CN113617366A - 一种用于降解废水有机污染物的材料 - Google Patents
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Abstract
本发明公开了一种用于降解废水有机污染物的材料,采用如下方法制备:称取硝酸镍和高锰酸钾溶于乙二醇‑水的混合液中,随后加入柠檬酸铵,将混合液转移到高压水热釜中,随后将移至微波超声水热合成仪中反应,干燥得到海胆状NiMnO3;将海胆状的NiMnO3溶于去离子水中,随后加入Co盐和镍盐、硫代乙酰胺,将混合溶液采用400~800W微波加热至100~220℃,保持恒温进行微波水热合成反应2~10h;得到的产物于空气气氛下进行热处理,得到产物NiMnO3/NiCo2S4,复合材料比表面积高,物理吸附性能强,能够有效抑制电子与空穴的复合,提高光催化剂降解污染物的效率。
Description
技术领域
发明属于污水处理领域,具体涉及一种自然光降解污水中有机污染物催化剂及其制备方法。
背景技术
近年来,抗生素被广泛的应用于用于农业和以及水产养殖等领域,从而导致湖泊、河流和海洋中的抗生素不断积累富集,对自然水环境造成了严重的污染,水中污染物进入人体,直接严重危害人体健康。目前,利用光催化材料对污水中的有机污染物进行光催化降解,被认为最具潜力和研究价值的污染治理途径之一。
二氧化钛因其氧化能力强,化学性质稳定无毒,成为世界上最重要的光催化材料之一,然而,TiO2由于其固有的宽带隙,其只能吸收紫外光,受光激发产生的电子和空穴极易复合,量子效率低。因此,开发一种新型光催化剂具有重要的现实意义。
发明内容
针对现有技术存在的技术问题,本发明提出一种复合光催化剂及其制备方法,制备得到的复合光催化剂能够高效地降解抗生素。
一种用于降解有机污染物的光催化材料,其特征在于,采用如下方法制备:
(1)称取硝酸镍和高锰酸钾溶于乙二醇-水的混合液中,乙二醇和水的体积比为1:(0.5-1),随后加入柠檬酸铵,将混合液转移到高压水热釜中,随后将移至微波超声水热合成仪中反应,干燥得到海胆状NiMnO3;超声水热反应的温度为150-180℃,超声频率为60~70KHz,反应时间为5~7h;
(2)将海胆状的NiMnO3溶于去离子水中,随后加入Co盐和镍盐、硫代乙酰胺,将混合溶液采用400~800W微波加热至100~220,保持恒温进行微波水热合成反应2~10h;
(3)将步骤(2)得到的产物于空气气氛下进行热处理,其中热处理温度为300-400℃,反应时间为1-2h,得到产物NiMnO3/NiCo2S4。
优选的,硝酸镍和高锰酸钾的摩尔比为1:1;
优选的,超声水热反应的温度为160-180℃,超声频率为65~70KHz,反应时间为6h;
技术效果:1.本发明制以超声水热法并通过调整溶剂比例,在水热过程中加入柠檬酸铵,精细调控材料结构制备得到海胆状的NiMnO3,比表面积高,对有机物吸附性能强,在可见光照射下,具有优异的光催化性能,采用微波加热控制NiCo2S4为纳米级,海胆状的NiMnO3作为负载体,有利于后期备的纳米的NiCo2S4在海胆状NiMnO3纳米针空隙的均匀分散,NiCo2S4与NiMnO3二者之间形成异质结,NiCo2S4带隙窄且有快速的电子传递速率,从而能够有效抑制电子与空穴的复合,提高光催化剂降解污染物的效率。
附图说明
图1为本申请NiMnO3的SEM图;
具体实施方式
实施例1
(1)称取5mmol硝酸镍和5mmol高锰酸钾溶于80ml乙二醇-水的混合液中,乙二醇和水的体积比为1:0.6,随后加入20mg的柠檬酸铵,将混合液转移到高压水热釜中,随后将其移至微波超声水热合成仪中反应,干燥得到海胆状NiMnO3;超声水热反应的温度为180℃,超声频率为60KHz,反应时间为5h;
(2)将海胆状的NiMnO3溶于去离子水中,随后加入4mmol硝酸钴和2mmol的硝酸镍、8mmol的硫代乙酰胺,将混合溶液采用500W微波加热至200℃,保持恒温进行微波水热合成反应10h;
(3)将步骤(2)得到的产物于空气气氛下进行热处理,其中热处理温度为350℃,反应时间为1h,得到产物NiMnO3/NiCo2S4。
对比例1
(1)称取5mmol硝酸镍和5mmol高锰酸钾溶于80ml乙二醇-水的混合液中,乙二醇和水的体积比为1:0.6,随后加入20mg的柠檬酸铵,将混合液转移到高压水热釜中,随后将其移至微波超声水热合成仪中反应,干燥得到海胆状NiMnO3;超声水热反应的温度为180℃,超声频率为60KHz,反应时间为5h;
(2)将步骤(1)得到的产物于空气气氛下进行热处理,其中热处理温度为350℃,反应时间为1h,得到产物NiMnO3。
对比例2
在去离子水中4mmol硝酸钴和2mmol的硝酸镍、8mmol的硫代乙酰胺,将混合溶液采用500W微波加热至200℃,保持恒温进行微波水热合成反应10h;得到的产物于空气气氛下进行热处理,其中热处理温度为350℃,反应时间为1h,得到产物NiCo2S4。
光催化性能测试:
称取50mg实施例1以及对比例1-2的光催化剂加入到100mL浓度为5mg/L的四环素抗生素溶液/左氧氟沙星溶液中,以300W氙灯照射进行光催化反应,60min后测试抗生素的降解率。
表1
四环素抗生素的降解率 | 左氧氟沙星的降解率 | |
实施例1 | 98.6% | 96.3% |
对比例1 | 84.3% | 82.9% |
对比例1 | 79.1% | 81.2% |
尽管已经示出和描述了本发明的实施例,对于本领域的普通技术人员而言,可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型,本发明的范围由所附权利要求等同物限定。
Claims (3)
1.一种用于降解废水有机污染物的材料,其特征在于,采用如下方法制备:
(1)称取硝酸镍和高锰酸钾溶于乙二醇-水的混合液中,乙二醇和水的体积比为1:(0.5-1),随后加入柠檬酸铵,将混合液转移到高压水热釜中,随后将移至微波超声水热合成仪中反应,干燥得到海胆状NiMnO3;超声水热反应的温度为150-180℃,超声频率为60~70KHz,反应时间为5~7h;
(2)将海胆状的NiMnO3作为负载载体溶于去离子水中,随后加入Co盐和镍盐、硫代乙酰胺,将混合溶液采用400~800W微波加热至100~220℃,保持恒温进行微波水热合成反应2~10h;
(3)将步骤(2)得到的产物于空气气氛下进行热处理,得到产物NiMnO3/NiCo2S4,纳米级的NiCo2S4负载于NiMnO3的孔隙中。
2.根据权利要求1所述的一种用于降解废水有机污染物的材料,硝酸镍和高锰酸钾的摩尔比为1:1。
3.根据权利要求1所述的一种用于降解废水有机污染物的材料,其中热处理温度为300-400℃,反应时间为1-2h。
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN114133773A (zh) * | 2022-01-10 | 2022-03-04 | 费县三鼎工程科技中心 | 一种空气净化涂料 |
CN114452974A (zh) * | 2022-02-21 | 2022-05-10 | 中南大学 | MnO2基除醛材料及其超声-微波辅助制备方法和在甲醛催化氧化中的应用 |
CN115282985A (zh) * | 2021-12-17 | 2022-11-04 | 伊犁师范大学 | 一种NiFe2S4/兰炭复合材料及其制备方法与应用 |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN115282985A (zh) * | 2021-12-17 | 2022-11-04 | 伊犁师范大学 | 一种NiFe2S4/兰炭复合材料及其制备方法与应用 |
CN114133773A (zh) * | 2022-01-10 | 2022-03-04 | 费县三鼎工程科技中心 | 一种空气净化涂料 |
CN114452974A (zh) * | 2022-02-21 | 2022-05-10 | 中南大学 | MnO2基除醛材料及其超声-微波辅助制备方法和在甲醛催化氧化中的应用 |
CN114452974B (zh) * | 2022-02-21 | 2023-05-23 | 中南大学 | MnO2基除醛材料及其超声-微波辅助制备方法和在甲醛催化氧化中的应用 |
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