CN111977696B - 石榴状磁性可见光非均相Fenton催化剂材料制备方法及应用 - Google Patents
石榴状磁性可见光非均相Fenton催化剂材料制备方法及应用 Download PDFInfo
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Abstract
本专利涉及到一种磁性可见光非均相Fenton催化剂ZnFe2O4材料的制备方法和应用，所得到的ZnFe2O4光催化剂材料具有石榴状结构，该纳米球是由许多超小的ZnFe2O4单元组装而成，二级单元粒径小于5 nm，具有较大的比表面积和吸附能力等特点，有利于电子的顺利传输。本发明的制备方法简单，成本低廉，所制备的ZnFe2O4光催化剂材料，在具备优异的Fenton光催化能力的前提下，还能够通过磁性分离，反复回收和重复使用的特点。Fenton光催化测试结果表明，在可见光照射下，ZnFe2O4光催化剂具有优异的降解性能，可用于土霉素(OTC),诺氟沙星(NFX),盐酸四环素(TCH),罗丹明B(RhB),甲基橙（MO）降解和还原Cr(Ⅵ)。
Description
技术领域
本发明属于水处理技术领域，具体涉及到一种石榴状可见光Fenton催化剂ZnFe2O4纳米球的制备方法及对有机废水深度降解。
背景技术
水，是大自然一种宝贵的资源，同样也是人类赖以生存的源泉。而如今，随着现代化工业的高速发展，工业废水的排放越来越多，其中有很大一部分废水含有有机污染物，这些有机污染物难以被自然降解，导致水污染问题日趋加重。工业发展的同时，其用水需求越来越大，水质问题使得我国水资源短缺和经济发展的矛盾日益突出，因此，废水处理成为当今社会面临的一大难题。
自 1964年，H. R. Eisehnonser首次使用Fenton试剂处理苯酚及烷基苯废水，均相Fenton氧化技术作为一种高级氧化技术被广泛应用于工业废水的降解。王滨松等研究了均相 Fenton 氧化技术处理三种乙烯砜型商业活性染料，发现：20℃，pH为 2-5，nFe 2+为0.5mmol/L，双氧水浓度 167-333 mg/L，降解 400 mg/L 的染料，20 min 三种活性染料色度的去除率都可达 99%以上。大量研究表明：均相 Fenton 体系作为高级氧化技术能处理难降解的废水，是由于Fe2+催化双氧水产生的羟基自由基（·OH）具有强氧化能力，能与绝大多数有机物反应，使其变成小分子的CO2和H2O。但是该体系应用于废水的降解还存在着一些问题：均相Fenton体系中适宜的pH范围较窄（pH为3-5）；在碱性条件下铁离子容易沉淀形成铁泥，造成催化剂的流失；体系中羟基自由基的利用率不高，降解实际消耗的羟基自由基比理论需要的多。由于均相Fenton反应条件的限制以及原料较昂贵，使得均相Fenton体系降解效率不高，处理成本偏大。因此，开发一种高效、成本低廉、绿色、环保的深度处理技术具有十分重要的意义。
光催化技术能够在太阳光的照射下发生电子跃迁，产生具有强氧化能力的电子-空穴对将废水中的有机污染物氧化分解为二氧化碳、水和无机小分子。为了提高催化剂的催化活性，复合催化技术受到广泛关注。其中非均相Fenton复合光催化剂是利用Fenton技术与光催化技术结合，不仅可以有效的提高催化剂的催化活性从而提升废水处理效率，而且技术操作简单，环境友好，因此，如果构建高效的污水处理体系成为人们追逐的研究重点。非均相Fenton技术结合了光催化和芬顿氧化的优点，即能够做到节能，方便回收利用，又能保证较好的废水降解效果，在实际应用中有很大潜力。
发明内容
本发明的目的在于，针对现有技术的上述不足，提出一种制备方法简单，成本低廉、降解率高的石榴状可见光Fenton催化剂ZnFe2O4纳米球及处理有机废水的方法。
为解决上述技术问题，本发明采用如下技术方案：
本发明的石榴状可见光Fenton催化剂ZnFe2O4纳米球制备方法，包括以下步骤：
采用一步法合成了石榴状可见光Fenton催化剂ZnFe2O4纳米球。 100 ~ 200 mg聚丙烯酸、500 ~ 1500 μL氨水和200-300 mg硝酸锌依次加入到容器中，搅拌混合均匀后，将300 ~ 500 mL异丙醇滴加至溶液中，滴加完毕后再向溶液中加入200 ~ 400 mg四水合氯化亚铁，室温下搅拌反应10 ~12 h；得到的混合溶液进行离心分离，沉淀在烘箱中烘干12 ~20 h；置于马弗炉中，在空气中500 ~ 600 ℃煅烧12 ~ 20 h，得到石榴状可见光Fenton催化剂ZnFe2O4纳米球。最终得到石榴状可见光Fenton催化剂ZnFe2O4纳米球。所得到的石榴状可见光Fenton催化剂ZnFe2O4纳米球，ZnFe2O4纳米球的平均尺寸为 210-230nm, 是由许多超小的ZnFe2O4单元组装而成，二级单元粒径小于5 nm。所得到的石榴状可见光Fenton催化剂ZnFe2O4纳米球可应用于降解有机废水方面。能在短短5-60分钟内，分别对土霉素(OTC)，诺氟沙星 (NFX)，盐酸四环素 (TCH)， 罗丹明 B (RhB)， 甲基橙（MO）和还原Cr(Ⅵ)，降解率高达95-98%。
与现有技术相比，本发明的优势在于：
（1）本发明提供一种操作简单，成本低廉、降解率高，稳定性好且绿色经济的磁性多组分光芬顿催化剂，适用工业化生产。
（2）本发明能够通过磁性分离，易于回收，可重复性使用。
（3）本发明适用于较宽的pH范围；使用复合催化体系的联用技术，发现多种催化体系之间可以产生协同效应，能显著地提高可见光利用率，最终增强污染物的去除效果。
（4）本发明为非均相Fenton复合光催化剂提供了深刻见解。
附图说明：
图一是实施案例1所得到的XRD图
图二是实施案例1所得到的扫描和透射照片图
图三是实施案例1所得到的样品的降解性能图
图四是实施案例1所得到的样品的循环性能图
具体实施方式：
下面结合实施例对本发明作更进一步的说明。
实施例1
200 mg 的聚丙烯酸，加入1 mL 去离子水中超声溶解，搅拌中滴入100 ml去离子水中超声，再滴入700 μL 氨水超声30 min，称取223 mg 硝酸锌加入上述溶液，再向溶液中缓慢滴加 400 ml 异丙醇。称 取 300 mg 的四水合氯化亚铁加入上述溶液搅拌12 h，将所得混合溶液进行离心分离(5000rpm, 8min)，将沉淀用去离子水和乙醇洗涤数次，在 65 °C烘箱中干燥 15 h，取出置于马弗炉中，空气氛围500°C煅烧12h，最终得到ZnFe2O4光催化材料。
实施例2
100 mg 的聚丙烯酸，加入1 mL 去离子水中超声溶解，搅拌中滴入100 ml去离子水中超声，再滴入500 μL 氨水超声30 min，称取200 mg 硝酸锌加入上述溶液，再向溶液中缓慢滴加 300 ml 异丙醇。称 取 200 mg 的四水合氯化亚铁加入上述溶液搅拌10 h，将所得混合溶液进行离心分离(4000rpm, 8min)，将沉淀用去离子水和乙醇洗涤数次，在 65 °C烘箱中干燥 12 h，取出置于马弗炉中，空气氛围500°C煅烧18h，最终得到ZnFe2O4光催化材料。
实施例3
150 mg 的聚丙烯酸，加入1 mL 去离子水中超声溶解，搅拌中滴入100 ml去离子水中超声，再滴入1000 μL 氨水超声30 min，称取250 mg 硝酸锌加入上述溶液，再向溶液中缓慢滴加 400 ml 异丙醇。称 取 250 mg 的四水合氯化亚铁加入上述溶液搅拌12 h，将所得混合溶液进行离心分离(4500rpm, 8min)，将沉淀用去离子水和乙醇洗涤数次，在 65°C烘箱中干燥 16 h，取出置于马弗炉中，空气氛围550°C煅烧15 h，最终得到ZnFe2O4光催化材料。
实施例4
200 mg 的聚丙烯酸，加入1 mL 去离子水中超声溶解，搅拌中滴入100 ml去离子水中超声，再滴入1500 μL 氨水超声30 min，称取300 mg 硝酸锌加入上述溶液，再向溶液中缓慢滴加 500 ml 异丙醇。称 取 400 mg 的四水合氯化亚铁加入上述溶液搅拌12 h，将所得混合溶液进行离心分离(5000rpm, 8min)，将沉淀用去离子水和乙醇洗涤数次，在 65°C烘箱中干燥 20 h，取出置于马弗炉中，空气氛围600°C煅烧20 h，最终得到ZnFe2O4光催化材料。
Claims (9)
1.一种石榴状可见光Fenton催化剂ZnFe2O4纳米球的制备方法，其特征在于：100 ~200mg聚丙烯酸、500 ~ 1500μL氨水和200-300 mg硝酸锌依次加入到容器中，搅拌混合均匀后，将300 ~ 500 mL异丙醇滴加至溶液中，滴加完毕后再向溶液中加入200 ~ 400 mg四水合氯化亚铁，室温下搅拌反应10 ~12 h；得到的混合溶液进行离心分离，沉淀在烘箱中烘干12 ~20 h；置于马弗炉中，在空气中500 ~ 600℃煅烧12 ~ 20 h，得到石榴状可见光Fenton催化剂ZnFe2O4纳米球。
2.根据权利要求1所述的制备方法，其特征在于：所述烘箱的烘干温度为65℃。
3.根据权利要求1所述的制备方法，其特征在于：所述得到的混合溶液进行离心分离，离心时间为8 min。
4.根据权利要求1所述的制备方法，其特征在于：煅烧过程5℃/min的升温速度程序升温至500 ~ 600℃。
5.如权利要求1-4中任意一项所述的制备方法制备得到的一种石榴状可见光Fenton催化剂ZnFe2O4纳米球。
6.根据权利要求5所述的一种石榴状可见光Fenton催化剂ZnFe2O4纳米球，其特征在于：该石榴状可见光Fenton催化剂ZnFe2O4纳米球，尺寸为210-230nm，是由多个ZnFe2O4单元组装而成，二级单元粒径小于5 nm。
7.如权利要求5或6所述的一种石榴状可见光Fenton催化剂ZnFe2O4纳米球在降解有机废水方面的应用。
8.根据权利要求7所述的应用，其特征在于：可见光条件下，具有优异的降解性能，降解土霉素OTC、诺氟沙星NFX、盐酸四环素TCH、罗丹明 B RhB、甲基橙MO，降解和还原Cr（ Ⅵ） 。
9.根据权利要求8所述的应用，其特征在于：所述土霉素OTC、诺氟沙星NFX、盐酸四环素TCH、罗丹明B RhB、甲基橙MO、Cr（ Ⅵ） 浓度范围均为30-150 ppm。
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