均匀，再依次加入7.5ml乙醇、3.2ml水和0.4ml的0.1mol/L盐酸，超声分散处理半小时，得到溶胶凝胶；在溶胶凝胶中加入步骤S1制备的Cr-ZnO/γ-Fe2O3，超声分散1h混合均匀；然后将混有Cr-ZnO/γ-Fe2O3的溶胶凝胶涂覆在光纤芯体表面，或者将光纤芯体浸入溶胶凝胶中通过提拉法将Cr-ZnO/γ-Fe2O3包埋在光纤芯体表面，每次涂覆后或者每次提拉出光纤芯体后，在60℃下干燥，重复涂覆或提拉5次后，将包埋Cr-ZnO/γ-Fe2O3的光纤在室温下老化一周，即得到光催化剂。
优选的是，所述步骤S1具体为：将2mmol的Zn(NO3)2·6H2O、0.12mmol的Cr(NO3)3·9H2O、0.12mmol的Fe(NO3)3·9H2O溶于40ml乙醇中，并在室温下搅拌20min，得到溶液A；将40ml浓度4mol/L的NaOH乙醇溶液在搅拌条件下加入到溶液A中，并在室温下搅拌1h，然后将反应液转移至特氟隆反应釜中，并在120℃条件下恒温反应12h，冷却至室温，离心分离出沉淀物，先后用去离子水和乙醇清洗沉淀物，在80℃下干燥12h，得到含有γ-Fe2O3的Cr掺杂ZnO，即Cr-ZnO/γ-Fe2O3。
本发明的有益之处在于：
(1)利用溶剂热法合成一种清洁无污染可二次利用的金属铬掺杂氧化锌磁性纳米材料，这种磁性纳米材料对水体中的染料有很好的吸附性能和光催化降解效果，而且该催化剂与液体分离简单，便于回收重复利用催化剂。
(2)Cr-ZnO/γ-Fe2O3包埋于光纤表面，提供了更高的比表面积，光在光纤内由光密射向光疏介质时，光会发生内全反射，进而会在裸露光纤界面产生与入射光波长一致的渐逝场，其渐逝场可以作为光催化剂的光源，能够对光进行充分利用；光纤能够进行远距离的传输且在传播过程中光没有损失，可用于光照难到达区域的污水光催化降解处理；对于普通的多孔性载体来说，位于载体孔内深处的光催化剂得不到光照，造成光催化剂的浪费，而将光催化剂包埋在光纤中就有效地避免了这一缺点，能够最大限定利用光催化剂。
(3)包埋于光纤表面的光催化剂Cr-ZnO/γ-Fe2O3可对偶氮染料，例如亚甲基蓝(MB)或甲基橙(MO)进行吸附和降解，吸附率和降解率均在90％以上。
附图说明
图1、甲基橙溶液吸附前、吸附后的紫外可见吸光度曲线对比图。
图2、甲基橙染料溶液的吸光度随光照时间的变化曲线。
图3、甲基橙溶液在无光照射以及光照射150min后的紫外吸收峰对比图。
具体实施方式
以下结合附图对本发明的优选实施例进行说明，应当理解，此处所描述的优选实施例仅用于说明和解释本发明，并不用于限定本发明。
一、制备方法实施例
一种用于吸附和降解偶氮染料的光催化剂的制备方法，包括如下步骤：
步骤1、制备含磁性材料的Cr掺杂ZnO：将2mmol的Zn(NO3)2·6H2O、0.12mmol的Cr(NO3)3·9H2O、0.12mmol的Fe(NO3)3·9H2O溶于40ml乙醇中，并在室温下搅拌20min，得到溶液A；将40ml浓度4mol/L的NaOH乙醇溶液在搅拌条件下加入到溶液A中，并在室温下搅拌1h，然后将反应液转移至特氟隆反应釜中，并在120℃条件下恒温反应12h，冷却至室温，离心分离出沉淀物，先后用去离子水和乙醇清洗沉淀物，在80℃下干燥12h，得到含有γ-Fe2O3的Cr掺杂ZnO，即Cr-ZnO/γ-Fe2O3。
步骤2、光纤包埋Cr-ZnO/γ-Fe2O3：首先，用陶瓷片切取一定长度的含有外包层的光纤(i.d.＝700um，南京春晖有限公司)，将需要去除外包层材料的光纤部分置于丙酮溶液中浸泡10-20分钟后，取出光纤用外力去除光纤表面的外包层裸露出光纤芯体；然后将光纤芯体浸泡在1mol/L的氢氧化钠溶液中10分钟左右，取出光纤芯体用水清洗干净并用高级擦镜纸擦干，待用；取7.5ml偶联剂与3.5ml四乙氧基硅烷混合均匀，再依次加入7.5ml乙醇、3.2ml水和0.4ml的0.1mol/L盐酸，超声分散处理半小时，得到溶胶凝胶；在溶胶凝胶中加入步骤1制备的Cr-ZnO/γ-Fe2O3，超声分散1h混合均匀；然后将混有Cr-ZnO/γ-Fe2O3的溶胶凝胶涂覆在光纤芯体表面，或者将光纤芯体浸入溶胶凝胶中通过提拉法将Cr-ZnO/γ-Fe2O3包埋在光纤芯体表面，每次涂覆后或者每次提拉出光纤芯体后，在60℃下干燥，重复涂覆或提拉5次后，将包埋Cr-ZnO/γ-Fe2O3的光纤在室温下老化一周，即得到光催化剂。所述偶联剂为三氟丙基三甲氧基硅烷、丙基三甲氧基硅烷或3-氨基丙基三乙氧基硅烷中的一种。
二、应用实施例
(1)固载于光纤上的Cr-ZnO/γ-Fe2O3光催化剂对染料的吸附
配制浓度分别为1ppm、2ppm、5ppm、8ppm、10ppm、20ppm、30ppm的甲基橙(MO)染料溶液，分别向各溶液中加入固载于光纤上的Cr-ZnO/γ-Fe2O3光催化剂，确保光催化剂完全浸没在溶液中，在避光条件下震荡时间3h以达到吸附平衡，然后测定初始染料溶液及吸附后染料溶液的紫外可见吸光度，根据公式qe＝(C0-Ce)*V/M，计算出吸附量qe；根据公式Dyeremoval％＝(C0-Ce)/Ce*100％，计算出吸附率Dye removal％，其中，C0为初始浓度，Ce为吸附后浓度，V为所用染料体积，M为所用吸附剂重量。图1为浓度20ppm的甲基橙溶液吸附前、吸附后的紫外可见吸光度曲线对比图。可以看出，吸附后的甲基橙溶液吸光度值明显低于吸附前初始甲基橙溶液的吸光度值，这是因为该光催化剂中含有的Fe2O3具有较好的吸附性能，将溶液中的甲基橙分子吸附于光催化剂上。
(2)固载于光纤上的Cr-ZnO/γ-Fe2O3光催化剂对染料的光催化降解
向浓度10ppm的甲基橙染料溶液中加入固载于光纤上的Cr-ZnO/γ-Fe2O3光催化剂，确保光催化剂完全浸没在溶液中，在避光条件下搅拌3h，使光催化剂对染料进行充分吸附；然后将波长365nm的光源与光纤一端耦合，使得光线在光纤内部传播，并每隔30min取溶液样品测定紫外可见吸光度，得出光催化剂对甲基橙染料的光催化降解随时间的变化关系，见图2。可以看出，随着光照时间的延长，甲基橙溶液的吸光度明显减小，说明绝大部分甲基橙被光催化剂分解，该光催化剂具有显著的催化性能。图3是浓度20ppm的甲基橙溶液在无光照射以及光照射150min后的紫外吸收峰对比图。同样可以看出，经过光照射反应后的甲基橙溶液的吸收峰明显低于没有光照的甲基橙溶液。由此说明，光照过程中，光作用于光催化剂上，催化降解甲基橙分子，体现出优异的光催化性能。而且，染料溶液催化降解处理完成后，只需取出其中的光催化剂，省去了复杂的固液分离步骤，使得污水处理过程高效，简单化。取出的光催化剂可以重复使用，有效利用率高，避免资源浪费，节约成本。
综上所述，本发明结合溶剂热法和包埋技术合成了一种新型、清洁无污染可二次利用固载于光纤上的Cr-ZnO/γ-Fe2O3光催化剂，这种光催化剂不仅对水体中的染料有很好的吸附性能，而且对染料还有光催化降解效果。
以上所述，仅是本发明的较佳实施例而已，并非对本发明作任何形式上的限制，虽然本发明已以较佳实施例揭露如上，然而并非用以限定本发明，任何熟悉本专业的技术人员，在不脱离本发明技术方案范围内，当可利用上述揭示的技术内容作出些许更动或修饰为等同变化的等效实施例，但凡是未脱离本发明技术方案的内容，依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰，均仍属于本发明技术方案的范围内。
Claims (5)
1.一种用于吸附和降解偶氮染料的光催化剂，其特征在于，该光催化剂为固载在光纤上的含磁性材料的Cr掺杂ZnO，所述磁性材料为γ-Fe2O3，所述光纤为去除外包层的光纤芯体；该催化剂的制备方法包括如下步骤：
S1、制备含磁性材料的Cr掺杂ZnO：将可溶性的锌盐、铬盐、铁盐溶于乙醇中得到溶液A，将NaOH的乙醇溶液加入到溶液A中，搅拌，加热反应后，离心分离，干燥沉淀物，得到含有γ-Fe2O3的Cr掺杂ZnO，即Cr-ZnO/γ-Fe2O3；
S2、光纤包埋Cr-ZnO/γ-Fe2O3，具体步骤：S21、将含有外包层的光纤置于丙酮溶液中浸泡腐蚀10-20min，然后用外力去除光纤表面的外包层裸露出光纤芯体，将光纤芯体浸泡在氢氧化钠溶液中10min，再用清水清洗，擦干待用；S22、将偶联剂与四乙氧基硅烷混合均匀，再依次加入乙醇、水和0.1mol/L的盐酸，超声分散处理，得到溶胶凝胶；在溶胶凝胶中加入步骤S1制备的Cr-ZnO/γ-Fe2O3，超声分散均匀；然后将混有Cr-ZnO/γ-Fe2O3的溶胶凝胶涂覆在光纤芯体表面，或者将光纤芯体浸入溶胶凝胶中通过提拉法将Cr-ZnO/γ-Fe2O3包埋在光纤芯体表面，每次涂覆后或者每次提拉出光纤芯体后，在60℃下干燥，重复涂覆或提拉3-5次后，将包埋Cr-ZnO/γ-Fe2O3的光纤在室温下老化，即得到光催化剂。
2.一种如权利要求1所述的用于吸附和降解偶氮染料的光催化剂的制备方法，其特征在于，包括如下步骤：
S1、制备含磁性材料的Cr掺杂ZnO：
将可溶性的锌盐、铬盐、铁盐溶于乙醇中得到溶液A，将NaOH的乙醇溶液加入到溶液A中，搅拌，加热反应后，离心分离，干燥沉淀物，得到含有γ-Fe2O3的Cr掺杂ZnO，即Cr-ZnO/γ-Fe2O3；
S2、光纤包埋Cr-ZnO/γ-Fe2O3，包括步骤：
S21、去除光纤表面的外包层，裸露出光纤芯体，具体操作为：将含有外包层的光纤置于丙酮溶液中浸泡腐蚀10-20min，然后用外力去除光纤表面的外包层裸露出光纤芯体，将光纤芯体浸泡在氢氧化钠溶液中约10min，再用清水清洗，擦干待用；
S22、采用溶胶凝胶法在光纤芯体表面包埋Cr-ZnO/γ-Fe2O3，具体操作为：将偶联剂与四乙氧基硅烷混合均匀，再依次加入乙醇、水和0.1mol/L的盐酸，超声分散处理，得到溶胶凝胶；在溶胶凝胶中加入步骤S1制备的Cr-ZnO/γ-Fe2O3，超声分散均匀；然后将混有Cr-ZnO/γ-Fe2O3的溶胶凝胶涂覆在光纤芯体表面，或者将光纤芯体浸入溶胶凝胶中通过提拉法将Cr-ZnO/γ-Fe2O3包埋在光纤芯体表面，每次涂覆后或者每次提拉出光纤芯体后，在60℃下干燥，重复涂覆或提拉3-5次后，将包埋Cr-ZnO/γ-Fe2O3的光纤在室温下老化，即得到光催化剂。
3.如权利要求2所述的用于吸附和降解偶氮染料的光催化剂的制备方法，其特征在于，所述偶联剂为三氟丙基三甲氧基硅烷、丙基三甲氧基硅烷或3-氨基丙基三乙氧基硅烷中的一种。
4.如权利要求3所述的用于吸附和降解偶氮染料的光催化剂的制备方法，其特征在于，所述步骤S22具体为：取7.5ml偶联剂与3.5ml四乙氧基硅烷混合均匀，再依次加入7.5ml乙醇、3.2ml水和0.4ml的0.1mol/L盐酸，超声分散处理半小时，得到溶胶凝胶；在溶胶凝胶中加入步骤S1制备的Cr-ZnO/γ-Fe2O3，超声分散1h混合均匀；然后将混有Cr-ZnO/γ-Fe2O3的溶胶凝胶涂覆在光纤芯体表面，或者将光纤芯体浸入溶胶凝胶中通过提拉法将Cr-ZnO/γ-Fe2O3包埋在光纤芯体表面，每次涂覆后或者每次提拉出光纤芯体后，在60℃下干燥，重复涂覆或提拉5次后，将包埋Cr-ZnO/γ-Fe2O3的光纤在室温下老化一周，即得到光催化剂。
5.如权利要求2所述的用于吸附和降解偶氮染料的光催化剂的制备方法，其特征在于，所述步骤S1具体为：将2mmol的Zn(NO3)2·6H2O、0.12mmol的Cr(NO3)3·9H2O、0.12mmol的Fe(NO3)3·9H2O溶于40ml乙醇中，并在室温下搅拌20min，得到溶液A；将40ml浓度4mol/L的NaOH乙醇溶液在搅拌条件下加入到溶液A中，并在室温下搅拌1h，然后将反应液转移至特氟隆反应釜中，并在120℃条件下恒温反应12h，冷却至室温，离心分离出沉淀物，先后用去离子水和乙醇清洗沉淀物，在80℃下干燥12h，得到含有γ-Fe2O3的Cr掺杂ZnO，即Cr-ZnO/γ-Fe2O3。
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