CN112058246A - 一种微纳米Fe3O4@BiOCl复合材料及其合成方法 - Google Patents
一种微纳米Fe3O4@BiOCl复合材料及其合成方法 Download PDFInfo
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 45
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Abstract
本发明公开一种微纳米Fe3O4@BiOCl复合材料及其合成方法，通过简单水解沉淀法合成Fe3O4@BiOCl复合材料。首先采用水热法制备出单分散Fe3O4纳米材料，然后在室温下与Bi3+溶液相混合，在弱酸性条件下通过水解‑沉淀法合成Fe3O4@BiOCl复合材料，该材料形貌由片状BiOCl和颗粒状Fe3O4组成，小颗粒Fe3O4附着在BiOCl纳米片的表面，Fe3O4粒径为20‑40nm，BiOCl主晶面为(001)晶面，晶体颗粒长宽为0.5‑1μm，厚度为10‑20nm。该材料具有较大的比表面积、较好的磁性和分散性以及对可见光催化响应。该方法提高了样品的回收率和光催化降解有机污染物的循环稳定性，为解决粉体光催化剂在降解有机污染物的回收问题提供了一种有效的途径。
Description
技术领域
本发明属于化学材料制备领域，具体涉及一种微纳米Fe3O4@BiOCl复合材料及其合成方法，通过简单的水热和水解法制备Fe3O4@BiOCl复合材料，在光催化降解处理工业废水方面有着非常重要的用途。
背景技术
光催化技术是一种新型的绿色氧化还原技术，广泛应用于水体中难降解有机物的去除。目前，在新型层状半导体光催化剂的发展中，氯氧化铋(BiOCl)因为其具有独特的层状结构、合适的能带结构以及高化学和光学稳定性、无毒、低成本以及耐腐蚀等性能受到广大科研工作者的青睐。然而，该材料在实际应用中仍然存在诸如太阳光光响应区间窄、量子效率低、粉体回收利用率低等问题。因此提高该材料的光吸收范围和利用率成为目前研究的重点。
目前，在BiOCl粉体的制备过程中多采用水热法或溶剂热法，高温高压的能耗及有机溶剂等对人体和环境均有一定的影响，其成本也大大提高。针对上述困难，选择黑色的具有磁性的Fe3O4与BiOCl相复合，可得到颜色较深的复合粉体，可同时解决提高光响应和粉体回收率的问题。
本发明基于工艺简单、绿色无污染的原则，首先采用水热法制备出单分散Fe3O4纳米材料，然后在室温下与Bi3+溶液相混合，在弱酸性条件下通过水解-沉淀法合成Fe3O4@BiOCl复合材料，该材料具有较好的磁性、分散性以及优异的可见光催化性能，为解决粉体光催化剂在降解有机污染物后的回收问题提供了一种有效的方法。
发明内容
本发明提供一种微纳米Fe3O4@BiOCl复合材料及其合成方法。制备步骤如下：
(1)水热法制备Fe3O4粉体。取10-13mmol NaOH溶于定量的乙二醇中，搅拌至溶解得到澄清溶液。将3-5mmol FeCl3·6H2O溶于定量的乙二醇中，搅拌至溶解得到棕黄色溶液。将两种溶液混合搅拌均匀后放入水热釜中200℃水热反应10h。自然冷却至室温，离心、洗涤、干燥，得到黑色Fe3O4粉体。
(2)水解法制备Fe3O4@BiOCl复合粉体。取0-1g黑色Fe3O4粉体放入50-250mL去离子水中，超声均匀，记为A。将定量的Bi2O3粉体溶于定量的盐酸中搅拌至完全溶解，记为B。在电动搅拌下，将B缓慢地滴加到A中，并继续反应1h得到深褐色沉淀。将沉淀物离心、洗涤、干燥后，得到Fe3O4@BiOCl复合粉体。
(3)优选的制备工艺，水解法制备Fe3O4@BiOCl复合粉体。Fe3O4粉体为0.3g，去离子水为50mL。(0.1mmol，0.5mmol，1mmol，1.5mmol)的Bi2O3粉体为1mmol，盐酸为3mL。
此工艺制备的Fe3O4@BiOCl复合材料形貌由片状BiOCl和颗粒状Fe3O4组成，小颗粒Fe3O4附着在BiOCl纳米片的表面，Fe3O4粒径为20-40nm，BiOCl长宽为0.5-1μm，厚度为10-20nm。
本发明的主要优点如下：
(1)Fe3O4磁性颗粒沿着片状BiOCl的(001)晶面表面沉积，制得的Fe3O4@BiOCl复合材料的长宽约为0.5-1μm，具有较大的比表面积，提高了材料的吸附性，同时复合材料具有可见光响应特性。
(2)Fe3O4@BiOCl复合材料具有较强的磁性，可提高粉体的回收率及循环利用率。
附图说明
图1是实施例1中Fe3O4@BiOCl的扫描电子显微镜图。
图2是实施例1中Fe3O4@BiOCl的透射电子显微镜图。
图3是实施例1中Fe3O4@BiOCl的高分辨透射电子显微镜图。
图4是实施例1中Fe3O4@BiOCl的XRD图。
图5是实施例1中Fe3O4@BiOCl的磁铁回收样品图。
图6是实施例1中Fe3O4@BiOCl的光催化可见光降解罗丹明B图。
图7是实施例1中Fe3O4@BiOCl的光催化可见光循环降解罗丹明B图。
具体实施方式
下面通过具体实施例和附图对本发明作进一步的说明。本发明的实施例是为了更好地使本领域的技术人员更好地理解本发明，并不对本发明作任何的限制。
实施例1
(1)水热法制备Fe3O4粉体。取12.5mmol NaOH溶于20mL的乙二醇中，搅拌至溶解得到澄清溶液。将4mmol FeCl3·6H2O溶于20mL的乙二醇中，搅拌至溶解得到棕黄色溶液。将两种溶液混合搅拌均匀后放入水热釜中，200℃水热反应10h。自然冷却至室温，离心、洗涤、干燥，得到Fe3O4粉体。
(2)水解法制备Fe3O4@BiOCl复合粉体。取上述(1)制备的0.3g Fe3O4粉体放入50mL去离子水中，超声均匀，记为A。将1mmol的Bi2O3粉体溶于3mL的盐酸中搅拌至完全溶解，记为B。在电动搅拌下，将B缓慢地滴加到A中，并继续反应1h得到深褐色沉淀。将沉淀物离心、洗涤、干燥后，得到Fe3O4@BiOCl复合粉体。
(3)采用5W的低功率可见光光源和浓度为10mg/L罗丹明B，对Fe3O4@BiOCl复合材料光催化性能测试进行评估。采用公式
计算降解率，其中C和C0分别表示反应时间t min和0min处罗丹明B的浓度。
图1为本实施例中Fe3O4@BiOCl复合粉体的扫描电子显微镜图，可以看出产物Fe3O4@BiOCl由片状和不规则的球状组成，整体分散性良好。
图2、图3分别为本实施例中Fe3O4@BiOCl复合粉体的透射电子显微镜图和高分辨透射电子显微镜图，可以看出产物Fe3O4@BiOCl的整体形貌是由不规则的球状附着在纳米片上的复合结构。
图4为本实施例中Fe3O4@BiOCl复合粉体的XRD图，可以看出Fe3O4@BiOCl晶体为BiOCl和Fe3O4复合晶型，峰形尖锐且强度高，表明晶体结构完整。
图5为本实施例中Fe3O4@BiOCl复合粉体的样品回收图，可以看出样品有较好的磁性功能，可轻松实现固液分离，提高粉体的回收使用性。
图6为本实施例中Fe3O4@BiOCl复合粉体在可见光下光催化降解罗丹明B图及循环降解罗丹明B图，可以看出Fe3O4@BiOCl有较好的吸附性及可见光响应，暗反应30min后的吸附率达52.6％，光照60min后对罗丹明B的降解率达100％。
图7为本实施例中Fe3O4@BiOCl复合粉体在可见光下光催化循环降解罗丹明B图，可以看出Fe3O4@BiOCl在可见光下8次光催化循环降解罗丹明B的降解率为98.7％，提高了粉体回收再利用的稳定性。
实施例2
(1)水热法制备Fe3O4粉体。取12.5mmol NaOH溶于20mL的乙二醇中，搅拌至溶解得到澄清溶液。将4mmol FeCl3·6H2O溶于20mL的乙二醇中，搅拌至溶解得到棕黄色溶液。将两种溶液混合搅拌均匀后放入水热釜中，200℃水热反应10h。自然冷却至室温，离心、洗涤、干燥，得到Fe3O4粉体。
(2)水解法制备Fe3O4@BiOCl复合粉体。取上述(1)制备的0.3g Fe3O4粉体放入50mL去离子水中，超声均匀，记为A。将1.5mmol的Bi2O3粉体溶于3mL的盐酸中搅拌至完全溶解，记为B。在电动搅拌下，将B缓慢地滴加到A中，并继续反应1h得到深褐色沉淀。将沉淀物离心、洗涤、干燥后，得到Fe3O4@BiOCl复合粉体。
图6为本实施例中Fe3O4@BiOCl复合粉体在可见光下光催化降解罗丹明B图，可以看出Fe3O4@BiOCl在暗反应30min后的吸附率达34.6％，在光照60min后对罗丹明B的降解率达85.7％。
对比实施例1
(1)水热法制备Fe3O4粉体。取12.5mmol NaOH溶于20mL的乙二醇中，搅拌至溶解得到澄清溶液。将4mmol FeCl3·6H2O溶于20mL的乙二醇中，搅拌至溶解得到棕黄色溶液。将两种溶液混合搅拌均匀后放入水热釜中，200℃水热反应10h。自然冷却至室温，离心、洗涤、干燥，得到Fe3O4粉体。
(2)水解法制备Fe3O4@BiOCl复合粉体。取上述(1)制备的0.3g Fe3O4粉体放入50mL去离子水中，超声均匀，记为A。将0.1mmol的Bi2O3粉体溶于3mL的盐酸中搅拌至完全溶解，记为B。在电动搅拌下，将B缓慢地滴加到A中，并继续反应1h得到深褐色沉淀。将沉淀物离心、洗涤、干燥后，得到Fe3O4@BiOCl复合粉体。
图6为本实施例中Fe3O4@BiOCl复合粉体在可见光下光催化降解罗丹明B图，可以看出Fe3O4@BiOCl在暗反应30min后的吸附率为11.2％，在光照60min后对罗丹明B的降解率为47.9％。生成少量的BiOCl粉体，会降低Fe3O4@BiOCl复合粉体的吸附性和光催化性能。
对比实施例2
(1)水热法制备Fe3O4粉体。取12.5mmol NaOH溶于20mL的乙二醇中，搅拌至溶解得到澄清溶液。将4mmol FeCl3·6H2O溶于20mL的乙二醇中，搅拌至溶解得到棕黄色溶液。将两种溶液混合搅拌均匀后放入水热釜中，200℃水热反应10h。自然冷却至室温，离心、洗涤、干燥，得到Fe3O4粉体。
(2)水解法制备Fe3O4@BiOCl复合粉体。取上述(1)制备的0.3g Fe3O4粉体放入50mL去离子水中，超声均匀，记为A。将0.5mmol的Bi2O3粉体溶于3mL的盐酸中搅拌至完全溶解，记为B。在电动搅拌下，将B缓慢地滴加到A中，并继续反应1h得到深褐色沉淀。将沉淀物离心、洗涤、干燥后，得到Fe3O4@BiOCl复合粉体。
图6为本实施例中Fe3O4@BiOCl复合粉体在可见光下光催化降解罗丹明B图，可以看出Fe3O4@BiOCl在暗反应30min后的吸附率为14.8％，在光照60min后对罗丹明B的降解率为42.8％。说明生成BiOCl粉体的较少，会降低Fe3O4@BiOCl复合材料的光催化性能和吸附性。
尽管上面对本发明的优选实施例进行了描述，但是本发明并不局限于上述的具体实施方式，上述的具体实施方式仅仅是示意性的，并不是限制性的，本领域的普通技术人员在本发明的启示下，在不脱离本发明宗旨和权利要求所保护的范围情况下，还可以做出很多形式的具体变换，这些均属于本发明的保护范围之内。
Claims (5)
1.一种微纳米Fe3O4@BiOCl复合材料及其合成方法，其特征在于，该方法包括如下步骤：
步骤一：将10-13mmol NaOH和3-5mmol FeCl3·6H2O分别溶于一定量的乙二醇中，搅拌至溶解。将两种溶液混合搅拌均匀后放入水热釜中，200℃水热反应10h。自然冷却至室温，离心、洗涤、干燥，得到Fe3O4粉体。
步骤二：取步骤一中得到的0-1g黑色Fe3O4粉体放入一定量去离子水中，超声均匀。将0.1-1.5mmol Bi2O3粉体溶于3mL的HCl中搅拌至完全溶解后，缓慢地滴加到Fe3O4粉体与去离子水的混合溶液中，并继续反应1h得到褐色沉淀。将沉淀物离心、洗涤、干燥后，得到Fe3O4@BiOCl复合粉体。
2.根据权利要求1中所述的一种微纳米Fe3O4@BiOCl复合材料及其合成方法，其特征在于，所述步骤一具体为将10-13mmol NaOH和3-5mmol FeCl3·6H2O分别溶于20-60mL的乙二醇中，搅拌至溶解。
3.根据权利要求1中所述的一种微纳米Fe3O4@BiOCl复合材料及其合成方法，其特征在于，所述步骤二具体为将骤一中得到的0-1g黑色Fe3O4粉体放入50-250mL的去离子水中，超声均匀。
4.根据权利要求1中所述的一种微纳米Fe3O4@BiOCl复合材料及其合成方法，其特征在于，所述步骤二具体为将0.1-1.5mmol Bi2O3粉体溶于3mL的HCl中，搅拌至完全溶解。
5.根据权利要求1中所述的一种微纳米Fe3O4@BiOCl复合材料及其合成方法，其特征在于，Fe3O4@BiOCl复合材料的形貌由片状BiOCl和颗粒状Fe3O4组成，小颗粒Fe3O4附着在BiOCl纳米片的表面，Fe3O4粒径为20-40nm，BiOCl主晶面为(001)晶面，晶体颗粒长宽为0.5-1μm。良好的分散性及复合结构的特征，具有较好的吸附性、可见光响应及可回收循环降解罗丹明B的稳定性。
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