CN115228492A - 一种碘化银/碳酸根自掺杂碳酸氧铋光催化材料的制备方法和应用 - Google Patents
一种碘化银/碳酸根自掺杂碳酸氧铋光催化材料的制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种碘化银/碳酸根自掺杂碳酸氧铋光催化材料的制备方法和应用，制备方法包括：(1)将五水合硝酸铋、尿素和柠檬酸钠溶解在去离子水中，搅拌后将溶液转移到聚四氟乙烯内衬的水热反应釜中进行水热反应，反应结束后离心分离取沉淀，经洗涤，干燥，研磨得到产物CO3 2‑‑Bi2O2CO3；(2)将CO3 2‑‑Bi2O2CO3溶解于超纯水中，超声后加入AgNO3溶液，搅拌，再加入KI溶液，搅拌，经离心收集沉淀，洗涤，干燥，研磨后得到光催化剂AgI/CO3 2‑‑Bi2O2CO3。用氙灯作为光源，通过滤波片将低波长的光滤去(λ<420nm)，对AgI/CO3 2‑‑Bi2O2CO3复合光催化材料进行光催化性能测试。用2‑羟基‑1,4‑萘醌、左氧氟沙星的降解率来表征AgI/CO3 2‑‑Bi2O2CO3复合光催化材料的光催化性能。该材料具有化学稳定性高、光吸收能力较强、制备方法简单、成本低等优点。
Description
技术领域
本发明属于光催化材料制备领域，尤其是可见光催化材料技术领域，具体涉及一种碘化银/碳酸根自掺杂碳酸氧铋光催化材料的制备方法和应用。
背景技术
在污水处理中，光催化氧化作为一种新型高级氧化技术，在光化学氧化基础上发展起来，氧化能力强，无二次污染，其可在常温常压下进行，具有环保、节能等特点。
铋基半导体是近年发展起来的新型光催化材料。由于Bi原子的特殊结构，其化合物很容易形成层状结构，产生具有可见光响应能力的铋系化合物。Bi2O2CO3作为一种很有前途的光催化剂，由于其化学稳定性、无毒性和低成本，在光降解有毒离子或化合物的环境净化方面受到了广泛关注。Bi2O2CO3作为一种典型的奥里维里斯(Aurivillius)型氧化物，属于四方晶系，具有[Bi2O2]2+层和[CO3]2+层交替组成的独特层状结构；同时，极化作用产生的内电场有利于光生电子与空穴的分离，从而使其有较高的光催化性能。然而，Bi2O2CO3较大的带隙值(3.1～3.5eV)对可见光的吸收有较大限制。鉴于Bi2O2CO3的内部阴离子基团和适合修饰的层状结构，Bi2O2CO3作为一种可行的衬底，用于探测阴离子基团自掺杂对宽禁带半导体的影响。因此，制备了对可见光吸收性能更好的CO3 2-自掺杂的Bi2O2CO3(CO3 2--Bi2O2CO3)。但改进后CO3 2--Bi2O2CO3在光催化应用中依旧存在电子-空穴对的快速复合的缺点。通过对其形成异质结可以促进太阳能的吸收和利用，加速光生载流子的传输。
近年来，科学家发现AgX是降解各种有机化合物的良好可见光光催化剂，AgI深受人们关注，因为它是一种n型半导体，具有2.7-2.8eV的可见范围带隙。越负的CB位置使光生电子具有较强的还原能力。故认为，将AgI与CO3 2--Bi2O2CO3复合制备高效光催化剂是可行的。
发明内容
本发明提供一种碘化银/碳酸根自掺杂碳酸氧铋光催化材料的制备方法和应用，光催化剂的制备方法简单、成本低、可见光响应程度提高、光催化性能好，对于2-羟基-1,4-萘醌和左氧氟沙星有较好的去除效果，无二次污染。
具体步骤为：
(1)将五水合硝酸铋、尿素和柠檬酸钠溶解在去离子水中，搅拌，获得均匀的悬浮液；
(2)将步骤(1)所得溶液转移到聚四氟乙烯内衬的水热反应釜中进行水热反应；
(3)将步骤(2)得到的反应液过滤收集沉淀，洗涤，干燥，研磨得到产物CO3 2--Bi2O2CO3；
(4)称取上述步骤所得产物CO3 2--Bi2O2CO3溶解于超纯水中，超声一段时间；
(5)向步骤(4)所得溶液加入AgNO3溶液，并搅拌；
(6)向步骤(5)所得溶液加入KI溶液，搅拌，离心收集沉淀，洗涤，干燥，研磨后得到光催化剂AgI/CO3 2--Bi2O2CO3。
优选的，所述步骤(1)磁力搅拌时间均为60min。
优选的，所述步骤(2)的水热反应温度为160℃，并在此温度下保持24h。
优选的，所述步骤(3)烘箱干燥温度为60℃，时间为20h；
优选的，所述步骤(4)超声时间为30min；
优选的，所述步骤(5)磁力搅拌时间为15min；
优选的，所述步骤(6)磁力搅拌时间为2h，烘箱干燥温度为80℃，时间为12h。
本发明方法的优点：
(1)本发明主要采用自掺杂、形成异质结的方法对光催化剂进行改性。形成异质结是提高可见光响应的一种重要方法，可以利用价带、能级的差异，促进光催化剂中电子传递，减少光电子和空穴的复合，从而提高光催化剂对2-羟基-1,4-萘醌和左氧氟沙星的去除效果。
(2)本发明是以Bi2O2CO3为基础，通过自掺杂的方式形成CO3 2--Bi2O2CO3。通过简单的静电驱动自组装方法制备了不同复合比例的AgI/CO3 2--Bi2O2CO3，制备方法简单易操作。制备的AgI/CO3 2--Bi2O2CO3光催化材料具有在可见光下有效降解2-羟基-1,4-萘醌、左氧氟沙星的性能。
(3)制备的AgI/CO3 2--Bi2O2CO3光催化材料具有较好的循环稳定性，避免了进行一次光催化后材料的光催化效率大幅度降低的问题。
(4)运用简单，只需要将制备的AgI/CO3 2--Bi2O2CO3光催化材料粉末投入到一定浓度的2-羟基-1,4-萘醌或左氧氟沙星中，在可见光下就可以进行降解。
附图说明
图1：AgI/CO3 2--Bi2O2CO3光催化材料的XRD谱图；
图2：AgI/CO3 2--Bi2O2CO3光催化材料的SEM图；
图3：AgI/CO3 2--Bi2O2CO3光催化材料的傅里叶红外光谱图；
图4：AgI/CO3 2--Bi2O2CO3光催化材料的紫外-可见漫反射光谱图(a)及禁带宽度图(b)；
图5：AgI/CO3 2--Bi2O2CO3光催化材料的PL图；
图6：AgI/CO3 2--Bi2O2CO3光催化材料的光电流响应(a)和EIS图(b)；
图7：AgI/CO3 2--Bi2O2CO3光催化材料降解2-羟基-1,4-萘醌的C/C0图(a)和动力学拟合图(b)；降解左氧氟沙星的C/C0图(c)和动力学拟合图(d)；
图8：AgI/CO3 2--Bi2O2CO3光催化材料降解2-羟基-1,4-萘醌的循环实验图。
具体实施方式
下面结合说明书附图，对本发明做进一步的详细说明，所述是对本发明的解释而不是限定。
实施例1：可见光催化剂的制备及应用实验
一、制备
(一)CO3 2--Bi2O2CO3的制备：
将1mmol五水合硝酸铋、2mmol尿素和0.4412g柠檬酸钠溶解在35mL去离子水中。将混合物磁力搅拌1h，然后将其转移到聚四氟乙烯内衬的水热反应釜中。将水热反应釜加热至160℃，并在此温度下保持24h。之后，过滤产品，用蒸馏水洗涤，并在60℃下干燥20h，研磨后即得CO3 2--Bi2O2CO3粉末，命名为CBOC。
(二)AgI/CO3 2--Bi2O2CO3(0.05ACBOC)光催化材料的制备：
称取0.25g CO3 2--Bi2O2CO3放入装有50mL超纯水的烧杯中，超声30min后，向分散溶液中加入0.2mol/L的AgNO3溶液0.05mL，剧烈搅拌15min后向其中加入0.2mol/L KI溶液0.05mL，磁力搅拌2h后，离心收集沉淀，并用超纯水洗涤多次后将所得产物置于80℃烘箱中干燥12h，生成浅黄色的复合材料表示为0.05ACBOC。
(三)AgI/CO3 2--Bi2O2CO3(0.1ACBOC)光催化材料的制备：
称取0.25g CO3 2--Bi2O2CO3放入装有50mL超纯水的烧杯中，超声30min后，向分散溶液中加入0.2mol/L的AgNO3溶液0.1mL，剧烈搅拌15min后向其中加入0.2mol/L KI溶液0.1mL，磁力搅拌2h后，离心收集沉淀，并用超纯水洗涤多次后将所得产物置于80℃烘箱中干燥12h，生成浅黄色的复合材料表示为0.1ACBOC。
(四)0.5AgI/CO3 2--Bi2O2CO3(0.5ACBOC)光催化材料的制备：
称取0.25g CO3 2--Bi2O2CO3放入装有50mL超纯水的烧杯中，超声30min后，向分散溶液中加入0.2mol/L的AgNO3溶液0.5mL，剧烈搅拌15min后向其中加入0.2mol/L KI溶液0.5mL，磁力搅拌2h后，离心收集沉淀，并用超纯水洗涤多次后将所得产物置于80℃烘箱中干燥12h，生成浅黄色的复合材料表示为0.5ACBOC。
(五)1AgI/CO3 2--Bi2O2CO3(1ACBOC)光催化材料的制备：
称取0.25g CO3 2--Bi2O2CO3放入装有50mL超纯水的烧杯中，超声30min后，向分散溶液中加入0.2mol/L的AgNO3溶液1mL，剧烈搅拌15min后向其中加入0.2mol/L KI溶液1mL，磁力搅拌2h后，离心收集沉淀，并用超纯水洗涤多次后将所得产物置于80℃烘箱中干燥12h，生成浅黄色的复合材料表示为1ACBOC。
二、表征
图1为实施例1中所制备材料的XRD图，CBOC的衍射峰可分别标为四方Bi2O2CO3(JCPDS 41-1488)，对于纯AgI样品，在2θ＝23.71°、39.13°、46.31°处有三个衍射峰分别对应于立方结构AgI(JCPDS 09-0399)的(111)、(220)和(311)面，0.5ACBOC的衍射峰表明样品结晶良好，显著增强的(013)衍射峰显示(013)晶面的择优取向。
图2为实施例1中所制备材料的SEM图,可以看出0.5ACBOC和原来的玫瑰花状CBOC相比，将AgI与CBOC进行复合后，AgI均匀的分布于CBOC的玫瑰花状表面，其三维的形态有利于增强光在催化剂表面的散射与折射，有望增强光催化活性。
图3为实施例1中所制备材料的傅里叶红外图，3430cm-1处的峰可以归因于吸收水的O-H拉伸。峰值约551cm-1归因于Bi-O的拉伸振动。可以观察到对应于在V2(846cm-1)、V3(1392和1461cm-1)处CO3 2-的特征带组归因于CO3 2--Bi2O2CO3的存在。
图4为实施例1中所制备材料的紫外可见漫反射光谱图，纯CBOC在紫外区域(250nm-300nm)表现出强烈的光吸收，其光吸收边缘约为360nm。对于复合后的光催化剂0.5ACBOC，370nm-460nm范围内的峰值强度增强，出现了明显的可见光光吸收现象。
图5为实施例1中所制备材料的PL图，CBOC的发光强度高于0.5ACBOC，这表明AgI均匀的分布在CBOC表面有利于光生载流子的分离和转移，能极大的提高电荷分离效率。
图6为实施例1中所制备材料的光电流响应及EIS图，与AgI和CBOC相比，0.5ACBOC产生了更高的光电流响应，表明电荷分离更好。0.5ACBOC半圆的半径小于AgI和CBOC的半径，表明复合样品具有较小的电荷转移阻抗和较高的电荷分离能力。
三、应用实验
使用天平称取50mg光催化材料分别置于装有体积100mL浓度为10mg/L的2-羟基-1,4-萘醌溶液(左氧氟沙星溶液)的烧杯中，在黑暗条件下磁力搅拌30min，使其达到吸附饱和平衡的状态后进行光照反应。光源选用300W的氙灯，并安装紫外滤光片于其上滤掉紫外光(λ＞420nm)。在不同的时间段吸取5mL反应液，并过0.22μm的一次性滤膜，通过紫外-可见分光光度计在最大波长(λmax＝269nm)下测定2-羟基-1,4-萘醌的浓度，在最大波长(λmax＝289nm)测定左氧氟沙星的浓度。
图7为实施例1中所制备材料降解2-羟基-1,4-萘醌的C/C0图(a)和动力学拟合图(b)。可见光照射90min后，0.05ACBOC、0.1ACBOC、0.5ACBOC、1ACBOC四个复合比例的光催化剂降解效率分别为：58％，62.3％，67.5％，56％。顺序为：0.5ACBOC>0.1ACBOC>0.05ACBOC>1ACBOC。对反应速率进行一级动力学拟合，得反应速率常数k，Bi2O2CO3、AgI、0.05ACBOC、0.1ACBOC、0.5ACBOC、1ACBOC反应速率常数分别为0.006min-1、0.005min-1、0.010min-1、0.011min-1、0.03min-1、0.0089min-1。速率由高到低顺序为：0.5ACBOC>0.1ACBOC>0.5ACBOC>1ACBOC>Bi2O2CO3>AgI，0.5ACBOC的反应速率为纯CBOC和纯AgI的2倍多。由所制备材料降解左氧氟沙星的C/C0图(c)和动力学拟合图(d)可看出，0.5ACBOC和纯CBOC在90min内对左氧氟沙星的降解率分别为78％和63％，反应速率常数分别为0.019min-1，0.010min-1。表明复合材料中适量的AgI对CBOC光催化性能的提高起着关键作用。
图8为实施例1中所制备材料0.5ACBOC降解2-羟基-1,4-萘醌的循环实验图。0.5ACBOC光催化剂在可见光照射下连续四次降解2-羟基-1,4-萘醌后，2-羟基-1,4-萘醌降解减少了5.5％，去除效率变化不大，表明该复合催化剂具有较好的循环稳定性，可以用作稳定的光降解催化剂。
Claims (10)
1.一种碘化银/碳酸根自掺杂碳酸氧铋光催化材料的制备方法和应用，包括如下步骤：
(1)将五水合硝酸铋、尿素和柠檬酸钠溶解在去离子水中，搅拌，获得均匀的悬浮液；
(2)将步骤(1)所得溶液转移到聚四氟乙烯内衬的水热反应釜中进行水热反应；
(3)将步骤(2)得到的反应液过滤收集沉淀，洗涤，干燥，研磨得到产物CO3 2--Bi2O2CO3；
(4)称取上述步骤所得产物CO3 2--Bi2O2CO3溶解于超纯水中，超声一段时间；
(5)向步骤(4)所得溶液加入AgNO3溶液，并搅拌；
(6)向步骤(5)所得溶液加入KI溶液，搅拌，离心收集沉淀，洗涤，干燥，研磨后得到光催化剂AgI/CO3 2--Bi2O2CO3。
2.根据权利要求1所述的方法，其特征在于：所述步骤(1)磁力搅拌时间均为60min。
3.根据权利要求1所述的方法，其特征在于：所述步骤(2)的水热反应温度为160℃，并在此温度下保持24h。
4.根据权利要求1所述的方法，其特征在于：(3)烘箱干燥温度为60℃，时间为20h。
5.根据权利要求1所述的方法，其特征在于：所述步骤(4)超声时间为30min。
6.根据权利要求1所述的方法，其特征在于：所述步骤(5)磁力搅拌时间为15min。
7.根据权利要求1所述的方法，其特征在于：所述步骤(6)磁力搅拌时间为2h，烘箱干燥温度为80℃，时间为12h。
8.根据权利要求1～7所述的方法得到的AgI/CO3 2--Bi2O2CO3光催化材料。
9.根据权利要求8所述的方法得到的AgI/CO3 2--Bi2O2CO3光催化材料处理2-羟基-1,4-萘醌溶液(左氧氟沙星溶液)，其特征在于，包括如下步骤：
向反应器中加入2-羟基-1,4-萘醌溶液(左氧氟沙星溶液)及所述光催化剂，暗反应30min，再进行光照反应。
10.根据权利要求9所述的方法，其特征在于：2-羟基-1,4-萘醌溶液(左氧氟沙星溶液)的浓度为10mg/L，光催化剂的投加量为50mg。
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