CN106111212A - 一种纳米TiO2光催化剂及其制备方法 - Google Patents
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Abstract
本发明公开了一种纳米TiO2光催化剂及其制备方法。为以活性炭纤维毡为基底贝塔‑环糊精修饰Fe3+掺杂的纳米TiO2光催化剂；包括以下步骤：将活性炭纤维毡用浓度30wt％的H2O2浸泡，使其表面羟基化，烘干；将预处理后的活性炭纤维毡浸入体积浓度0.5％～2％的硅烷偶联剂甲苯溶液，洗涤、烘干；向TiCl4‑HCl溶液中加入β‑CD和无机铁盐水溶液，然后再加入自组装单分子层，在70～80℃恒温搅拌4h～6h后取出，洗涤、烘干得到所述光催化剂。以活性炭纤维毡为基底，负载纳米TiO2半导体，从Fe3+掺杂与β‑CD对TiO2表面改性的角度优化TiO2光催化性能，并诱发吸附—光催化协同效应，大大提高TiO2的光催化效率。
Description
技术领域
本发明属于光催化技术领域，具体涉及一种活性炭纤维毡为基底纳米TiO2光催化剂及其制备方法。
背景技术
光催化技术是一种半导体光催化剂表面受光激发后产生电子e-和空穴h+使污染物发生氧化还原反应最终被降解而光催化剂本身性质不变的一种深度处理技术。纳米TiO2作为光催化领域内最为活跃的半导体材料，具有价廉、无毒、良好的化学稳定性等优点，但也存在光量子效率低，光生电子-空穴容易复合，光谱响应范围窄，粉体TiO2易团聚，难回收等缺点限制其在实际中的应用。为了抑制光生电子-空穴的复合，可通过过渡金属(Cr，Co，Ni，Fe，Mn等)元素的掺杂使TiO2形成晶格缺陷，更好的捕获和传递电子，提高TiO2的光催化活性。在工程技术领域，近年来研究人员运用粉体烧结、浸涂、气相沉积、溶胶一凝胶、磁控溅射、等技术方法将纳米TiO2负载到生物碳质、矿物、有机高分子聚合物等比表面积大、孔洞结构多的吸附剂中，在吸附剂和TiO2的协同作用下，污染物被不断地吸附到TiO2的活性位点，降解速率也大大提高。然而这些方法存在着制备工艺复杂，成本过高，复合材料中纳米TiO2结合不牢固分布不均匀，机械强度不高，粉体材料依旧难于回收利用等缺陷。
发明内容
本发明目的在于提供一种纳米TiO2光催化剂及其制备方法剂用于降解污染物的应用中，特别是针对含有水相的污染物处理。
为达到上述目的，采用技术方案如下：
一种纳米TiO2光催化剂，以活性炭纤维毡为基底贝塔-环糊精(β-CD)修饰Fe3+掺杂的纳米TiO2光催化剂；活性炭纤维毡的表面和孔隙结构中生长着5-20nm不等的针状纳米TiO2颗粒，纳米TiO2颗粒沿垂直方向堆积并形成新的微孔结构。
上述纳米TiO2光催化剂的制备方法，包括以下步骤：
1)活性炭纤维毡的预处理：将活性炭纤维毡用浓度30wt％的H2O2浸泡，使其表面羟基化，烘干；
2)自组装单分子层(巯基)(Self-assembled monolayers,SAMs)(-SH)的制备：将预处理后的活性炭纤维毡浸入体积浓度0.5％～2％的硅烷偶联剂甲苯溶液，洗涤、烘干；
3)贝塔-环糊精修饰Fe3+掺杂纳米TiO2的自组装：向TiCl4-HCl溶液中加入β-CD(C42H70O35)和无机铁盐水溶液，然后再加入步骤2所得自组装单分子层，在70～80℃恒温搅拌4h～6h后取出，洗涤、烘干得到所述光催化剂。
按上述方案，所述的活性炭纤维毡比表面积1400～1500m2/g，碘吸附量1300～1400mg/g。
按上述方案，硅烷偶联剂甲苯溶液是甲苯中加入3-巯基丙基三甲氧基硅烷得到。
按上述方案，所述的无机铁盐为Fe(NO3)3·9H2O或FeCl3·6H2O。
按上述方案，所述TiCl4-HCl溶液为TiCl4中加入盐酸制得，浓度为0.05～0.2mol/L。
按上述方案，步骤3中Ti与Fe元素的摩尔比为20：1～120：1。
按上述方案，所述贝塔-环糊精的加入量与溶液中Ti的摩尔比为1：200～1：1000。
光催化性能的评价：
光催化剂放入多功能光化学反应仪中，光源为低功率(350W)氙灯(模拟可见光)降解40mL(5mg/L)罗丹明B溶液，180min时间后，取少量反应液于5mL离心管中，离心10min(转速为6000r/min)，取上清液在553nm处测其吸光度。降解率按式η＝(A0-A1)/A0×100％计算得到，其中η为降解率，A0为光照前溶液的吸光度；A1为光照180min后溶液的吸光度。
活性炭纤维作为第三代高效吸附材料，因具有含碳量高，比表面积大，微孔丰富且结构致密，吸附速度和容量大等优点被用于溶剂回收、空气净化等工艺过程，且活性炭纤维不像传统活性炭只具有颗粒状表态，还具有毡、布等存在形式，因此其作为催化剂载体，更有利于回收利用。
环糊精是6～8个吡喃葡萄糖单元通过1,4-糖苷键以椅式构象相连，表观形态为上窄下宽的环状空腔结构的化合物，空腔因“外亲水、内疏水”的特性，能吸附芳环烃化合物、酯类有机物、大分子氨基酸等疏水性分子和一些重金属离子。近年来，研究人员发现贝塔-环糊精能够维持TiO2胶体在水溶液的分散性和稳定性并促进TiO2界面的电子转移，协同TiO2光催化降解有机物反应进行。利用这一性质，用自组装的方法将β-CD修饰Fe3+掺杂的纳米TiO2负载于活性炭纤维毡表面，制备具有吸附—光催化协同效应的光催化剂是本发明的创新之处。
本发明所采用的分子自组装技术是在热力学平衡条件下，原子和分子依赖分子间的作用力，自发连接成结构稳定、复杂有序且具有某种特定功能的分子聚集体或超分子结构的过程。该技术方法简单，操作简便，制备的复合材料具有结构稳定，空间排布有序，易控制等优点，现已成为纳米材料常用的制造技术之一。
本发明具有以下优点：
以活性炭纤维毡为基底，负载纳米TiO2半导体，从Fe3+掺杂与β-CD对TiO2表面改性的角度优化TiO2光催化性能，并诱发吸附—光催化协同效应，大大提高TiO2的光催化效率。
特别适用于毒性大、低浓度难降解的化学染料、抗生素等有机废水的处理。
制备工艺简单易行、条件温和、原料廉价易得，且所光催化剂环境友好，易于回收利用、催化性能优异。
具体实施方式
为了更好地理解本发明，下面结合实施例进一步阐明本发明的内容，但本发明的内容不仅仅局限于下面的实施例。
实施例1
活性炭纤维毡的预处理：
取面积为1cm2，厚度为3mm的活性炭纤维毡，用质量浓度30％的H2O2进行表面预处理1h，使其表面羟基化，置于80℃烘箱干燥待用；
SAMs(-SH)单层的制备：
将预处理后的活性炭纤维毡浸入含有体积浓度1％的MPTMS甲苯溶液,20℃水浴搅拌器中搅拌4h。再先后用甲苯、乙醇、蒸馏水洗涤，放入110℃烘箱干燥。
β-CD修饰Fe3+掺杂纳米TiO2的自组装：
用蒸馏水配制pH＝3的稀盐酸100mL，向稀盐酸中加入1.1mL的TiCl4(低温，无水通风状态，边滴TiCl4边搅拌)，配置浓度为0.1mol/L TiCl4-HCl溶液，并取40mL于烧杯中。再向烧杯中加入0.1mmol的β-CD(C42H70O35)和浓度为5mmol/L FeCl3溶液6.85mL(此时烧杯里溶液中的Fe/Ti质量比为1％)。将镀上SAMs(-SH)的活性炭纤维毡放入烧杯中，在80℃水浴锅中恒温搅拌6h后取出，蒸馏水洗涤，110℃烘箱干燥得到所述光催化剂。
光催化性能的评价：
所得光催化剂放入多功能光化学反应仪中，光源为低功率(350W)氙灯(模拟可见光)降解40mL(5mg/L)罗丹明B溶液，180min时间后，取少量反应液于5mL离心管中，离心10min(转速为6000r/min)，取上清液在553nm处测其吸光度。降解率按式η＝(A0-A1)/A0×100％计算得到，其中η为降解率，A0为光照前溶液的吸光度；A1为光照180min后溶液的吸光度。40mL(5mg/L)罗丹明B溶液经降解后测吸光度变化并计算η为80.35％。
实施例2
活性炭纤维毡的预处理：
取面积为1cm2，厚度为3mm的活性炭纤维毡，用质量浓度30％的H2O2进行表面预处理1h，使其表面羟基化，置于80℃烘箱干燥待用；
SAMs(-SH)单层的制备：
将预处理后的活性炭纤维毡浸入含有体积浓度1％的MPTMS甲苯溶液，20℃水浴搅拌器中搅拌4h。再先后用甲苯、乙醇、蒸馏水洗涤，放入110℃烘箱干燥。
β-CD修饰Fe3+掺杂纳米TiO2的自组装：
用蒸馏水配制pH＝2的稀盐酸100mL，向稀盐酸中加入1.1mL的TiCl4(低温，无水通风状态，边滴TiCl4边搅拌)，配置浓度为0.1mol/L TiCl4-HCl溶液，并取35mL于烧杯中。再向烧杯中加入0.2mmol的β-CD(C42H70O35)和浓度为5mmol/L FeCl3溶液12mL(此时烧杯里溶液中的Fe/Ti质量比为2％)。将镀上SAMs(-SH)的活性炭纤维毡放入烧杯中，在80℃水浴锅中恒温搅拌4h后取出，蒸馏水洗涤，110℃烘箱干燥得到所述光催化剂。
光催化活性的评价：
采用与实施例1相同的光催化性能评价方法，40mL(5mg/L)罗丹明B溶液经降解后测吸光度变化并计算η为87.09％。
实施例3
活性炭纤维毡的预处理：
取面积为1cm2，厚度为3mm的活性炭纤维毡，用质量浓度30％的H2O2进行表面预处理1h，使其表面羟基化，置于80℃烘箱干燥待用；
SAMs(-SH)单层的制备：
将预处理后的活性炭纤维毡浸入含有体积浓度1％的MPTMS甲苯溶液,20℃水浴搅拌器中搅拌4h。再先后用甲苯、乙醇、蒸馏水洗涤，放入110℃烘箱干燥。
β-CD修饰Fe3+掺杂纳米TiO2的自组装：
用蒸馏水配制pH＝1的稀盐酸100mL，向稀盐酸中加入1.1mL的TiCl4(低温，无水通风状态，边滴TiCl4边搅拌)，配置浓度为0.1mol/L TiCl4-HCl溶液，并取25mL于烧杯中。再向烧杯中加入0.5mmol的β-CD(C42H70O35)和浓度为5mmol/L Fe(NO3)3溶液24.5mL(此时烧杯里溶液中的Fe/Ti质量比为5％)。将镀上SAMs(-SH)的活性炭纤维毡放入烧杯中，在70℃水浴锅中恒温搅拌5h后取出，蒸馏水洗涤，110℃烘箱干燥得到所述光催化剂。
光催化活性的评价：
采用与实施例一相同的光催化性能评价方法，40mL(5mg/L)罗丹明B溶液经降解后测吸光度变化并计算η为81.96％。
实施例4
活性炭纤维毡的预处理：
取面积为1cm2，厚度为3mm的活性炭纤维毡，用质量浓度30％的H2O2进行表面预处理1h，使其表面羟基化，置于80℃烘箱干燥待用；
SAMs(-SH)单层的制备：
将预处理后的活性炭纤维毡浸入含有体积浓度1％的MPTMS甲苯溶液，20℃水浴搅拌器中搅拌4h。再先后用甲苯、乙醇、蒸馏水洗涤，放入110℃烘箱干燥。
β-CD修饰Fe3+掺杂纳米TiO2的自组装：
用蒸馏水配制pH＝2的稀盐酸100mL，向稀盐酸中加入1.1mL的TiCl4(低温，无水通风状态，边滴TiCl4边搅拌)，配置浓度为0.1mol/L TiCl4-HCl溶液，并取35mL于烧杯中。再向烧杯中加入0.3mmol的β-CD(C42H70O35)和浓度为5mmol/L Fe(NO3)3溶液12mL(此时烧杯里溶液中的Fe/Ti质量比为2％)。将镀上SAMs(-SH)的活性炭纤维毡放入烧杯中，在70℃水浴锅中恒温搅拌5h后取出，蒸馏水洗涤，110℃烘箱干燥得到所述光催化剂。
光催化活性的评价：
采用与实施例一相同的光催化性能评价方法，40mL(5mg/L)罗丹明B溶液经降解后测吸光度变化并计算η为82.65％。
需要强调指出的是，上述实施例仅仅是为了清楚地说明本发明所作的举例，而并非对实施方式的完全限定。所属领域的普通技术人员在上述实施例的基础上还可以做出其它不同形式的变动，这里无法也无需对所有实施方式给出实施例，但由此而引申出的显而易见的变动仍处于本发明的保护范围。
Claims (8)
1.一种纳米TiO2光催化剂，其特征在于以活性炭纤维毡为基底贝塔-环糊精修饰Fe3+掺杂的纳米TiO2光催化剂；活性炭纤维毡的表面和孔隙结构中生长着5-20nm不等的针状纳米TiO2颗粒，纳米TiO2颗粒沿垂直方向堆积并形成新的微孔结构。
2.权利要求1所述纳米TiO2光催化剂的制备方法，其特征在于包括以下步骤：
1)活性炭纤维毡的预处理：将活性炭纤维毡用浓度30wt％的H2O2浸泡，使其表面羟基化，烘干；
2)自组装单分子层(巯基的制备：将预处理后的活性炭纤维毡浸入体积浓度0.5％～2％的硅烷偶联剂甲苯溶液，洗涤、烘干；
3)贝塔-环糊精修饰Fe3+掺杂纳米TiO2的自组装：向TiCl4-HCl溶液中加入贝塔-环糊精和无机铁盐水溶液，然后再加入步骤2所得自组装单分子层，在70～80℃恒温搅拌4h～6h后取出，洗涤、烘干得到所述光催化剂。
3.如权利要求2所述纳米TiO2光催化剂的制备方法，其特征在于所述的活性炭纤维毡比表面积1400～1500m2/g，碘吸附量1300～1400mg/g。
4.如权利要求2所述纳米TiO2光催化剂的制备方法，其特征在于硅烷偶联剂甲苯溶液是甲苯中加入3-巯基丙基三甲氧基硅烷得到。
5.如权利要求2所述纳米TiO2光催化剂的制备方法，其特征在于所述的无机铁盐为Fe(NO3)3·9H2O或FeCl3·6H2O。
6.如权利要求2所述纳米TiO2光催化剂的制备方法，其特征在于所述TiCl4-HCl溶液为TiCl4中加入盐酸制得，浓度为0.05～0.2mol/L。
7.如权利要求2所述纳米TiO2光催化剂的制备方法，其特征在于步骤3中Ti与Fe元素的摩尔比为20：1～120：1。
8.如权利要求2所述纳米TiO2光催化剂的制备方法，其特征在于所述贝塔-环糊精的加入量与溶液中Ti的摩尔比为1：200～1：1000。
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