CN105688918A - 一种粘土-钙钛矿复合材料的制备方法及其应用 - Google Patents
一种粘土-钙钛矿复合材料的制备方法及其应用 Download PDFInfo
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 27
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 24
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- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims abstract description 12
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 10
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- 229910052793 cadmium Inorganic materials 0.000 claims description 33
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 8
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- 150000001875 compounds Chemical class 0.000 abstract description 2
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- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 abstract 3
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- CYDMQBQPVICBEU-UHFFFAOYSA-N chlorotetracycline Natural products C1=CC(Cl)=C2C(O)(C)C3CC4C(N(C)C)C(O)=C(C(N)=O)C(=O)C4(O)C(O)=C3C(=O)C2=C1O CYDMQBQPVICBEU-UHFFFAOYSA-N 0.000 description 11
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- CYDMQBQPVICBEU-XRNKAMNCSA-N chlortetracycline Chemical compound C1=CC(Cl)=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O CYDMQBQPVICBEU-XRNKAMNCSA-N 0.000 description 11
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- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明属于能源化工领域，具体涉及到一种以粘土为载体、钙钛矿型化合物纳米颗粒为活性组分的纳米材料的制备方法及其光催化降解抗生素的应用。将硝酸镧、硝酸铁、硝酸铈、柠檬酸、粘土加入到去离子水中搅拌，然后转移到水浴锅中蒸发得到湿凝胶，干燥，煅烧，烘干研磨即得铁酸镧/粘土纳米结构复合材料。采用该复合材料光催化降解抗生素，利用(铈掺杂的)铁酸镧的高光催化活性，使抗生素在可见光下能够快速的分解；粘土载体在降解抗生素过程中，有利于抗生素分子的吸附，抗生素吸附到催化剂表面后与铁酸镧接触，在可见光的照射下抗生素分子分解产生其他活性物种。
Description
技术领域
本发明属于能源化工领域，具体涉及到一种以粘土为载体、钙钛矿型化合物纳米颗粒为活性组分的纳米材料的制备方法及其光催化降解抗生素的应用。
背景技术
近年来，环境污染问题日益严重，能源紧缺问题也迫在眉睫。在面临上述两大危机的势态之下，人们展开了污染治理、保护环境的科学研究。以半导体为催化剂，利用太阳光催化氧化降解污染物质作为一种有效的治理污染方法，成为环境保护科学研究的一个热点。
四环素是一种广泛使用的抗生素，并已成为世界上使用量第二大的抗生素。四环素被大量的使用，特别是在发展中国家的过度使用和滥用会导致很多潜在的环境问题，四环素可以随着排泄的粪便和尿液进行代谢。因此，四环素广泛存在于水环境中，可以积累在生物群，生产多抗性环境中的细菌菌株。将四环素从废水和地表水中除去将是很严峻的挑战。
发明内容
为解决上述技术问题，本发明提供了一种铈掺杂的铁酸镧/粘土纳米结构复合材料及其制备方法和用途，遴选合适的原料及配比使其能通过光催化降解抗生素，
本发明采用的具体技术方案为：
提供一种(铈掺杂的)铁酸镧/粘土复合材料，是以粘土为载体，在粘土上负载(铈掺杂的)铁酸镧后得到的复合材料，
本发明复合材料的组成通式表示为：μ％La1-xCexFeO3/Clay；式中，μ＝10-20，x取值为0、0.05、0.1、0.15或0.2；Clay为粘土载体，可以是凹凸棒石、埃洛石或海泡石，
(铈掺杂的)铁酸镧(La1-xCexFeO3)是一种典型的具有钙钛矿(ABO3)结构的稀土复合金属氧化物，具有稳定的晶体结构,这有利于其应用于光催化降解；La1-xCexFeO3由于是颗粒状且粒径很小(小于10nm)，容易聚集，需要使用载体使钙钛矿粒子能够均匀的负载，以便能够提高活性组分的光催化性能。
本发明还提供了一种上述(铈掺杂的)铁酸镧/粘土复合材料的制备工艺，将硝酸镧、硝酸铁、(硝酸铈、)柠檬酸、粘土加入到去离子水中搅拌，然后转移到水浴锅中蒸发得到湿凝胶，干燥，煅烧，烘干研磨即得(铈掺杂的)铁酸镧/粘土纳米结构复合材料，
本发明采用一步溶胶凝胶法制备得到(铈掺杂的)铁酸镧/粘土纳米结构复合材料，反应过程简单，原料便宜易得，粘土具有较大的比表面积，可以使(铈掺杂的)铁酸镧较为均匀地负载在上面，能够提高该复合材料的催化性能，
其中，硝酸镧、(硝酸铈、)硝酸铁与粘土的加入量，按照(铈掺杂的)铁酸镧相对于粘土的质量比为1:5～1:8来计算，
上述的水浴温度为70～90℃，水浴时间为16～24h，煅烧温度为550℃～600℃。
本发明还提供了一种上述(铈掺杂的)铁酸镧/粘土复合材料的应用，即采用该复合材料光催化降解抗生素，利用(铈掺杂的)铁酸镧的高光催化活性，使抗生素在可见光下能够快速的分解。
本发明的有益效果在于：
1、本发明采用一步sol-gel法制备得到铈掺杂的铁酸镧/粘土复合材料，钙钛矿粒径小于10nm，负载均匀，分散均匀，在降低了成本的同时，发挥了两者协同催化的作用；
2、本发明中络合剂能将液相中所有的金属阳离子聚合反应，粘土载体本身所含的镁离子、铝离子也能参与其中，这是通过调节pH，使金属阳离子共沉淀所不能实现的；镁、铝离子对稀土钙钛矿的掺杂，增加了活性组分的晶格缺陷，有利于催化活性的提高；
3、本发明中粘土载体在降解金霉素过程中，有利于金霉素分子的吸附，金霉素吸附到催化剂表面后与铁酸镧接触，在可见光的照射下金霉素分子分解产生其他活性物种。
附图说明
图1为实施例1制备的La0.8Ce0.2FeO3/Halloysites、LaFeO3/Halloysites(在实施例1工艺的基础上通过调整投料比得到)、LaFeO3、Halloysites样品的XRD谱图；
图2为LaFeO3/Halloysites(在实施例1工艺的基础上通过调整投料比得到)样品50nm标尺范围的TEM照片；
图3为实施例1制备的La0.8Ce0.2FeO3/Halloysites样品20nm标尺范围的TEM照片；
图4为实施例1制备的La0.8Ce0.2FeO3/Halloysites、LaFeO3/Halloysites(在实施例1工艺的基础上通过调整投料比得到)、LaFeO3、Halloysites样品对金霉素的降解曲线。
具体实施方式
实施例1
首先称取0.214g的硝酸镧，0.07146g的硝酸铈，0.33g的硝酸铁溶于100ml的去离子水，再加入0.336g的络合剂柠檬酸，最后加入1g的埃洛石，搅拌2h得到混合溶液,然后放置于水浴锅中70℃水浴18h，水蒸发得到湿凝胶，放于干燥箱中80℃烘干，等湿凝胶成为干凝胶时,放置于马弗炉中以550℃，1℃/min煅烧，最后研磨得到负载量为20wt％的铈掺杂的铁酸镧/埃洛石纳米结构复合材料。
对所得的上述样品进行X射线粉末衍射实验，并在透射电镜下观察其形貌和结构，按照实施例1的工艺参数制得的铈掺杂的铁酸镧/埃洛石纳米结构复合材料与铁酸镧、埃洛石、铁酸镧/埃洛石纳米结构复合材料的XRD图谱如图1所示：复合材料的XRD中出现了铁酸镧和埃洛石各自的特征衍射峰，说明铁酸镧成功负载到埃洛石上；在2θ＝27°左右出现了二氧化铈的特征峰，说明有CeO2析出，Ce取代部分铁酸镧中的La；XRD图中La0.8Ce0.2FeO3/Halloysites、LaFeO3/Halloysites比纯的LaFeO3谱线上峰位有轻微的往右偏移，这说明粘土载体本身所含的镁离子、铝离子也参与了对稀土钙钛矿的掺杂，增加了活性组分的晶格缺陷。
实施例1制得的铈掺杂的铁酸镧/埃洛石纳米结构复合材料的TEM照片如图3所示。从图中可以看出，铁酸镧颗粒小于10nm且与埃洛石较为均匀复合在一起，与XRD的结果一致。
然后取0.1g上述制备的铈掺杂的铁酸镧/埃洛石纳米结构复合材料放入光化学反应仪中，加入100ml其中含有0.01g金霉素样的待测液，暗反应30min，然后开氙灯反应1h，分别在10min，20min，30min，40min，50min，60min中取3ml反应液，离心得到降解金霉素后的液体，运用液相色谱检测浓度从而得到降解率。
利用高效液相色谱测得实施例1制得的La0.8Ce0.2FeO3/HNTs、LaFeO3/HNTs、LaFeO3、HNTs样品对金霉素的降解率曲线如图4所示，从图中可以看出，LaFeO3对金霉素的去除率约为70％，LaFeO3/HNTs样品对金霉素的去除率达90％以上，La0.8Ce0.2FeO3/HNTs样品对金霉素的去除率达97％以上。
实施例2
首先称取0.211g的硝酸镧和0.234g，0.11g的硝酸铈和硝酸铁溶于100ml的去离子水，再加入0.168g的络合剂柠檬酸，最后加入1g的埃洛石，搅拌2h得到混合溶液，然后放置于水浴锅中70℃水浴18h，水蒸发得到湿凝胶，放于干燥箱中80℃烘干，等湿凝胶成为干凝胶时，放置于马弗炉中以550℃，1℃/min煅烧，最后研磨得到负载量为20wt％的铈掺杂的铁酸镧/埃洛石纳米结构复合材料，后续检测如实施例1。
实施例3
首先称取0.166g的硝酸镧和0.211g，0.21g的硝酸铈，硝酸铁溶于100ml的去离子水，再加入0.168g的络合剂柠檬酸，最后加入1g的埃洛石，搅拌2h得到混合溶液，然后放置于水浴锅中70℃水浴18h，水蒸发得到湿凝胶，放于干燥箱中80℃烘干，等湿凝胶成为干凝胶时，放置于马弗炉中以550℃，1℃/min煅烧，最后研磨得到负载量为20wt％的铈掺杂的铁酸镧/埃洛石纳米结构复合材料，后续检测如实施例1。
实施例4
首先称取0.182g的硝酸镧，0.18g的硝酸铈，0.289g的硝酸铁溶于100ml的去离子水，再加入0.168g的络合剂柠檬酸，最后加入1g的埃洛石，搅拌2h得到混合溶液，然后放置于水浴锅中70℃水浴18h，水蒸发得到湿凝胶，放于干燥箱中80℃烘干，等湿凝胶成为干凝胶时,放置于马弗炉中以550℃，1℃/min煅烧，最后研磨得到负载量为20wt％的铈掺杂的铁酸镧/埃洛石纳米结构复合材料，后续检测如实施例1。
实施例5
首先称取0.222g的硝酸镧，0.24g的硝酸铈，0.345g的硝酸铁溶于100ml的去离子水，再加入0.168g的络合剂柠檬酸，最后加入1g的埃洛石，搅拌2h得到混合溶液，然后放置于水浴锅中70℃水浴18h，水蒸发得到湿凝胶，放于干燥箱中80℃烘干，等湿凝胶成为干凝胶时,放置于马弗炉中以550℃，1℃/min煅烧，最后研磨得到负载量为20wt％的铈掺杂的铁酸镧/埃洛石纳米结构复合材料，后续检测如实施例1。
Claims (10)
1.一种粘土-钙钛矿复合材料，其特征在于：所述的复合材料以粘土为载体，所述粘土上负载有铁酸镧。
2.一种粘土-钙钛矿复合材料，其特征在于：所述的复合材料以粘土为载体，所述粘土上负载有铈掺杂的铁酸镧。
3.如权利要求1所述的粘土-钙钛矿复合材料的制备方法，其特征在于：所述的制备方法为，将硝酸镧、硝酸铁、柠檬酸、粘土加入到去离子水中搅拌，然后转移到水浴锅中蒸发得到湿凝胶，干燥，煅烧，烘干研磨即得铁酸镧/粘土纳米结构复合材料。
4.如权利要求2所述的粘土-钙钛矿复合材料的制备方法，其特征在于：所述的制备方法为，将硝酸镧、硝酸铁、硝酸铈、柠檬酸、粘土加入到去离子水中搅拌，然后转移到水浴锅中蒸发得到湿凝胶，干燥，煅烧，烘干研磨即得铁酸镧/粘土纳米结构复合材料。
5.如权利要求3或4所述的粘土-钙钛矿复合材料的制备方法，其特征在于：所述的粘土是凹凸棒石、埃洛石或海泡石。
6.如权利要求3所述的粘土-钙钛矿复合材料的制备方法，其特征在于：硝酸镧、硝酸铁与粘土的加入量，按照铁酸镧相对于粘土的质量比为1:5～1:8来计算。
7.如权利要求4所述的粘土-钙钛矿复合材料的制备方法，其特征在于：硝酸镧、硝酸铈、硝酸铁与粘土的加入量，按照铈掺杂的铁酸镧相对于粘土的质量比为1:5～1:8来计算。
8.如权利要求3或4所述的粘土-钙钛矿复合材料的制备方法，其特征在于：水浴温度为70～90℃，水浴时间为16～24h。
9.如权利要求3或4所述的粘土-钙钛矿复合材料的制备方法，其特征在于：所述的煅烧温度为550℃～600℃。
10.如权利要求1或2所述的粘土-钙钛矿复合材料的应用，其特征在于：所述的应用为，采用粘土-钙钛矿复合材料光催化降解抗生素。
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