CN111068656A - Bi2WO6/HRP光酶耦合人工催化剂及其制备方法和应用 - Google Patents
Bi2WO6/HRP光酶耦合人工催化剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明属于纳米材料合成技术领域,涉及一种Bi2WO6/HRP光酶耦合人工催化剂的制备方法和应用。本发明通过滴加搅拌的方法,利用金属Ni的桥联作用将HRP稳定的固定在Bi2WO6的表面,本发明选择了光催化剂和生物酶结合的方式制备出Bi2WO6/HRP光酶耦合人工催化剂,并在可见光光照的联合作用下,用于对酚类污染物的降解;本发明催化剂制作成本廉价,易操作,可用于大规模生产,绿色无害,符合环境友好要求。
Description
技术领域
本发明属于纳米材料合成技术领域,涉及一种Bi2WO6/HRP光酶耦合人工催化剂的制备方法和应用。
背景技术
科技的发展、创新为时代的进步提供不断前行的动力,然而科技的进步总伴随着环境的污染,汽车尾气、工业废水的肆意排放不仅给水生物带来毁灭性破坏,还对人体健康方面产生巨大威胁。
目前在水中污染物净化方面,主要分为物理法、化学法以及生物降解法。物理法是采用沉淀、过滤、吸附等手段,将大颗粒以及部分有机污染物除去,但是其不能完全除去水中溶解的污染物,远远达不到排放标准。采用化学法,很大程度上能够除去污染物,但是二次污染成为了技术难题。生物降解法是目前降解有机物方面最优的选择,但是生物试剂价格过高也是成为了污水处理的难题。
因此,开发一种简单高效的降解材料及降解方法来治理水中有机污染物是环境治理急需解决的问题。
发明内容
本发明的目的在于提供一种Bi2WO6/HRP光酶耦合人工催化剂的制备方法
和应用。本发明的技术方案中通过金属Ni的桥联作用,使用滴加搅拌的方式将HRP负载到Bi2WO6表面,构建成Bi2WO6/HRP光酶耦合人工催化剂,实现在可见光下对多种有机污染物的降解。
为实现上述技术目的,本发明首先提供一种Bi2WO6/HRP光酶耦合人工催化剂,所述催化剂中HRP的负载量为1%-4%,即最终得到的材料中,HRP和钨酸铋的质量比为1-4:100。
本发明还提供一种Bi2WO6/HRP光酶耦合人工催化剂的制备方法,所述方法包括:
准确称取一定量的Bi2WO6于反应容器中,加入少量去离子水,超声分散均匀;向其中滴加一定量的Ni(OAc)2溶液,进行搅拌;滴加HRP溶液,搅拌一段时间后离心分离,移去上清液,即得Bi2WO6/HRP催化剂。
其中,所述Bi2WO6的用量为45-55mg,优选的Bi2WO6的用量为50mg。
所述Ni(OAc)2的浓度为1.0mg/mL,用量为1.8-2.2mL,搅拌时间为1 h。优选的Ni(OAc)2的用量为2.0 mL。
所述HRP的浓度为0.8-1.2mg/mL,用量为0.5-2.0mL,优选的HRP溶液浓度为1.0mg/mL,用量为1mL。
所述得到的Bi2WO6/HRP光酶耦合人工催化剂中HRP的负载量为1%-4%,即最终得到的材料中,HRP和钨酸铋的质量比为1-4:100。
本发明还提供所得Bi2WO6/HRP光酶耦合人工催化剂降解双酚A的用途,具体应用如下:
将上述样品Bi2WO6/HRP光酶耦合人工催化剂加入到一定浓度污染物溶液中在可见光下进行降解。
Bi2WO6/HRP催化剂与的双酚A溶液 (BAP)混合后,首先暗反应不低于30 min,使催化剂在污染物溶液中达到吸脱附平衡,污染物在水中的浓度不在改变,随后进行光反应,用注射器取样2~3 mL,使用0.45 μm水系滤膜过滤获取清液,期间每10 min取样一次。最后用紫外分光光度计在波长276 nm处测量清液的吸光度,记录,绘制成图。
本发明的有益效果:
本发明通过滴加搅拌的方法,利用金属Ni的桥联作用将HRP稳定的固定在Bi2WO6的表面,本发明选择了光催化剂和生物酶结合的方式制备出Bi2WO6/HRP光酶耦合人工催化剂,在可见光光照的联合作用下,显著的提高了对酚类污染物的降解率,达到除去废水中有机污染物的效果;本发明制作成本廉价,易操作,可用于大规模生产,绿色无害,符合环境友好要求。光催化技术凭借着太阳能绿色无污染、适合大规模开发利用等特点受到广泛关注。
本发明选择负载辣根过氧化物酶(HRP),因其比活性高、稳定、分子量小以、易制备。本发明中的载体Bi2WO6是最简单的铋层状结构氧化物之一,其具有较窄的禁带宽度(约为2.8 eV),能够在可见光下响应,且活性较高。同时,钨酸铋的制作成本较低、对环境友好,在实际应用方面能够实现最佳经济效益。Bi2WO6超薄纳米片组成的中空形貌有利于载流子的传输和分离、有机污染物传输到催化剂的内部,还有利于助催化剂负载到Bi2WO6的表面。因此,本发明提出了Bi2WO6/HRP光酶耦合人工催化剂,用于可见光下降解多种有机污染物。
附图说明
图1为制备得到的Bi2WO6和Bi2WO6/HRP的XRD谱图。
图2为Bi2WO6的TEM谱图;其中a为中空Bi2WO6球,b为组成Bi2WO6球的超薄纳米片。
图3为Bi2WO6/HRP的激光共聚焦显微镜的明场(a)和荧光场(b)图片
图4为Bi2WO6和Bi2WO6/HRP的固体紫外吸收谱图。
图5为光催化降解BPA时,HRP、Bi2WO6和Bi2WO6/HRP(1%)的降解动力学曲线。
图6为光催化降解BPA时,Bi2WO6、Bi2WO6/HRP(1.0%)、Bi2WO6/HRP(2.0%)、Bi2WO6/HRP(3.0%)、Bi2WO6/HRP(4.0%)的降解动力学曲线。
具体实施方式
以下通过各实施方式对本发明进行详细描述。但这些实施例仅用于说明本发明而不用于限制本发明的范围。此外,在阅读本发明所述的内容之后,本领域技术人员可以对本发明做各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。
实施例1:Bi2WO6/HRP光酶耦合人工催化剂的制备
(1)制备中空球状Bi2WO6光催化剂:
中空球状Bi2WO6的合成采用的是酸刻蚀合成法
取0.3mL浓硝酸加入到10mL去离子水中,搅拌使其混合均匀,随后加入1mmol硝酸铋(Bi(NO3)3·5H2O),充分搅拌至完全溶解;称取0.5mmol钨酸钠 (Na2WO4·2H2O)加入到10mL去离子水中,超声使其完全溶解;将钨酸钠溶液缓慢滴加到硝酸铋溶液中后搅拌2h,随后将悬浊液转移至25mL反应釜中,160 ℃下进行水热反应24 h;冷却到室温后,先用去离子水洗3次,后用乙醇洗3次,最后放置80 ℃烘箱干燥20 h,最终获得中空球状Bi2WO6。
(2)制备Bi2WO6/HRP光酶耦合人工催化剂
制备Bi2WO6/HRP光酶耦合人工催化剂:准确称取50 mg的Bi2WO6于50 mL烧杯中,加入15mL去离子水,超声分散均匀;向其中滴加1 mg/mL的Ni(OAc)2溶液2.0 mL,搅拌反应1 h;继续滴加1.0 mg/mL的HRP溶液1mL,继续搅拌;搅拌4 h后8000r/min离心分离,移去上清液,即得样品。
本发明中,利用X射线衍射(XRD)、紫外可见分光光度计、紫外可见漫反射分光光度计等手段对Bi2WO6/HRP复合体系进行表征。
图1是Bi2WO6和Bi2WO6/HRP的XRD谱图,从Bi2WO6的衍射谱中能够发现,酸刻蚀法合成的Bi2WO6样品为纯相,样品XRD衍射峰较尖锐且没有其他杂相形成。和Bi2WO6的衍射峰相比,Bi2WO6/HRP的峰位置不变,说明金属Ni和HRP负载到Bi2WO6上没有改变Bi2WO6的结构,也没有出现杂峰。
图2为制备得到的中空球状Bi2WO6的透射图,由图可以看出Bi2WO6样品单个粒径尺寸约为4μm,形貌呈均匀分布的花球状分级结构,花球的边缘和内部有明显的亮度区别,证实了Bi2WO6中空球状结构。右图可以看出花球的边缘是由超薄的2D纳米片组装而成,这种组装方式能够产生多种纳米孔隙,有利于载流子的传输和分离、有机污染物传输到催化剂的内部,还有利于有机污染物向结构内部扩散。
图3是Bi2WO6/HRP激光共聚焦显微镜的明场(a)和荧光场(b)图片,将FITC(异硫氰酸荧光素)固定在HRP上后,在激发波长和发射波长为491和527nm的激光共聚焦显微镜下观察到Bi2WO6/HRP的明场和荧光场图片。在明场图片中能够清晰的看到球形Bi2WO6,而在荧光场中则能够看到发出绿荧光的HRP,这证明了HRP负载到了Bi2WO6的表面。
图4是Bi2WO6和Bi2WO6/HRP的固体紫外吸收谱图,两者相比,Bi2WO6/HRP光酶体系的吸收边发生微弱的红移现象,同时在450nm~ 750 nm吸收边位置更高意味着其对可见光的吸收能力增强,有利于增强Bi2WO6/HRP光酶体系可见光下催化活性。
实施例2:Bi2WO6/HRP光酶耦合人工催化剂的制备
中空球状Bi2WO6光催化剂的制备方法同实施例1的步骤(1),Bi2WO6/HRP光酶耦合人工催化剂的制备过程中,改变HRP溶液的用量,分别为0.5mL、1.5mL、2.0mL。按照实施例1中的方法制备得到Bi2WO6/HRP光酶耦合人工催化剂。
所述得到的Bi2WO6/HRP光酶耦合人工催化剂中HRP的负载量为1%、3%、4%,即最终得到的材料中,HRP的质量占钨酸铋质量的1%、3%、4%,记为Bi2WO6/HRP(1%)、Bi2WO6/HRP(3%)、Bi2WO6/HRP(4%),同样的,实施例1中得到的催化剂中HRP的负载量为2%,即最终得到的材料中,HRP的质量占钨酸铋质量的2%,记为Bi2WO6/HRP(2%)。
实施例3:Bi2WO6/HRP光酶耦合人工催化剂的制备
中空球状Bi2WO6光催化剂的制备方法同实施例1的步骤(1),然后制备Bi2WO6/HRP光酶耦合人工催化剂:
准确称取45 mg的Bi2WO6于50 mL烧杯中,加入15 mL去离子水,超声分散均匀;向其中滴加1.0mg/mL的Ni(OAc)2溶液1.8 mL,搅拌反应1 h;继续滴加0.8mg/mL的HRP溶液0.5mL,继续搅拌;搅拌4 h后8000r/min离心分离,移去上清液,即得样品。
实施例4:Bi2WO6/HRP光酶耦合人工催化剂的制备
中空球状Bi2WO6光催化剂的制备方法同实施例1的步骤(1),然后制备Bi2WO6/HRP光酶耦合人工催化剂:
准确称取55 mg的Bi2WO6于50 mL烧杯中,加入15 mL去离子水,超声分散均匀;向其中滴加1.0mg/mL的Ni(OAc)2溶液2.2 mL,搅拌反应1 h;继续滴加1.2mg/mL的HRP溶液2.mL,继续搅拌;搅拌4 h后8000r/min离心分离,移去上清液,即得样品。
实施例5:Bi2WO6/HRP光酶耦合人工催化剂降解双酚A
将制备得到的Bi2WO6/HRP光酶耦合人工催化剂与100 mL的双酚A溶液 (BAP,20 mg/L)混合后,首先暗反应30 min,然后进行光反应,用注射器取样2~3 mL,使用0.45 μm水系滤膜过滤获取清液,期间每10 min取样一次。最后用紫外分光光度计在波长276 nm处测量清液的吸光度,记录,绘制成图。
结果发现,金属Ni在Bi2WO6和HRP之间起到桥联作用,能够使HRP稳定的负载到Bi2WO6的表面。负载不同量的HRP,发现当HRP的负载量为2%时,Bi2WO6/HRP光酶耦合人工催化剂的降解率最高,90 min其降解率能够达到85%左右,负载0、1.0、3.0、4.0%则分别降解了57、80、83、36%。如图6所示,为光催化降解BPA时,Bi2WO6、Bi2WO6/HRP(1%)、Bi2WO6/HRP(2%)、Bi2WO6/HRP(3%)、Bi2WO6/HRP(4%)的降解动力学曲线。
与此同时,本发明中还将HRP、Bi2WO6和Bi2WO6/HRP的降解率做对比,结果发现Bi2WO6/HRP的降解速率远高于HRP和Bi2WO6,如图5所示,为光催化降解BPA时,HRP、Bi2WO6和Bi2WO6/HRP(1%)的降解动力学曲线。
Claims (10)
1.一种Bi2WO6/HRP光酶耦合人工催化剂,所述催化剂中HRP的负载量为1wt%-4wt%,即最终得到的材料中,HRP和钨酸铋的质量比为1-4:100。
2.一种Bi2WO6/HRP光酶耦合人工催化剂的制备方法,所述方法包括:
准确称取一定量的Bi2WO6于反应容器中,加入少量去离子水,超声分散均匀;向其中滴加一定量的Ni(OAc)2溶液,进行搅拌;滴加HRP溶液,搅拌一段时间后离心分离,移去上清液,即得Bi2WO6/HRP催化剂。
3.根据权利要求2所述的方法,其特征在于,所述Bi2WO6的用量为45-55mg。
4.根据权利要求3所述的方法,其特征在于,所述Bi2WO6的用量为50mg。
5.根据权利要求2所述的方法,其特征在于,所述Ni(OAc)2的浓度为1.0 mg/mL,用量为1.8-2.2mL,搅拌时间为1 h。
6.根据权利要求5所述的方法,其特征在于,所述的Ni(OAc)2的用量为2.0 mL。
7.根据权利要求2所述的方法,其特征在于,所述HRP的浓度为0.8-1.2mg/mL,用量为0.5-2.0 mL。
8.根据权利要求7所述的方法,其特征在于,所述HRP溶液浓度为1.0mg/mL,用量为1mL。
9.权利要求1所述的Bi2WO6/HRP光酶耦合人工催化剂降解双酚A的用途。
10.根据权利要求9所述的用途,其特征在于,将Bi2WO6/HRP光酶耦合人工催化剂加入到污染物溶液中在可见光下进行降解。
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112619711A (zh) * | 2020-11-13 | 2021-04-09 | 江苏大学 | 一种HRP/CN-Cu3(PO4)2纳米花及其制备方法和应用 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102328988A (zh) * | 2011-07-12 | 2012-01-25 | 大连理工大学 | 辣根过氧化物酶对酰胺类农药废水原位处理的方法 |
CN105717181A (zh) * | 2016-02-25 | 2016-06-29 | 济南大学 | 一种基于双金属原位复合二维纳米材料的电化学马拉硫磷生物传感器的制备方法及应用 |
CN108355669A (zh) * | 2018-01-25 | 2018-08-03 | 太原理工大学 | 一种磁性纳米洋葱碳负载Bi2WO6的光催化剂及其制备方法和应用 |
CN108435249A (zh) * | 2018-03-29 | 2018-08-24 | 江苏大学 | g-C3N4/Ni-HRP复合光催化剂及其制备方法和应用 |
CN109234261A (zh) * | 2018-08-21 | 2019-01-18 | 江苏大学 | 辣根过氧化物酶磁性纳米花及其制备方法和应用 |
CN110237870A (zh) * | 2019-06-27 | 2019-09-17 | 河南大学 | 一种聚苯酚/二氧化钛复合材料及制备方法和应用 |
-
2019
- 2019-11-04 CN CN201911066393.5A patent/CN111068656A/zh active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102328988A (zh) * | 2011-07-12 | 2012-01-25 | 大连理工大学 | 辣根过氧化物酶对酰胺类农药废水原位处理的方法 |
CN105717181A (zh) * | 2016-02-25 | 2016-06-29 | 济南大学 | 一种基于双金属原位复合二维纳米材料的电化学马拉硫磷生物传感器的制备方法及应用 |
CN108355669A (zh) * | 2018-01-25 | 2018-08-03 | 太原理工大学 | 一种磁性纳米洋葱碳负载Bi2WO6的光催化剂及其制备方法和应用 |
CN108435249A (zh) * | 2018-03-29 | 2018-08-24 | 江苏大学 | g-C3N4/Ni-HRP复合光催化剂及其制备方法和应用 |
CN109234261A (zh) * | 2018-08-21 | 2019-01-18 | 江苏大学 | 辣根过氧化物酶磁性纳米花及其制备方法和应用 |
CN110237870A (zh) * | 2019-06-27 | 2019-09-17 | 河南大学 | 一种聚苯酚/二氧化钛复合材料及制备方法和应用 |
Non-Patent Citations (1)
Title |
---|
CHUNMEI LI ET AL.: "A thin empty-shell bismuth tungstate hierarchical structure constructed by the acid sculpture effect with improved visible-light photocatalytic activity", 《 NEW J. CHEM.》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112619711A (zh) * | 2020-11-13 | 2021-04-09 | 江苏大学 | 一种HRP/CN-Cu3(PO4)2纳米花及其制备方法和应用 |
CN112619711B (zh) * | 2020-11-13 | 2023-01-17 | 江苏大学 | 一种HRP/CN-Cu3(PO4)2纳米花及其制备方法和应用 |
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