CN106984321B - 一种磁性BiVO4量子点复合光催化剂及制备方法和用途 - Google Patents
一种磁性BiVO4量子点复合光催化剂及制备方法和用途 Download PDFInfo
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Abstract
本发明提供了一种磁性BiVO4量子点复合光催化剂及制备方法和用途,制备步骤如下:步骤1、Fe3O4/C的制备;步骤2、BiVO4量子点的制备;步骤3、磁性BiVO4量子点复合光催化剂的制备。本发明的优点在于构建一个以酵母菌为碳源制备的磁性Fe3O4/C/q‑BiVO4复合光催化材料,将其作为光催化剂降解废水中的四环素和环丙沙星具有很好的光催化性能。
Description
技术领域
本发明涉及以酵母菌为碳源制备磁性酵母炭基负载BiVO4量子点(Fe3O4/C/q-BiVO4)光催化剂,并将所制备得到的磁性复合光催化剂用于光催化降解抗生素废水的研究。属于环境材料制备技术领域。
背景技术
随着医药行业中抗生素的研制和发展,抗生素被广泛应用在人类和动物的疾病治疗以及农业生产活动中,环境中残留的抗生素越来越多。另外抗生素生产的过程中会排放出大量的抗生素废水。当抗生素被释放到水体中,会影响水生生物的生长,诱导抗药细菌的产生,毒性大、成分复杂、难于处理;同时抗生素废水中残留的抗生素所带来的负面效应对人体的健康造成了威胁。四环素类抗生素被广泛用于动物疾病的治疗,大量使用使其在环境中普遍存在, 并导致了细菌耐药性,长期摄入人体会引起胃肠道刺激、二重感染、会形成四环素牙,会抑制婴儿骨骼发育,会引起严重肝损伤或加重原有的肾损伤,会引起光敏反应和前庭反应。环丙沙星是合成的第三代喹诺酮类抗菌药物,被广泛用于医疗、畜牧业、农业和水产养殖业等行业,可以通过很多渠道进入到环境水体中。环丙沙星可以对人体产生中枢系统毒性、肝肾毒性、血液系统毒性以及光毒性,也可以使环境中的细菌对其产生抗性。
光催化技术可有效地降解工业废水中的有机物浓度,且具有性能稳定、反应条件温和、无二次污染等优点,具有很好的应用前景。BiVO4作为一种低碳环保、具有多种形貌的金属氧化物和一种无毒,化学、生物性质稳定,具有可见光吸收能力的半导体材料,越来越受到广大科研工作者的关注,在光催化降解有机污染物,光电气敏,光催化分解水,光致发光等方面都有潜在的应用。然而,虽然BiVO4具有很好的可见光吸收特性,但存在导电性差,电子传输能力不强,回收能力差等缺点,材料本身有一定局限性。为提高了回收利用率又提高了光催化剂的性能,因此,引入了Fe3O4,以酵母菌为碳源,制备了Fe3O4/C/q-BiVO4,该复合光催化剂既具有磁性又具有较大比表面积,同时对水中较低浓度的污染物进行迅速的表面富集和净化,从而加快了光催化降解的反应速度,提高光催化活性。
发明内容
本发明的目的是以水热法、溶剂热、高温煅烧为技术手段,制备出磁性BiVO4量子点复合光催化剂。
技术方案如下:
一种磁性BiVO4量子点复合光催化剂,所述复合光催化剂是由碳、Fe3O4和BiVO4量子点复合而成的;碳为片状,Fe3O4呈球状,Fe3O4尺寸为20nm~60nm,碳和Fe3O4复合形成Fe3O4/C,BiVO4量子点负载在Fe3O4/C表面。
一种磁性BiVO4量子点复合光催化剂的制备方法,步骤如下:
步骤1、Fe3O4/C的制备
称取酵母菌和九水硝酸铁溶解在适量乙醇中,磁力搅拌;将产品离心干燥后放入管式炉中,在惰性气体条件下煅烧;
步骤2、BiVO4量子点(q-BiVO4)的制备
称取油酸钠和Bi(NO3)3·5H2O,加入蒸馏水,得到溶液A;称取Na3VO4·12H2O,加入蒸馏水,得到溶液B,将溶液B缓慢注入溶液A中,剧烈搅拌,得到混合液,将混合液转移到聚四氟乙烯衬里的高压釜中,密封,加热反应,反应完毕后,冷却到室温,最后将得到的固体产物洗涤,得到BiVO4量子点,记为q-BiVO4,冷冻;
步骤3、磁性BiVO4量子点复合光催化剂的制备
称取BiVO4量子点和Fe3O4/C加入到乙醇中,磁力搅拌,用去离子水洗涤三遍,干燥,得到磁性BiVO4量子点复合光催化剂,记为Fe3O4/C/q-BiVO4。
步骤1中,所述的酵母菌、九水硝酸铁、乙醇的用量比为6g:3g:200mL;所述惰性气体为氮气,所述煅烧的温度为450~650℃。
步骤2中,溶液A中,所述油酸钠与Bi(NO3)3·5H2O的质量浓度比为2:1,所述油酸钠的质量浓度为20mg/mL;溶液B中,所述Na3VO4·12H2O的质量浓度为10mg/mL;所述溶液 A与溶液B的体积比为1:1;所述加热反应的温度为100℃,反应时间为12h。
步骤3中,所述BiVO4量子点、Fe3O4/C、乙醇的用量比为0.1g~1g:0.1g~1g:50mL~100mL,所述磁力搅拌的时间为3h。
步骤3中,所述BiVO4量子点、Fe3O4/C的质量比为1:1。
按照以上所述的制备方法得到的磁性BiVO4量子点复合光催化剂,应用于降解四环素和环丙沙星。
本发明的有益效果:
本发明的优点在于构建一个以酵母菌为碳源制备的磁性Fe3O4/C/q-BiVO4复合光催化材料,将其作为光催化剂降解废水中的四环素和环丙沙星具有很好的光催化性能。磁性材料的加入使得光催化剂可以利用外加磁场迅速分离回收,而且在该发明中,由于导电C材料的引入,极大地提高了q-BiVO4光生电子和光致空穴的分离,使得所制备的磁性复合光催化剂高效的光催化活性得以发挥,同时避免了催化剂在溶液中残留造成的二次污染,该方法不会造成资源浪费,且操作简便,成本较低,是一种绿色环保的高效处理技术。
附图说明
图1为q-BiVO4和Fe3O4/C/q-BiVO4的TEM图;
图2为不同碳含量的光催化剂在含有四环素废水中的光催化降解效果图,a.Fe3O4/C/q-BiVO4-450,b.Fe3O4/C/q-BiVO4-500,c.Fe3O4/C/q-BiVO4-550, d.Fe3O4/C/q-BiVO4-600,e.Fe3O4/C/q-BiVO4-650;
图3为不同碳含量的光催化剂在含有环丙沙星废水中的光催化降解效果图,a.Fe3O4/C/q-BiVO4-450,b.Fe3O4/C/q-BiVO4-500,c.Fe3O4/C/q-BiVO4-550, d.Fe3O4/C/q-BiVO4-600,e.Fe3O4/C/q-BiVO4-650;
图4为磁性Fe3O4/C/q-BiVO4-0.3(性能最佳)复合光催化剂光催化降解四环素溶液的5 次循环光催化效果图;
图5为磁性Fe3O4/C/q-BiVO4-0.3(性能最佳)复合光催化剂光催化降解四环素溶液的5 次循环光催化效果图;
图6为复合光催化剂的磁分离特性谱图,a.Fe3O4,b.Fe3O4/C/q-BiVO4。
具体实施方式
下面结合具体实施实例对本发明做进一步说明。
本发明中所制备的光催化剂的光催化活性评价:在DW-01型光化学反应仪(购自扬州大学城科技有限公司)中进行,将100mL四环素模拟废水加入反应器中,然后加入制得的光催化剂0.1g,磁力搅拌30min后,开启氙灯和曝气装置通入空气保持催化剂处于悬浮或飘浮状态,光照过程中间隔20min取样分析,离心分离后取上层清液在分光光度计λmax=357nm处测定吸光度,并通过公式:Dr=(C0-C)×100/C0算出其降解率Dr,其中C0为达到吸附平衡后浓度, C为t时刻测定的四环素溶液的浓度,t为反应时间。
本发明中所制备的光催化剂的光催化活性评价:在DW-01型光化学反应仪(购自扬州大学城科技有限公司)中进行,将100mL环丙沙星模拟废水加入反应器中,然后加入制得的光催化剂0.1g,磁力搅拌30min后,开启氙灯和曝气装置通入空气保持催化剂处于悬浮或飘浮状态,光照过程中间隔20min取样分析,离心分离后取上层清液在分光光度计λmax=278nm处测定吸光度,并通过公式:Dr=(C0-C)×100/C0算出其降解率Dr,其中C0为达到吸附平衡后浓度,C为t时刻测定的环丙沙星溶液的浓度,t为反应时间。
实施例1:
(1)Fe3O4/C的制备
称取6g酵母菌和3g九水硝酸铁溶解在适量乙醇中(完全溶解),磁力搅拌3h。将产品离心干燥后,将样品放入管式炉中,在氮气条件下,2°/min,分别在650℃、600℃、550℃、500℃、450℃不同温度下煅烧。
(2)BiVO4量子点的制备
称取0.4g油酸钠和0.2g Bi(NO3)3·5H2O,加入20ml蒸馏水,再称取0.2g Na3VO4·12H2O,加入20ml蒸馏水,然后将该溶液缓慢注入上述溶液中,剧烈搅拌2h,将混合物转移到一个 50ml的聚四氟乙烯衬里的高压釜中,密封,加热100℃反应12h,冷却到室温,最后将得到的固体产物用正己烷和无水乙醇洗涤三遍,冷冻。
(3)Fe3O4/C/q-BiVO4的制备
a.称取0.1g q-BiVO4和0.1g Fe3O4/C(不同温度下)加入乙醇溶液中,磁力搅拌3h,用去离子水洗涤三遍,放到60℃烘箱干燥,样品记作Fe3O4/C/q-BiVO4-450,Fe3O4/C/q-BiVO4-500, Fe3O4/C/q-BiVO4-550,Fe3O4/C/q-BiVO4-600,Fe3O4/C/q-BiVO4-650。
实施例2:
(1)Fe3O4/C的制备
称取6g酵母菌和3g九水硝酸铁溶解在适量乙醇中(完全溶解),磁力搅拌3h。将产品离心干燥后,将样品放入管式炉中,在氮气条件下,2°/min,分别在650℃、600℃、550℃、500℃、450℃不同温度下煅烧。
(2)BiVO4量子点的制备
称取0.4g油酸钠和0.2g Bi(NO3)3·5H2O,加入20ml蒸馏水,再称取0.2g Na3VO4·12H2O,加入20ml蒸馏水,然后将该溶液缓慢注入上述溶液中,剧烈搅拌2h,将混合物转移到一个 50ml的聚四氟乙烯衬里的高压釜中,密封,加热100℃反应12h,冷却到室温,最后将得到的固体产物用正己烷和无水乙醇洗涤三遍,冷冻。
(3)Fe3O4/C/q-BiVO4的制备
b.称取0.5g q-BiVO4和0.5g Fe3O4/C(不同温度下)加入乙醇溶液中,磁力搅拌3h,用去离子水洗涤三遍,放到60℃烘箱干燥,样品记作Fe3O4/C/q-BiVO4-450,Fe3O4/C/q-BiVO4-500, Fe3O4/C/q-BiVO4-550,Fe3O4/C/q-BiVO4-600,Fe3O4/C/q-BiVO4-650。
实施例3:
(1)Fe3O4/C的制备
称取6g酵母菌和3g九水硝酸铁溶解在适量乙醇中(完全溶解),磁力搅拌3h。将产品离心干燥后,将样品放入管式炉中,在氮气条件下,2°/min,分别在650℃、600℃、550℃、500℃、450℃不同温度下煅烧。
(2)BiVO4量子点的制备
称取0.4g油酸钠和0.2g Bi(NO3)3·5H2O,加入20ml蒸馏水,再称取0.2g Na3VO4·12H2O,加入20ml蒸馏水,然后将该溶液缓慢注入上述溶液中,剧烈搅拌2h,将混合物转移到一个 50ml的聚四氟乙烯衬里的高压釜中,密封,加热100℃反应12h,冷却到室温,最后将得到的固体产物用正己烷和无水乙醇洗涤三遍,冷冻。
(3)q-BiVO4/Fe3O4/C的制备
c.称取1g q-BiVO4和1g Fe3O4/C(质量比为1:1)加入乙醇溶液中,磁力搅拌3h,用去离子水洗涤三遍,放到60℃烘箱干燥,样品记作Fe3O4/C/q-BiVO4-450,Fe3O4/C/q-BiVO4-500, Fe3O4/C/q-BiVO4-550,Fe3O4/C/q-BiVO4-600,Fe3O4/C/q-BiVO4-650。
实施例:4:
按实施例1制备工艺同样步骤进行,不同的是(3)中称取0.1g的Fe3O4/C/q-BiVO4-450 样品在光化学反应仪中进行光催化降解试验,测得该光催化剂对四环素的降解率在120min 内达到54%,对环丙沙星的降解率在120min内达到62%。
实施例5:
按实施例1制备工艺同样步骤进行,不同的是(3)中称取0.1g的Fe3O4/C/q-BiVO4-500 样品在光化学反应仪中进行光催化降解试验,测得该光催化剂对四环素的降解率在120min 内达到17%,对环丙沙星的降解率在120min内达到50%。
实施例6:
按实施例1制备工艺同样步骤进行,不同的是(3)中称取0.1g的Fe3O4/C/q-BiVO4-550 样品在光化学反应仪中进行光催化降解试验,测得该光催化剂对四环素的降解率在120min 内达到29%,对环丙沙星的降解率在120min内达到44%。
实施例7:
按实施例1制备工艺同样步骤进行,不同的是(3)中称取0.1g的Fe3O4/C/q-BiVO4-600 样品在光化学反应仪中进行光催化降解试验,测得该光催化剂对四环素的降解率在120min 内达到44%,对环丙沙星的降解率在120min内达到38%。
实施例8:
按实施例1制备工艺同样步骤进行,不同的是(3)中称取0.1g的Fe3O4/C/q-BiVO4-650 样品在光化学反应仪中进行光催化降解试验,测得该光催化剂对四环素的降解率在120min 内达到70%,对环丙沙星的降解率在120min内达到30%。
从图1a是BiVO4量子点的TEM图,从图1b Fe3O4/C/q-BiVO4的TEM图,从b中可以看出碳为片状,Fe3O4呈球状,尺寸约在20nm~60nm之间,同时可以明显看出BiVO4量子点负载在Fe3O4/C表面。
从图2中可以看出,Fe3O4/C/q-BiVO4-650降解四环素的活性最好,降解率达到70%。
从图3中可以看出,Fe3O4/C/q-BiVO4-450降解环丙沙星的活性最好,降解率达到62%。
图4展示Fe3O4/C/q-BiVO4-650降解四环素溶液的5次循环实验,磁性 Fe3O4/C/q-BiVO4-650复合光催化剂光催化降解率的变化很小,说明所制备的磁性 Fe3O4/C/q-BiVO4-650复合光催化剂具有良好的光化学稳定性。
图5展示Fe3O4/C/q-BiVO4-450降解环丙沙星溶液的5次循环实验,磁性 Fe3O4/C/q-BiVO4-450复合光催化剂光催化降解率的变化很小,说明所制备的磁性 Fe3O4/C/q-BiVO4-450复合光催化剂具有良好的光化学稳定性。
从图6中可以看出Fe3O4/C磁性最好,磁饱和强度可达64emu/g左右,相对于Fe3O4,Fe3O4/C/q-BiVO4磁性减弱,磁饱和强度可达50emu/g左右,仍具有较好的磁分离特性。
Claims (5)
1.一种磁性BiVO4量子点复合光催化剂,其特征在于,所述复合光催化剂是由碳、Fe3O4和BiVO4量子点复合而成的;碳为片状,Fe3O4呈球状,Fe3O4尺寸为20nm~60nm,碳和Fe3O4复合形成Fe3O4/C,BiVO4量子点负载在Fe3O4/C表面;步骤如下:
步骤1、Fe3O4/C的制备
称取酵母菌和九水硝酸铁溶解在适量乙醇中,磁力搅拌;将产品离心干燥后放入管式炉中,在惰性气体条件下煅烧;所述的酵母菌、九水硝酸铁、乙醇的用量比为6g:3g:200mL;
步骤2、BiVO4量子点的制备
称取油酸钠和Bi(NO3)3·5H2O,加入蒸馏水,得到溶液A;称取Na3VO4·12H2O,加入蒸馏水,得到溶液B,将溶液B缓慢注入溶液A中,剧烈搅拌,得到混合液,将混合液转移到聚四氟乙烯衬里的高压釜中,密封,加热反应,反应完毕后,冷却到室温,最后将得到的固体产物洗涤,得到BiVO4量子点,冷冻;
步骤3、磁性BiVO4量子点复合光催化剂的制备
称取BiVO4量子点和Fe3O4/C加入到乙醇中,磁力搅拌,用去离子水洗涤三遍,干燥,得到磁性BiVO4量子点复合光催化剂;所述BiVO4量子点、Fe3O4/C、乙醇的用量比为0.1g~1g:0.1g~1g:50mL~100mL,所述BiVO4量子点、Fe3O4/C的质量比为1:1。
2.如权利要求1所述的磁性BiVO4量子点复合光催化剂,其特征在于,步骤1中,所述惰性气体为氮气,所述煅烧的温度为450~650℃。
3.如权利要求1所述的磁性BiVO4量子点复合光催化剂,其特征在于,步骤2中,溶液A中,所述油酸钠与Bi(NO3)3·5H2O的质量浓度比为2:1,所述油酸钠的质量浓度为20mg/mL;溶液B中,所述Na3VO4·12H2O的质量浓度为10mg/mL;所述溶液A与溶液B的体积比为1:1;所述加热反应的温度为100℃,反应时间为12h。
4.如权利要求1所述的磁性BiVO4量子点复合光催化剂,其特征在于,步骤3中,所述磁力搅拌的时间为3h。
5.如权利要求1所述的磁性BiVO4量子点复合光催化剂的用途,其特征在于,所述磁性BiVO4量子点复合光催化剂应用于降解四环素和环丙沙星。
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