CN112108166B - 一种超薄Bi4O5Br2/Bi2O2CO3可见光催化剂及其制备方法与应用 - Google Patents
一种超薄Bi4O5Br2/Bi2O2CO3可见光催化剂及其制备方法与应用 Download PDFInfo
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Abstract
本发明公开了一种超薄Bi4O5Br2/Bi2O2CO3可见光催化剂及其制备方法与应用。该超薄Bi4O5Br2/Bi2O2CO3可见光催化剂通过简易的室温共结晶法制备，包括如下制备步骤：(1)在水中加入氨水，搅拌，得到溶液A；(2)将一定量的溴化钾或溴化钠加入到上述溶液A，搅拌一段时间，得到溶液B；(3)将铋盐溶于稀醋酸溶液，并逐滴加入溶液B中，搅拌过夜，得到悬浊液C；(4)悬浊液C经离心、水洗、干燥后即可得到所述可见光催化剂。本发明在中性室温可见光照条件下对难降解有毒有害有机污染物就具有很高的去除效率及光稳定性，且具有很好的固液分离效果。
Description
技术领域
本发明属于水处理功能材料领域，具体涉及一种超薄Bi4O5Br2/Bi2O2CO3可见光催化剂及其制备方法与应用。
背景技术
新兴有机污染物在全球水资源中频繁检出，并且已经证实其对生态和人类健康具有潜在危害，因此引起了全球的关注。目前已经在研究或讨论的有860种新兴有机污染物，包括医药和个人护理品、农药、内分泌干扰物等。由于新兴有机污染物的多样性和低浓度水平，其有效去除需要联合的水处理过程，包括传统的二级活性污泥法和三级处理如高级氧化过程、膜分离和吸附过程。工程纳米材料可以促进多种水处理功能的复合，并且可以同时去除水中不同污染物，因此具有绝对的竞争优势。这对于简化处理流程、减少碳足迹和增强处理效率非常重要。获得活性位点的高暴露是催化效率提高的关键。超薄二维纳米材料由于尺寸效应和大量活性位点的暴露能够极大地增加催化过程的效率。
卤氧铋是一种研究较多的可见光催化剂，由于其杂化的价带能够增强光生空穴的可移动性，并且相比氧化物半导体更利于氧化反应，因此具有应用于水处理氧化有机污染物的前景。为了提高其催化活性及稳定性，近年来，通过增加Bi:X比的富铋技术得到发展。已报道的富铋卤氧铋中，Bi4O5Br2因其有效的可见光吸收和结构稳定性已经被广泛的研究用于催化和能源转化。然而，目前Bi4O5Br2的制备通常需要高温高压条件下水热或溶剂热法，或者步骤繁杂的水解法，因而为了降低制备成本，寻求简易的制备方法势在必行。另外，为了实现二维纳米片的可循环利用，常规的构建方法即通过物理复合载体组分固定活性纳米片的方法，通常导致活性组分的聚集和活性衰减。为了进一步提高Bi4O5Br2的催化活性，同时避免其对水安全产生负效应，研制易于循环利用的高活性二维Bi4O5Br2纳米片至关重要。
发明内容
本发明的目的是提供一种可循环利用的高活性超薄Bi4O5Br2纳米片可见光催化剂及其制备方法与应用，该催化剂为纵向伫立于Bi2O2CO3薄片上的超薄Bi4O5Br2纳米片(厚度约10nm)，通过简易的室温共结晶法制备，Bi4O5Br2与Bi2O2CO3之间形成强相互作用，同时Bi4O5Br2表面形成氧空位，促使表面光生电荷快速分离并迁移到表面发生反应，相比商品化光催化剂P25、标准可见光催化剂N-TiO2和Bi4O5Br2(厚度约50nm)，其光催化效率分别提高了28.1、9.5和8.5倍。此外，实验证明Bi4O5Br2/Bi2O2CO3在光照下比较稳定，易于分离、可循环利用。解决目前可见光催化体系存在的催化活性差、太阳能转化效率低以及光稳定性差等问题。
本发明提供的超薄Bi4O5Br2/Bi2O2CO3可见光催化剂的制备方法，包括如下步骤：
(1)在水中加入氨水，搅拌，得到溶液A；
(2)将一定量的溴化钾或溴化钠加入到上述溶液A，搅拌一段时间，得到溶液B；
(3)将铋盐溶于稀醋酸溶液，并逐滴加入溶液B中，搅拌过夜，得到悬浊液C；
(4)悬浊液C经离心、水洗、干燥后得到所述超薄Bi4O5Br2/Bi2O2CO3可见光催化剂。
上述的制备方法，步骤(1)中，每148mL水中加入2～2.3ml的氨水，具体可为每148mL水中加入2.3ml氨水；所述搅拌的转速可为450～700转/分钟，具体可为450转/分钟。
上述的制备方法，步骤(2)中，所述溴化钾或溴化钠的摩尔量为0.2～0.4mmol，具体可为0.2mmol；所述搅拌的转速可为450～700转/分钟，具体可为450转/分钟，时间可为20～40分钟，具体可为30分钟。
上述的制备方法，步骤(3)中，所述铋盐稀醋酸溶液与所述溶液B的体积比为1:(10～18)，具体可为1：15；所述铋盐稀醋酸溶液中，以五水合硝酸铋计，所述铋盐的质量体积浓度为0.02～0.03g/mL，具体可为0.025g/mL，所述铋盐可为硝酸铋(具体可以五水合硝酸铋的形式进行添加)或氯化铋。
上述的制备方法，步骤(3)中，所述搅拌过夜在温度25～35℃(如25℃)的条件下进行，转速可为450～700转/分钟，具体可为450转/分钟，时间可为10～15小时，具体可为12小时。
上述的制备方法，步骤(4)中，所述离心的转速可为5000～8000rpm条件下进行，具体可为8000rpm，时间可为3～6分钟，具体可为3分钟；所述水洗的次数可为3～6遍，具体可为6遍，洗至pH值中性为宜；所述干燥在常规空气条件下，温度可为50～70℃，具体可为60℃，时间可为5～8小时，具体可为5小时。
上述的制备方法，所述方法在步骤(4)中所述干燥之后还包括将所述催化剂研磨，得粉末的步骤。
由上述的制备方法制备得到的超薄Bi4O5Br2/Bi2O2CO3可见光催化剂，也在本发明的保护范围内，该可见光催化剂是一种黄色的固体粉末；该可见光催化剂中超薄Bi4O5Br2纳米片的厚度约为10nm，纵向伫立于Bi2O2CO3薄片上；Bi4O5Br2与Bi2O2CO3之间存在强相互作用；需在液体环境中与太阳光或人工光照联合使用(光照具体也可为波长大于400纳米的可见光)，形成光催化体系。
超薄Bi4O5Br2/Bi2O2CO3可见光催化剂在下述1)-3)中的至少一种的应用，也在本发明的保护范围内：
1)高效处理有机污染物；
2)增强在有机污染物处理过程中耐光腐蚀、可重复循环利用能力；
3)提高有机污染物处理后Bi4O5Br2的固液分离能力。
上述的应用中，所述有机污染物可为苯酚、双酚A、2-氯酚、磺胺甲恶唑、环丙沙星、双氯芬酸的任一种。
上述的应用中，所述有机污染物的浓度可为5～100mg/L。
本发明与现有光催化体系相比具有以下优势：
(1)本发明去除有机污染物的效率很高，相比商品化光催化剂P25、标准可见光催化剂N-TiO2和Bi4O5Br2(厚度约50nm)，其光催化效率分别提高了28.1、9.5和8.5倍。；
(2)本发明在去除有机污染物的过程中具有很好的稳定性，无明显结构变化；
(3)本发明相比单纯的Bi4O5Br2薄片更易于固液分离；
(4)本发明制备方法简易，只需室温搅拌即可，且没有贵金属等掺杂，成本低廉，操作简单。
附图说明
图1为实施例1中制备得到的超薄Bi4O5Br2/Bi2O2CO3的XRD谱图。
图2为实施例1中制备得到的超薄Bi4O5Br2/Bi2O2CO3的扫描电镜的照片。
图3为实施例1中制备得到的超薄Bi4O5Br2/Bi2O2CO3的透射电镜的照片。
图4为实施例1中制备得到的超薄Bi4O5Br2/Bi2O2CO3对于2-氯苯酚的催化去除效果。
图5为实施例1中制备得到的超薄Bi4O5Br2/Bi2O2CO3对于2-氯苯酚降解的循环反复利用活性评价图。
具体实施方式
下述实施例中所使用的实验方法如无特殊说明，均为常规方法。
下述实施例中所用的材料、试剂等，如无特殊说明，均可从商业途径得到。
实施例1、可见光催化剂的制备及应用实验
一、制备
按照如下步骤制备超薄Bi4O5Br2/Bi2O2CO3可见光催化剂：
(1)将2.3mL氨水加入到148mL超纯水中，搅拌(转速为450转/分钟)，形成溶液A；
(2)将0.2mmol溴化钾或溴化钠加入到上述溶液A，搅拌30分钟(转速为450转/分钟)，得到溶液B；
(3)将0.25g五水合硝酸铋(Bi(NO3)3·5H2O)溶入10mL稀醋酸溶液中，并将该溶液逐滴加入溶液B中，搅拌过夜(搅拌时间12小时，转速为450转/分钟)，得到悬浊液C；
(4)将悬浊液C，8000rpm离心，并用超纯水清洗至中性(约洗涤6遍，每次离心时间3分钟)，60℃烘箱干燥5小时，在玛瑙研钵中充分研磨成粉末，即得到目标材料—超薄Bi4O5Br2/Bi2O2CO3可见光催化剂。
对比例1、
按照如下步骤制备Bi4O5Br2薄片：
(1)将4mmol五水合硝酸铋(Bi(NO3)3·5H2O)溶入40mL丙三醇中，搅拌30分钟，形成溶液A；
(2)将4mmol溴化钠(NaBr)溶于40mL丙三醇中，搅拌30分钟，并将该溶液逐滴加入到溶液A中，继续搅拌30分钟，得到均匀悬浊液B；
(3)将悬浊液B转移到100mL高压釜，160℃热处理16小时；冷却至室温后，8000rpm离心，并用超纯水和无水乙醇交替洗涤数次，80℃干燥12小时，得到固体C；将固体C在玛瑙研钵中充分研磨成粉末；
(4)将0.15g固体C分散于100mL超纯水，50℃水浴搅拌水解，固体C由黑色转变为浅黄色，最后用超纯水洗涤数次，80℃干燥后，即得到Bi4O5Br2薄片。
对比例2、
按照如下步骤制备氮掺杂纳米二氧化钛(N-TiO2)：
(1)将3.0mL硝酸加入到100mL超纯水中，形成溶液A；
(2)15mL钛酸四丁酯逐滴加入到溶液A中，剧烈搅拌4小时(转速为600转/分钟)后，得到半透明溶胶B；
(3)半透明溶胶B中加入30mL正丙醇，搅拌至半透明溶胶完全变成透明溶液后，加入尿素(25％w/v)，混合均匀后，转移至100℃烘箱中，干燥得到固体C；
(4)将固体C研磨均匀后，转移至马弗炉中焙烧，升温速率5℃/min，在450℃下焙烧2小时，自然降至室温后形成固体D；将固体D在玛瑙研钵中充分研磨成粉末，即得到N-TiO2。
二、表征
图1为实施例1中制备得到的超薄Bi4O5Br2/Bi2O2CO3、Bi4O5Br2以及Bi2O2CO3的XRD对比谱图，由该图可以看出，本实施例制备得到的催化剂具备明显的Bi4O5Br2和Bi2O2CO3的特征晶面峰。
图2为实施例1中制备得到的超薄Bi4O5Br2/Bi2O2CO3、Bi4O5Br2以及Bi2O2CO3的扫描电镜对比图，证实超薄Bi4O5Br2/Bi2O2CO3中Bi4O5Br2纳米片的厚度约为10nm，纵向伫立于Bi2O2CO3薄片上，而单纯Bi4O5Br2的厚度约为50nm。
图3为实施例1中制备得到的超薄Bi4O5Br2/Bi2O2CO3的透射电镜图，进一步证实超薄Bi4O5Br2/Bi2O2CO3中Bi4O5Br2纳米片伫立于Bi2O2CO3薄片上。
三、应用实验
将0.1g上述合成的催化剂投入60mL污染物溶液中，避光条件下搅拌30分钟，待污染物和催化剂之间达到吸附平衡后，开始照光(5W LED白灯珠)反应，在不同的时间点取样检测污染物的浓度及TOC浓度。
图4反映了该催化剂与Bi4O5Br2、Bi2O2CO3、N-TiO2和P25在中性条件下对于2-氯酚的去除效果对比图。从图中可以看出，超薄Bi4O5Br2/Bi2O2CO3可见光催化剂对于2-氯酚的催化降解速率分别是Bi4O5Br2、N-TiO2、P25和Bi2O2CO3的8.5、9.5、28.1和35.1倍。
待可见光催化反应结束后将催化剂滤出并用去离子水洗去表面吸附的污染物，在60℃下烘干后，重复上面的可见光催化反应步骤，考察超薄Bi4O5Br2/Bi2O2CO3可见光催化剂的循环反复利用活性。图5展示了该催化剂对于催化降解2-氯苯酚的循环反复利用活性评价图。从图中可以看出，催化剂循环使用8次，超薄Bi4O5Br2/Bi2O2CO3对于2-氯酚的矿化率仍然达到70％以上，可以应用于实际水体的处理。
Claims (6)
1.一种超薄Bi4O5Br2/Bi2O2CO3可见光催化剂的制备方法，包括如下步骤：
(1)在水中加入氨水，搅拌，得到溶液A，其浓度为2～2.3mL氨水/148mL水；
(2)将一定量的溴化钾或溴化钠加入到上述溶液A，搅拌一段时间，得到浓度为1.3～2.6mmol/L的含溴盐溶液B；
(3)将铋盐溶于稀醋酸溶液，以五水合硝酸铋计，得到浓度为0.02～0.03g/mL的铋盐稀醋酸溶液，并逐滴加入溶液B中，在温度25～35℃的条件下搅拌过夜，得到悬浊液C；
(4)将悬浊液C离心、水洗、空气烘箱干燥后即可得到所述超薄Bi4O5Br2/Bi2O2CO3可见光催化剂；
铋盐的溶解介质为稀醋酸；其原料的投加顺序为溴化钾或溴化钠加入到溶液A的顺序，以及溶于稀醋酸的铋盐溶液加入到溶液B的顺序；超薄Bi4O5Br2纳米片，厚度约10nm，表面存在氧空位，纵向伫立于Bi2O2CO3薄片上，Bi4O5Br2与Bi2O2CO3两组分间存在强相互作用，易于固液分离。
2.根据权利要求1所述的制备方法，其特征在于：步骤(1)中，所述搅拌的转速为450～700转/分钟。
3.根据权利要求1或2所述的制备方法，其特征在于：步骤(2)中，所述溴化钾或溴化钠的摩尔量为0.2～0.4mmol；所述搅拌的转速为450～700转/分钟，时间为20～40分钟。
4.根据权利要求3所述的制备方法，其特征在于：步骤(3)中，所述铋盐稀醋酸溶液与所述溶液B的体积比为1:(10～18)；所述铋盐稀醋酸溶液中，以五水合硝酸铋计，所述铋盐的质量体积浓度为0.02～0.03g/mL，所述铋盐为硝酸铋或氯化铋；所述搅拌过夜在温度25～35℃的条件下进行，转速为450～700转/分钟，时间为10～15小时。
5.根据权利要求4所述的制备方法，其特征在于：步骤(4)中，所述干燥在空气条件下，温度为50～70℃，时间为5～8小时。
6.权利要求5所述的制备方法制备得到的超薄Bi4O5Br2/Bi2O2CO3可见光催化剂，该催化剂的特征在于：超薄Bi4O5Br2纳米片，厚度约10nm，表面存在氧空位，纵向伫立于Bi2O2CO3薄片上，Bi4O5Br2与Bi2O2CO3两组分间存在强相互作用，易于固液分离。
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