CN110813325A - 一种BiOCl中空微球光催化剂的制备方法 - Google Patents
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- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 title claims abstract description 67
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Abstract
本发明涉及一种BiOCl中空微球光催化剂的制备方法,该方法是指:将壳聚糖分散液缓慢加入到铋盐溶液中,于5℃~20℃恒温搅拌10~100 min,使其为胶体态;再在搅拌条件下向体系中缓慢加入氯盐溶液,于5℃~20℃恒温搅拌10~100 min;然后将反应体系移入高压反应釜中,经均相反应、离心分离,得到产品;该产品经蒸馏水洗涤、干燥过夜,即得BiOCl中空微球光催化剂。本发明通过一步水热制备具有特定晶型暴露的BiCOl光催化剂,其方法简单、成本低廉,所制备的BiOCl中空微球光催化剂在模拟太阳光下对TC具有很好的催化降解性能,在光催化降解抗生素废水领域具有很好的应用前景。
Description
技术领域
本发明涉及微纳米材料技术领域和光催化技术领域,尤其涉及一种BiOCl中空微球光催化剂的制备方法。
背景技术
水资源在人类生产生活中是一种不可或缺的自然资源。然而,随着药学、有机化学和畜牧技术的协同发展,抗生素被广泛地应用于传染疾病的防治和牲畜饲养领域。四环素(TC)是一种大量生产和使用的抗生素。近年来,随着该类抗生素的过量使用,人们不断在水环境中检测到它的存在,这直接影响了人类用水安全。现如今,诸如吸附、电催化、膜分离、生物降解等方法被广泛用于TC的去除。基于半导体光催化剂在水处理领域所展现出的高效、低能耗、可持续特性,该类催化剂的光催化降解方法也被广泛应用于对TC的光催化降解。
作为一种廉价无毒的三元半导体材料,氯氧化铋(BiOCl)具有良好的化学稳定性和较强的光催化性能。BiOCl是一种潜力广阔的明星半导体光催化剂,广泛应用于光催化产氢、光催化N2固定、光催化水污染处理等领域。因此,已经开发了具有不同结构与形貌的BiOCl材料,例如:CN 109261174 A公开了一种BiOCl微米环及制备方法,其在可见光照射下具有良好的光催化降解活性。但带隙过宽、可见光吸收较少是BiOCl光催化剂的一大致命弱点。为解决这一问题,人们开发了诸如构建异质结、载体负载、等离子体敏化等方法。例如CN108097277 A公开了一种BiOCl/ZnO异质结高可见光催化活性材料及其制备方法;CN109607671 A公开了一种C/Bi/BiOCl三元复合光催化材料的制备方法。该方法制备的复合材料C/Bi/BiOCl与BiOCl相比具有更低的带隙宽的,在可见光区更优异的光吸收,以及更强的光催化效果。以上方法大多属于二元物质复合法。即将BiOCl与一种半导体材料、贵金属材料、微纳米级载体复合,构造负载与被负载的二元关系。这就导致了以上方法存在BiOCl与其他材料之间的接触面积有限,光生电子-空穴对的分离、转移速率受阻等客观问题。同时,上述大多数改善光催化性能的方法都需要通过诸如两步水热、水热-煅烧、沉降-煅烧等高耗能过程。
近些年,对具有特定晶型暴露、特定缺陷表面BiCOl光催化材料的研究还不甚明朗。申请人认为,以易在水热环境下分解的天然高分子聚合物为诱导剂与软模板,制备具有特异形貌、特定暴露晶面与表面缺陷的BiOCl光催化剂将是未来该种光催化剂的发展趋势之一。
发明内容
本发明所要解决的技术问题是提供一种方法简单、成本低廉、环保、无毒的BiOCl中空微球光催化剂的制备方法。
为解决上述问题,本发明所述的一种BiOCl中空微球光催化剂的制备方法,其特征在于:将壳聚糖分散液缓慢加入到铋盐溶液中,于5℃~ 20℃恒温搅拌10~100 min,使其为胶体态;再在搅拌条件下向体系中缓慢加入氯盐溶液,于5℃~20℃恒温搅拌10~100 min;然后将反应体系移入高压反应釜中,经均相反应、离心分离,得到产品;该产品经蒸馏水洗涤3~9次、50~200℃干燥过夜,即得BiOCl中空微球光催化剂;所述壳聚糖分散液与所述铋盐溶液的体积比为1:1.0~5.0;所述壳聚糖分散液与所述氯盐溶液的体积比为1:0.2~2.0。
所述壳聚糖分散液是指将0.5~5.0 g 壳聚糖溶解于5~50 mL混酸溶液中,于5℃~20℃恒温搅拌10~100 min即得。
所述壳聚糖的分子量为5~20 kDa。
所述铋盐溶液是指将1.5~15 g铋盐溶解于5~50 mL混酸溶液中,混合均匀即得;所述铋盐是指硝酸铋、醋酸铋、柠檬酸铋中的一种。
所述氯盐溶液是指将0.2~2.0g氯盐溶解于5~50 mL混酸溶液中,混合均匀即得;所述氯盐是指氯化钾、氯化钠、十六烷基氯化铵中的一种。
所述混酸溶液是指体积浓度为10 wt%的甲酸、乙酸、丙酸、丁酸四种中的两种按1:1的体积比混合均匀所得的混合液。
所述高压反应釜是指PTFE内衬反应釜或PPL内衬反应釜。
所述均相反应条件是指温度为50~300℃,旋转速率为3~30 rpm/min,时间为6~24h。
所述缓慢加入是指使用蠕动泵,控制2 mL/min的滴加速度将溶液注入反应容器。
所述恒温搅拌是指使用乙醇循环液的冷却循环泵充当冷阱控制反应温度。
本发明与现有技术相比具有以下优点:
1、本发明以壳聚糖CS为模板导向剂和结构诱导剂,通过聚合物水热辅助使铋盐与氯盐结合形成BiOCl,并通过CS分子链段中氨基基团诱导促使BiOCl光催化材料具有高度暴露的晶面(110)和丰富的氧空位,进而拓宽了该催化剂在可见光区的吸收,使得BiOCl中空微球光催化剂在模拟太阳光照射下具有很高的光催化活性。
2、本发明中的CS具有丰富的氨基,且廉价易得、无毒、环保。
3、采用扫描电镜观察本发明所得的BiOCl中空微球光催化剂的微观形貌,结果如图1所示,可以看出,BiOCl中空微球光催化剂具有典型的中空微球结构形貌,是通过BiOCl纳米片自组装构成的。每个BiOCl纳米片厚度大约为15 nm,纳米片与片之间的间隙在20~50nm不等,其自组装构成的BiOCl中空微球直径在5 μm左右。这种特殊形貌的CS杂化BiOCl光催化材料具有较大的比表面积、丰富的活性位点、更好的吸附与光催化效果。
4、通过Brunauer-Emmett-Teller(BET)比表面积测试本发明所得的BiOCl中空微球光催化剂,结果如图2所示,其氮吸附-解吸等温线显示出具有H3型磁滞回线的典型IV吸附-解吸等温线,其通过片状颗粒的积累产生狭缝孔。这一结果与SEM测试结果中材料所显示的多层结构相对应。其BET表面积计算为23.6m2/g。
5、采用X射线衍射测试本发明所得的BiOCl中空微球光催化剂,结果如图3所示。与BiOCl的标准卡片JCPDS 06-0249对比发现,通过CS水热辅助合成制备的BiOCl特征峰明显,没有出现杂质峰。这表明CS杂化BiOCl材料结晶情况良好,且无其它晶体杂质出现。同时,发现11.9°和32.5°为BiOCl中空微球光催化剂(001)和(110)晶面的衍射峰,并且均具有很强的信号,这表明在CS诱导下,BiOCl主要以暴露(110)、(001)晶面为主。说明通过CS水热辅助成功制备了BiOCl中空微球光催化剂,同时该多层级材料具有丰富的氧空位。
6、为了测试BiOCl中空微球光催化剂光催化活性,选用四环素(TC)为代表性抗生素,进行光催化降解试验。称取0.05 g本发明所得的BiOCl中空微球光催化剂,分散到50mL,10 mg/L的TC溶液中,暗反应30 min达到吸附平衡。然后,在光反应器中光催化35 min,每隔一定时间取样5 mL离心,上清液通过0.45 µm的滤膜,采用紫外可见分光光度法测定残余TC的浓度,计算脱色率。
如图4所示,结果表明:BiOCl中空微球光催化剂在暗反应30 min后对TC的脱色率达到28.5%,光照35 min后脱色率达到93.5%,说明主要是光催化降解发挥作用。以上结果说明,本发明制备的BiOCl中空微球光催化剂在模拟太阳光下对TC具有很好的催化降解性能,在光催化降解抗生素废水领域具有很好的应用前景。
7、本发明通过一步水热制备具有特定晶型暴露的BiCOl光催化剂,其方法简单、成本低廉。
附图说明
下面结合附图对本发明的具体实施方式作进一步详细的说明。
图1为本发明BiOCl中空微球光催化剂的扫描电镜图。
图2为本发明BiOCl中空微球光催化剂的BET测试。
图3为本发明BiOCl中空微球光催化剂的X射线衍射图。
图4为本发明BiOCl中空微球光催化剂对TC的光降解数据。
具体实施方式
实施例1 一种BiOCl中空微球光催化剂的制备方法是指:将1L壳聚糖分散液缓慢加入到1.0L铋盐溶液中,于5℃恒温搅拌100 min,使其为胶体态;再在搅拌条件下向体系中缓慢加入0.2L氯盐溶液,于5℃恒温搅拌100 min;然后将反应体系移入高压反应釜中,在温度为50℃、旋转速率为3 rpm/min的条件下均相反应24h,再离心分离,得到产品;该产品经蒸馏水洗涤3次、50℃干燥过夜,即得BiOCl中空微球光催化剂。
其中:壳聚糖分散液是指将0.5 g壳聚糖溶解于5 mL混酸溶液中,于5℃恒温搅拌100 min即得。
铋盐溶液是指将1.5 g铋盐溶解于5 mL混酸溶液中,混合均匀即得。
氯盐溶液是指将0.2g氯盐溶解于5 mL混酸溶液中,混合均匀即得。
混酸溶液是指体积浓度为10 wt%的甲酸和乙酸按1:1的体积比混合均匀所得的混合液。
实施例2 一种BiOCl中空微球光催化剂的制备方法是指:将1L壳聚糖分散液缓慢加入到5.0L铋盐溶液中,于20℃恒温搅拌10 min,使其为胶体态;再在搅拌条件下向体系中缓慢加入2.0L氯盐溶液,于20℃恒温搅拌10 min;然后将反应体系移入高压反应釜中,在温度为300℃、旋转速率为30 rpm/min的条件下均相反应6h,再离心分离,得到产品;该产品经蒸馏水洗涤9次、200℃干燥过夜,即得BiOCl中空微球光催化剂。
其中:壳聚糖分散液是指将5.0 g壳聚糖溶解于50 mL混酸溶液中,于20℃恒温搅拌10 min即得。
铋盐溶液是指将15 g铋盐溶解于50 mL混酸溶液中,混合均匀即得。
氯盐溶液是指将2.0g氯盐溶解于50 mL混酸溶液中,混合均匀即得。
混酸溶液是指体积浓度为10 wt%的丙酸和丁酸按1:1的体积比混合均匀所得的混合液。
实施例3 一种BiOCl中空微球光催化剂的制备方法是指:将1L壳聚糖分散液缓慢加入到3.0L铋盐溶液中,于15℃恒温搅拌50 min,使其为胶体态;再在搅拌条件下向体系中缓慢加入1.0L氯盐溶液,于15℃恒温搅拌60 min;然后将反应体系移入高压反应釜中,在温度为180℃、旋转速率为16 rpm/min的条件下均相反应15h,再离心分离,得到产品;该产品经蒸馏水洗涤6次、120℃干燥过夜,即得BiOCl中空微球光催化剂。
其中:壳聚糖分散液是指将2.5 g 壳聚糖溶解于25 mL混酸溶液中,于15℃恒温搅拌50 min即得。
铋盐溶液是指将8 g铋盐溶解于25mL混酸溶液中,混合均匀即得。
氯盐溶液是指将1.0g氯盐溶解于25 mL混酸溶液中,混合均匀即得。
混酸溶液是指体积浓度为10 wt%的甲酸和丁酸按1:1的体积比混合均匀所得的混合液。
上述实施例1~3中,壳聚糖的分子量为5~20 kDa。铋盐是指硝酸铋、醋酸铋、柠檬酸铋中的一种。氯盐是指氯化钾、氯化钠、十六烷基氯化铵中的一种。高压反应釜是指PTFE内衬反应釜或PPL内衬反应釜。均相反应通过使用可固定反应釜进行。缓慢加入是指使用蠕动泵,控制2 mL/min的滴加速度将溶液注入反应容器。恒温搅拌是指使用乙醇循环液的冷却循环泵充当冷阱控制反应温度。
Claims (10)
1.一种BiOCl中空微球光催化剂的制备方法,其特征在于:将壳聚糖分散液缓慢加入到铋盐溶液中,于5℃~ 20℃恒温搅拌10~100 min,使其为胶体态;再在搅拌条件下向体系中缓慢加入氯盐溶液,于5℃~20℃恒温搅拌10~100 min;然后将反应体系移入高压反应釜中,经均相反应、离心分离,得到产品;该产品经蒸馏水洗涤3~9次、50~200℃干燥过夜,即得BiOCl中空微球光催化剂;所述壳聚糖分散液与所述铋盐溶液的体积比为1:1.0~5.0;所述壳聚糖分散液与所述氯盐溶液的体积比为1:0.2~2.0。
2.如权利要求1所述的一种BiOCl中空微球光催化剂的制备方法,其特征在于:所述壳聚糖分散液是指将0.5~5.0 g 壳聚糖溶解于5~50 mL混酸溶液中,于5℃~ 20℃恒温搅拌10~100 min即得。
3.如权利要求2所述的一种BiOCl中空微球光催化剂的制备方法,其特征在于:所述壳聚糖的分子量为5~20 kDa。
4.如权利要求1所述的一种BiOCl中空微球光催化剂的制备方法,其特征在于:所述铋盐溶液是指将1.5~15 g铋盐溶解于5~50 mL混酸溶液中,混合均匀即得;所述铋盐是指硝酸铋、醋酸铋、柠檬酸铋中的一种。
5.如权利要求1所述的一种BiOCl中空微球光催化剂的制备方法,其特征在于:所述氯盐溶液是指将0.2~2.0g氯盐溶解于5~50 mL混酸溶液中,混合均匀即得;所述氯盐是指氯化钾、氯化钠、十六烷基氯化铵中的一种。
6.如权利要求2、4或5所述的一种BiOCl中空微球光催化剂的制备方法,其特征在于:所述混酸溶液是指体积浓度为10 wt%的甲酸、乙酸、丙酸、丁酸四种中的两种按1:1的体积比混合均匀所得的混合液。
7.如权利要求1所述的一种BiOCl中空微球光催化剂的制备方法,其特征在于:所述高压反应釜是指PTFE内衬反应釜或PPL内衬反应釜。
8.如权利要求1所述的一种BiOCl中空微球光催化剂的制备方法,其特征在于: 所述均相反应条件是指温度为50~300℃,旋转速率为3~30 rpm/min,时间为6~24h。
9.如权利要求1所述的一种BiOCl中空微球光催化剂的制备方法,其特征在于:所述缓慢加入是指使用蠕动泵,控制2 mL/min的滴加速度将溶液注入反应容器。
10.如权利要求1或2所述的一种BiOCl中空微球光催化剂的制备方法,其特征在于:所述恒温搅拌是指使用乙醇循环液的冷却循环泵充当冷阱控制反应温度。
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