CN110270354A - 一种光催化性能优良的新型卤氧化铋固溶体的制备工艺 - Google Patents
一种光催化性能优良的新型卤氧化铋固溶体的制备工艺 Download PDFInfo
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Abstract
本发明公开了一种光催化性能优良的新型卤氧化铋固溶体的制备工艺，涉及纳米材料光催化领域。步骤如下：将经过超声溶解的五水合硝酸铋、碘化钾和溴化钾组成的乙二醇前驱体溶液，放置于反应釜中进行溶剂热反应，得到新型BiOI1‑xBrx固溶体。本发明提供的超声辅助溶解溶剂热法所合成的新型固溶体比搅拌溶解溶剂热法所合成的常规固溶体降解污染物效果更好。同时新型固溶体的活性晶面暴露比、比表面积和光吸收能力明显高于BiOI，从而光催化性能更优良，能够在紫外光下高效去除水中的全氟化合物，在模拟太阳光下高效去除水中双酚A。为光催化反应在废水处理方面的应用提供良好的材料基础及改性方法。
Description
技术领域：
本发明涉及纳米光催化材料及环境应用领域，具体为一种新型卤氧化铋固溶体光催化材料的制备工艺及高效降解持久性有机污染物的应用研究。
背景技术：
利用太阳能降解污染物，特别是持久性有机污染物的光催化技术，是当前环境污染治理领域迫切需要的技术。
在当前水体污染状况日益严重的背景下，一类持久性有机污染物---全氟化合物(PFCs)的环境污染及去除技术受到了人们的重视。PFCs，由于其高键能的C-F键结构，具有热稳定性、化学稳定性和高表面活性等优点，在过去几十年中一直被广泛用作表面活性剂、阻燃剂等工农业产品生产中。近年来的调查发现，由于广泛的应用，PFCs已经在多种环境介质中广泛检出，其中检出频率最高，污染最高的是全氟辛酸(PFOA)和全氟辛烷磺酸(PFOS)两种。近年来大量的研究揭示了PFCs具有环境持久性、生物积累效应及广泛生物毒性。PFOS等已经被斯德哥尔摩公约组织定位持久性有机污染物。因此，寻找高效、而且经济的环境消除PFCs技术成为了当前环境领域研究的热点之一。其中，在各种处理技术中，光催化技术由于高效、环保、成本低等特点，在水处理中的应用前景备受关注。本专利尝试制备一种可高效降解PFCs的光催化材料及配套降解技术，为PFCs等污染物的环境去除提供有效的材料及技术。
碘氧化铋(BiOI)，由于其特殊的层状结构和良好的光催化性能，在众多的可见光催化材料当中占有重要的地位，具有非常良好的应用前景。但是，其光生电子-空穴易复和的弊端，大大限制了其应用。因此，许多研究者试图通过多种形貌、组成、结构等的调控来提高它催化活性的目的，其中，通过引入Cl、Br两种卤素来制备固溶体是增强BiOI性能的重要途径。由于BiOCl、BiOBr与BiOI具有相似的层状结构和原子排列，Cl、Br很容易掺入BiOI的晶格中，形成BiOI1-xYx(Y＝Cl，Br)的固溶体。固溶体的形成导致BiOI的晶体结构发生微调，带隙宽度改变，导带价带位置改变，促进光生电子-空穴对的有效分离，进而可大大提高BiOI的光催化性能。近年来，固溶体的材料制备报道很多，但是对于溴掺入量，特别是微量溴的掺入的影响，研究较少。目前，BiOI固溶体的制备，普遍采用溶剂热法工艺，而且，围绕铋源和碘源在溶剂中分散、溶解的关键工艺步骤中，人们普遍局限于常规的搅拌工艺，尚缺乏其他辅助分散、溶解工艺的引入对于材料性能的影响的研究。本专利采用微量溴掺杂、引入超声辅助分散溶解技术，尝试制备新型的BiOI1-xBrx固溶体，并用于降解PFOA和PFOS的应用。
发明内容：
本发明的目的在于提供一种新型BiOI1-xBrx固溶体的制备工艺，并通过该材料有效去除全氟化合物。通过此方法合成的新型BiOI1-xBrx固溶体对全氟化合物具有良好的降解效果，从而有效拓展了光催化材料的合成方法，丰富了去除难降解物质的应用。
本发明通过以下技术方案实现上述目的：
1.一种光催化性能优良的新型卤氧化铋固溶体的制备工艺，其具体步骤如下：
1)将Bi(NO3)3·5H2O溶解于乙二醇中，超声配成溶液；
2)将KI溶解于乙二醇中，超声配成溶液；
3)将2)溶液加入至1)溶液中；
4)将KBr加入到3)溶液中，超声直到KBr完全溶解；
5)将4)所制的溶液转入高压反应釜，置于烘箱中加热，然后冷却、清洗、烘干，得到BiOI1-xBrx(x＝0.05)。
2.如权利要求1所述新型BiOI1-xBrx固溶体的制备工艺，其特征在于：步骤1)中，Bi(NO3)3·5H2O为0.97g，乙二醇为20ml，超声30分钟。
3.如权利要求1所述新型BiOI1-xBrx固溶体的制备工艺，其特征在于：步骤2)中，KI为0.32g，乙二醇为20ml，超声30分钟。
4.如权利要求1所述新型BiOI1-xBrx固溶体的制备工艺，其特征在于：步骤4)中，KBr为0.01g，超声10分钟。
5.如权利要求1所述新型BiOI1-xBrx固溶体的制备工艺，其特征在于：步骤5)中，加热温度为160℃，保持12h，清洗为用乙醇和去离子水清洗，烘干温度和时间为60℃和12h。
本发明提供的新型BiOI1-xBrx固溶体材料的制备工艺极大提高了BiOI的比表面积和光电性能，而且使光生电子对有效分离，从而显著提高光催化剂的催化效果，使得在紫外光下能够高效去除水中的全氟化合物，丰富了材料合成的方法；同时过程简单，可适用于大批量生产。
附图说明：
图1为实施例1中BiOI及新型BiOI1-xBrx(x＝0.05)固溶体的X射线衍射(XRD)图谱；
图2为实施例1中BiOI及新型BiOI1-xBrx(x＝0.05)固溶体扫描电子显微镜(SEM)图；
图3为实施例1中BiOI及新型BiOI1-xBrx(x＝0.05)固溶体紫外-可见漫反射(UV-Vis)图谱；
图4为实施例2降解全氟辛酸(PFOA)的性能示意图；
图5为实施例3降解全氟辛烷磺酸(PFOS)的性能示意图；
图6为实施例4降解双酚A(BPA)的性能示意图。
具体实施方式：
以下实施例是对本发明的进一步说明，而不是对本发明的限制。
实施例1：制备新型BiOI1-xBrx(x＝0.05)固溶体
1)将0.97g Bi(NO3)3·5H2O溶解于20ml乙二醇中，超声30min配成溶液；
2)将0.32g KI溶解于另一20ml乙二醇中，超声30min配成溶液；
3)将2)所得碘化钾溶液缓慢加入到1)所得硝酸铋溶液中，摇匀得到黄色透明溶液；
4)将0.01g KBr加入到3)中超声得到黄色透明溶液；
5)将4)所制的前驱体溶液，转入50ml聚四氟乙烯高压反应釜中，密封置于烘箱中160℃加热12h，冷却；
6)滤膜过滤，用乙醇和去离子水清洗，60℃下烘干12h，得到新型BiOI1-xBrx(x＝0.05)固溶体。
7)其他掺杂量的复合材料分别改变KI和KBr的量即可。
8)将超声改为搅拌即得到常规BiOI1-xBrx(x＝0.05)固溶体。
实施例1中制得的新型BiOI1-xBrx(x＝0.05)固溶体通过XRD来确定晶面结构及组成，通过SEM进行形貌表征，通过紫外-可见漫反射表征其光吸收特性。如图1所示，经过分析，与BiOI相比，新型BiOI1-xBrx(x＝0.05)固溶体和常规BiOI1-xBrx(x＝0.05)固溶体所出现的特征峰稍微向高角度方向移动，而不是BiOI和BiOBr的简单叠加，说明所合成的材料并不是BiOI和BiOBr的简单物理混合，而是溴进入BiOI晶格内，形成复合材料；可以看出，新型BiOI1-xBrx(x＝0.05)固溶体中{001}晶面和{002}晶面对应的特征峰远远高于BiOI和常规BiOI1-xBrx(x＝0.05)固溶体中相应的峰，而其它峰的强度基本相等，这是因为在超声条件下，溴的加入改变了晶面取向，使得{001}晶面和{002}晶面更容易暴露。值得注意的是，超声和搅拌两种溶解方式只是对于BiOI1-xBrx固溶体的合成有区别，对于BiOI的合成结果并无差别。至于新型BiOI1-xBrx(x＝0.05)固溶体中只显示出{001}晶面和{002}晶面对应的特征峰，那是因为这两个峰的强度太大，使得其他峰看起来特别小甚至看不见，实际上经过软件分析，其他峰的强度相比BiOI并无多大变化。如图2所示，BiOI呈现花瓣状结构，新型BiOI1-xBrx(x＝0.05)固溶体呈现纳米片状结构，其孔结构明显比BiOI密集，从而大大增加了材料的比表面积、活性位点数量和传输通道，进而大大促进光催化反应。如图3所示，新型BiOI1-xBrx(x＝0.05)固溶体在600nm以下的光吸收强度约为BiOI的3倍，在600nm以上也有较强吸收，而BiOI在600nm以上光吸收强度几乎为零，这就使得在同等光照条件下，新型BiOI1-xBrx(x＝0.05)固溶体能够吸收利用更多的光，从而大大加快光催化反应。
实施例2：新型BiOI1-xBrx(x＝0.05)固溶体紫外光下去除全氟辛酸(PFOA)
用去离子水配制浓度为20mg/L的全氟辛酸(PFOA)水溶液，取30ml加入光反应用的石英管里，然后加入12mg新型BiOI1-xBrx(x＝0.05)材料，并加入磁力搅拌子，放入光反应装置，打开冷凝水控制反应温度为25℃，然后打开电源，开启搅拌按钮，先进行暗反应达到吸附脱附平衡，再打开灯，灯功率为300W汞灯，反应前后PFOA的浓度通过液相色谱测定，结果如图4所示，新型BiOI1-xBrx固溶体反应120分钟后去除率达到99％，而BiOI以及常规BiOI1- xBrx固溶体反应120分钟后去除率分别只达到70％和64％，报道的β-Ga2O3在254nm紫外光照射3h对PFOA的降解率仅为38％，TiO2在紫外光下照射8h降解率也仅为35％。说明新型BiOI1-xBrx固溶体对于PFOA有着非常好的催化降解性能。
实施例3：新型BiOI1-xBrx(x＝0.05)固溶体紫外光下去除全氟辛烷磺酸(PFOS)
用去离子水配制浓度为20mg/L的全氟辛烷磺酸(PFOS)水溶液，取30ml加入光反应用的石英管里，然后加入12mg新型BiOI1-xBrx(x＝0.05)材料，并加入磁力搅拌子，放入光反应装置，打开冷凝水控制反应温度为25℃，然后打开电源，开启搅拌按钮，先进行暗反应达到吸附脱附平衡，再打开灯，灯功率为300W汞灯，反应前后PFOS的浓度通过液相色谱质谱联用仪测定，结果如图5所示，反应120分钟后，PFOS去除率达到91％；据报道在P25催化作用下，PFOS在300W汞灯照射8h的去除率仅为19.9％，可见新型BiOI1-xBrx(x＝0.05)固溶体对于PFOS有着非常好的催化降解性能。
实施例4：新型BiOI1-xBrx(x＝0.05)固溶体模拟太阳光下高效去除双酚A(BPA)
为考察新型BiOI1-xBrx(x＝0.05)固溶体对其他难降解物质的降解效果以及模拟太阳光下的降解效率，选取具有代表性的双酚A(BPA)作为目标物。用去离子水配制浓度为10mg/L的双酚A(BPA)水溶液，取30ml加入光反应用的石英管里，然后加入15mg新型BiOI1- xBrx(x＝0.05)材料，并加入磁力搅拌子，放入光反应装置，打开冷凝水控制反应温度为25℃，然后打开电源，开启搅拌按钮，先进行暗反应达到吸附脱附平衡，再打开灯，灯功率为800W氙灯，反应前后BPA的浓度通过液相色谱测定，结果如图6所示，30分钟降解率达到100％，而据报道BiOI 30分钟内降解BPA的效率只有50％，可见新型BiOI1-xBrx(x＝0.05)固溶体对于PFOS有着非常好的催化降解性能。
Claims (5)
1.一种光催化性能优良的新型卤氧化铋固溶体的制备工艺，其具体步骤如下：
1)将Bi(NO3)3·5H2O溶解于乙二醇中，超声配成溶液；
2)将KI溶解于乙二醇中，超声配成溶液；
3)将2)溶液加入至1)溶液中；
4)将KBr加入到3)溶液中，超声直到KBr完全溶解；
5)将4)所制的溶液转入高压反应釜，置于烘箱中加热，然后冷却、清洗、烘干，得到BiOI1-xBrx(x＝0.05)。
2.如权利要求1所述新型BiOI1-xBrx固溶体的制备工艺，其特征在于：步骤1)中，Bi(NO3)3·5H2O为0.97g，乙二醇为20ml，超声30分钟。
3.如权利要求1所述新型BiOI1-xBrx固溶体的制备工艺，其特征在于：步骤2)中，KI为0.32g，乙二醇为20ml，超声30分钟。
4.如权利要求1所述新型BiOI1-xBrx固溶体的制备工艺，其特征在于：步骤4)中，KBr为0.01g，超声10分钟。
5.如权利要求1所述新型BiOI1-xBrx固溶体的制备工艺，其特征在于：步骤5)中，加热温度为160℃，保持12h，清洗为用乙醇和去离子水清洗，烘干温度和时间为60℃和12h。
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