CN108993527A - 半导体材料包覆铁酸盐复合催化剂及其制备方法和应用 - Google Patents
半导体材料包覆铁酸盐复合催化剂及其制备方法和应用 Download PDFInfo
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- 229910001866 strontium hydroxide Inorganic materials 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims 1
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- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims 1
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- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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Abstract
本发明涉及一种半导体材料包覆铁酸盐复合催化剂及其制备方法和应用。所述的半导体材料包覆铁酸盐复合催化剂是SrTiO3@MnFe2O4。本发明采用微波水热法得到的SrTiO3@MnFe2O4纳米粒子催化剂,结合紫外光‑微波协同作用,降解抗生素。本发明作为一种处理抗生素废水的新方法,具有降解效率高、速度快、成本低和无二次污染等优点,适合于大规模处理抗生素废水,可实现短时间快速彻底地降解抗生素废水。
Description
技术领域
本发明属于催化降解领域,具体地涉及微波水热法制备的半导体材料包覆铁酸盐复合催化剂应用于紫外光-微波协同催化降解水中抗生素。
背景技术
抗生素之前被称作抗菌素,它是一类具备抗病原体或别的活性的微生物次级代谢产物,及其化学半合成或全合成的衍生物,这些微生物主要是指细菌、真菌、放线菌属等,一些高等动植物在生长繁殖过程中也可以产生抗生素。抗生素具有很高活性,在低浓度下就能选择性地抑制某些生物生命活动。对于某些病原微生物,抗生素可以强烈的抑制其活性甚至将其杀死,因此,它常被用作预防感染性疾病。抗生素首要用于医治感染类疾病,涵盖各类细菌感染或致病微生物感染,无特殊情况下,它对宿主细胞不会造成严重的危害。除了用于治疗感染类疾病,抗生素还被用作包括抗肿瘤、抗病毒、抑制免疫、杀虫、除草等。
目前,随着四环素类抗生素制药工业的发展,四环素类抗生素使用量的增加,治理其排放的含四环素的有机污水越来越受到重视,治理与预防的手段和技术也是层出不穷,目前对于含抗生素的有机污水的处理大多采用生物降解和包含光降解、水解、氧化降解等形式的非生物降解方式。
四环素在环境中降解主要分为生物降解和非生物降解,其中生物降解主要是通过微生物的作用降解四环素,非生物降解主要分为光降解、水解和氧化降解,其中光降解就是利用紫外光、可见光等降解四环素,水解则是水环境中降解四环素的主要途径,氧化降解则是利用强氧化剂氧化降解四环素。然而现有的方法,降解速率慢,成本高,易造成二次污染。
发明内容
为了解决以上问题,本发明提供一种降解速率快,成本低,没有中间产物生成和不会造成二次污染的半导体材料包覆铁酸盐复合催化剂。
本发明的另一目的是提供利用半导体材料包覆铁酸盐复合催化剂协同紫外光-微波催化降解水中有机污染物的方法。
本发明是通过如下的技术方案实现的:一种半导体材料包覆铁酸盐复合催化剂,所述的半导体材料包覆铁酸盐复合催化剂是SrTiO3@MnFe2O4,由钛酸锶SrTiO3和铁酸锰MnFe2O4制得。优选的,按质量比,钛酸锶:铁酸锰=1:(0.5~2)。
一种半导体材料包覆铁酸盐复合催化剂的制备方法,方法如下:将硝酸铁与硝酸锰混合,溶于超纯水中,用NaOH调节pH至12.0,将混合物转移到微波消解罐中,然后封闭微波消解罐,置于微波消解仪中,微波功率400w,温度210℃,水热压力1.5MPa下,微波水热反应30min,沉淀物用超纯水洗至中性,过滤,干燥,得铁酸锰MnFe2O4固体;将氢氧化锶和二氧化钛混合均匀后,加入适量的铁酸锰MnFe2O4固体,将混合物转移到微波消解罐中,然后封闭微波消解罐,置于微波消解仪中,微波功率400w,温度210℃,水热压力1.5MPa下,微波水热反应30min,沉淀物用超纯水洗至中性,过滤,干燥,得目标产物。
优选的,上述的制备方法,按摩尔比,Sr3+:Ti3+=1:1。
优选的,上述的制备方法,按摩尔比,Fe3+:Mn2+=2:1。
上述的半导体材料包覆铁酸盐复合催化剂在紫外光-微波协同作用下催化降解水中有机污染物中的应用。优选的,所述的有机污染物为抗生素。更优选的,所述的抗生素是四环素。
半导体材料包覆铁酸盐复合催化剂协同紫外光-微波催化降解水中有机污染物的方法,方法如下:于含有有机污染物的溶液中加入上述的半导体材料包覆铁酸盐复合催化剂,于微波功率100-300W,紫外光功率200W下,催化降解15-25min。优选的,有机污染物的浓度为25mg/L。
紫外光-微波降解技术的基本原理是,微波照射液体能使其中的极性分子高速旋转而产生热效应,同时改变体系的热力学函数,降低反应的活化能和分子的化学键强度。因此半导体与铁酸盐的质量比,微波照射时间,不同组成技术和微波功率,重复使用次数等因素对降解四环素(TC)有很大的影响。
本发明采用微波水热法得到的SrTiO3@MnFe2O4纳米粒子催化剂,结合紫外光-微波协同作用,降解抗生素。当紫外光-微波照射时,钛酸锶禁带宽度(3.2eV)在紫外光下具有优异的光催化活性,在降解污染物方面有着较为广阔的应用前景。铁酸盐能强烈吸收微波,在其表面产生许多“热点”,这些“热点”温度很高,有机污染物与热点接触就能够被氧化分解。微波和光催化涉及相似的反应机制,即氧化分解产生羟基自由基,技术组合后可以更好的降解抗生素。因此,本发明作为一种处理抗生素废水的新方法,具有降解效率高、速度快、成本低和无二次污染等优点,适合于大规模处理抗生素废水,可实现短时间快速彻底地降解抗生素废水。
附图说明
图1是复合催化剂SrTiO3@MnFe2O4的SEM图。
图2是复合催化剂SrTiO3@MnFe2O4的XRD图。
图3是不同条件下降解四环素的UV-vis光谱。
其中,a:TC;b:TC+UV+MW;c:TC+SrTiO3;d:TC+SrTiO3@MnFe2O4;e:TC+MnFe2O4;f:TC+UV+MW+SrTiO3;g:TC+UV+MW+MnFe2O4;h:TC+UV+MW+SrTiO3@MnFe2O4。
具体实施方式
实施例1
(一)SrTiO3催化剂
称取TiO2(0.4518g)和Sr(OH)2.8H2O(1.5032g),放入微波消解罐,添加30mL蒸馏水,保证Sr、Ti元素摩尔比别为1:1。然后封闭微波消解罐,把微波消解罐放到微波消解仪的转盘之中,微波功率400w,温度210℃,压力为1.5MPa的条件下,微波反应30min,冷却到室温,用蒸馏水多次洗涤沉淀物直至中性。离心后去除上清液,剩余物质置于烘箱,在105℃的条件下干燥6小时,研磨,最终得到固体SrTiO3催化剂。
(二)MnFe2O4催化剂
将3.636g Fe(NO3)3·9H2O与0.5mL 50%Mn(NO3)2混合溶于超纯水中,将混合物转移到微波消解罐中,用NaOH调节pH至12.0,然后封闭微波消解罐,把微波消解罐放到微波消解仪的转盘之中,微波功率400w,温度210℃,压力为1.5MPa的条件下,微波水热反应30min,冷却至室温,沉淀物用超纯水洗至中性,过滤,干燥,得目标产物MnFe2O4催化剂。
(三)SrTiO3@MnFe2O4催化剂
称取TiO2(0.4518g)和Sr(OH)2·8H2O(1.5032g),放入微波消解罐中,添加30mL蒸馏水,保证Sr、Ti元素摩尔比为1:1。按质量比,钛酸锶:铁酸锰=1:1,加入(二)获得的MnFe2O4催化剂,然后将混合物转移到微波消解罐中,封闭微波消解罐,把微波消解罐放到微波消解仪的转盘之中,微波功率400w,温度210℃,压力为1.5MPa的条件下,微波反应30min,冷却到室温,用蒸馏水多次洗涤沉淀物直至中性。离心后去除上清液,剩余物质置于烘箱,在105℃的条件下干燥6小时,研磨。最终得到SrTiO3@MnFe2O4固体。
(四)SrTiO3@MnFe2O4催化剂表征说明
制备的SrTiO3@MnFe2O4的SEM和XRD图,如图1和图2所示,图1复合催化剂的SEM图,可以明显观察出海绵杆状的MnFe2O4和球形的SrTiO3存在。图2复合催化剂的XRD,2θ值相似于MnFe2O4(JCPDS Card No.74-2403)和SrTiO3(JCPDF Card NO.35-0734)的特征衍射峰,证明复合物中存在MnFe2O4和SrTiO3。
(五)钛酸锶和铁酸锰不同质量比对四环素降解率的影响
SrTiO3@MnFe2O4催化剂的制备方法同实施例1的(三),只是改变钛酸锶和铁酸锰的质量比,分别降解四环素,结果如表1。
紫外光-微波(UV+MW)降解方法如下:量取20.0mL的四环素溶液(25mg/L TC),分别加入不同质量比的催化剂粉末1g/L(SrTiO3@MnFe2O4)混合,用200W紫外光和100W微波照射15min。冷却至室温,过滤,在200-800nm测定其紫外光谱。取375nm处的吸光度计算四环素的降解率。
降解率(%)=(C0–C)/C0×100%
其中,C0:原液的浓度;C:样品的浓度
表1 钛酸锶和铁酸锰不同质量比对四环素降解率(%)的影响
由表1可见,在紫外光-微波催化体系中,四环素的降解程度,随着铁酸锰的加入量增多而增高,在质量比SrTiO3:MnFe2O4=1:1时,四环素的降解率最高。而当SrTiO3:MnFe2O4=2:1和0:1时,四环素的降解率分别为62.94%和61.05%。为了获得降解率并降低成本,以便投入实际生产,本发明选择SrTiO3:MnFe2O4=1:1为最佳质量比。
实施例2
制备SrTiO3@MnFe2O4:
将3.636g Fe(NO3)3·9H2O与0.5mL 50%Mn(NO3)2混合,溶于超纯水中,用NaOH调节pH至12.0,将混合物转移到微波消解罐中,然后封闭微波消解罐,置于微波消解仪中,微波功率400w,温度210℃,水热压力1.5MPa下,微波水热反应30min,沉淀物用超纯水洗至中性,过滤,干燥,得目标产物MnFe2O4固体。
称取TiO2(0.4518g)和Sr(OH)2·8H2O(1.5032g),放入微波消解罐,添加30mL蒸馏水,保证Sr、Ti元素摩尔比别为1:1。然后按质量比,钛酸锶:铁酸锰=1:1,加入MnFe2O4固体,封闭微波消解罐,把微波消解罐放到微波消解仪的转盘之中,微波功率400w,温度210℃,压力为1.5MPa的条件下,微波反应30min,冷却到室温,用蒸馏水多次洗涤沉淀物直至中性。离心后去除上清液,剩余物质置于烘箱,在105℃的条件下干燥6小时,研磨。最终得到SrTiO3@MnFe2O4固体。
紫外光-微波(UV+MW)降解方法:量取20.0mL的四环素溶液(25mg/L TC),分别加入催化剂粉末1g/L(SrTiO3@MnFe2O4),紫外光功率200W,转速r=200r/min,用0-300W微波照射0-25min。冷却至室温,过滤,在200-800nm测定其紫外光谱。取375nm处的吸光度计算四环素的降解率。
(一)不同条件随时间对四环素降解率的影响
改变组成技术和降解时间,微波功率100W,紫外光功率200W,转速r=200r/min,催化剂投加量为1g/L。结果见表2。
表2 紫外光-微波不同组成技术随时间对四环素降解率的影响
由表2可见,随着照射时间的增加,降解率增大。当MW与UV技术联用时,四环素的降解率比单独使用MW和UV时要高,证明MW与UV有协同作用。当UV+MW照射25min时,SrTiO3@MnFe2O4/UV+MW体系中降解率为85%。比较而言,在0-25min范围内,SrTiO3@MnFe2O4/UV+MW体系的降解效率始终最高。
(二)微波功率随时间变化对四环素降解率的影响
改变微波功率,紫外光200W,转速r=200r/min,照射0-25min,催化剂投加量为1g/L。结果见表3。
表3 微波功率随时间变化对四环素降解率的影响
由表3可见,降解率与微波(MW)功率呈正相关系。表明较高的微波功率,能够获得高的微波照射强度,有利于催化剂吸收更多的微波能,使更多的四环素能够被降解。而且,在微波功率300W,微波照射时间25min时,SrTiO3@MnFe2O4结合紫外光—微波体系中降解率最大,为99.12%。
(三)改变催化剂使用次数对四环素降解率的影响
紫外光200W,转速r=200r/min,微波100W下照射15min,只改变催化剂使用次数。结果见表4。
表4 催化剂重复使用次数对四环素降解率的影响
任何催化剂的稳定性和可重用性在实际应用中是至关重要的。如表4所示,可以发现,随着催化剂复用次数的增加,催化剂活性略有下降,一直保持较高的降解率。
(四)对比实验
本发明:SrTiO3@MnFe2O4+MW+UV;
对比例1:SrTiO3+MW+UV;
对比例2:MnFe2O4+MW+UV;
对比例3:单独MW+UV;
对比例4:单独SrTiO3;
对比例5:单独MnFe2O4;
对比例6:单独SrTiO3@MnFe2O4;
紫外光功率200W,微波功率100W,转速r=200r/min,降解20.0min,计算不同情况下四环素的降解率,并进行比较,结果见表5和图3。
表5 不同情况下四环素降解率的比较
由表5和图2可见,当单紫外光—微波照射,不加催化剂时,吸收峰只有微弱降低。说明单紫外光-微波时只有极小的降解率。此外,单独使用SrTiO3,MnFe2O4and SrTiO3@MnFe2O4时,四环素的去除率分别为12.58%、18.85%、15.31%。然而,紫外光-微波与SrTiO3,MnFe2O4and SrTiO3@MnFe2O4结合时,吸收峰下降明显。这意味着,在紫外光-微波照射下,SrTiO3,MnFe2O4and SrTiO3@MnFe2O4都能吸收紫外光和微波,而使抗生素降解。因此,紫外光-微波结合三种催化剂,对于去除溶液中四环素具有协同效应。而且,SrTiO3@MnFe2O4/UV+MW体系的降解效果最好。
以上实施例中,抗生素采用的是四环素,但是并不限制本发明降解的抗生素为四环素,本发明的方法还适用于降解染料。如偶氮品红(Azo fuchsine),酸性红B(AR B)等。
Claims (10)
1.一种半导体材料包覆铁酸盐复合催化剂,其特征在于,所述的半导体材料包覆铁酸盐复合催化剂是SrTiO3@MnFe2O4,由钛酸锶SrTiO3和铁酸锰MnFe2O4制得。
2.根据权利要求1所述的一种半导体材料包覆铁酸盐复合催化剂,其特征在于,按质量比,钛酸锶:铁酸锰=1:(0.5~2)。
3.权利要求1或2所述的一种半导体材料包覆铁酸盐复合催化剂的制备方法,其特征在于,方法如下:将硝酸铁与硝酸锰混合,溶于超纯水中,用NaOH调节pH至12.0,将混合物转移到微波消解罐中,然后封闭微波消解罐,置于微波消解仪中,微波功率400w,温度210℃,水热压力1.5MPa下,微波水热反应30min,沉淀物用超纯水洗至中性,过滤,干燥,得铁酸锰MnFe2O4固体;将氢氧化锶和二氧化钛混合均匀后,加入适量的铁酸锰MnFe2O4固体,将混合物转移到微波消解罐中,然后封闭微波消解罐,置于微波消解仪中,微波功率400w,温度210℃,水热压力1.5MPa下,微波水热反应30min,沉淀物用超纯水洗至中性,过滤,干燥,得目标产物。
4.根据权利要求3所述的制备方法,其特征在于,按摩尔比,Sr3+:Ti3+=1:1。
5.根据权利要求3所述的制备方法,其特征在于,按摩尔比,Fe3+:Mn2+=2:1。
6.权利要求1或2所述的半导体材料包覆铁酸盐复合催化剂在紫外光-微波协同作用下催化降解水中有机污染物中的应用。
7.根据权利要求6所述的应用,其特征在于,所述的有机污染物为抗生素。
8.根据权利要求7所述的应用,其特征在于,所述的抗生素是四环素。
9.根据权利要求6、7或8所述的应用,其特征在于,方法如下:于含有有机污染物的溶液中加入权利要求1或2所述的半导体材料包覆铁酸盐复合催化剂,于微波功率100-300W,紫外光功率200W下,催化降解15-25min。
10.根据权利要求9所述的应用,其特征在于,有机污染物的浓度为25mg/L。
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