CN113509942A - 一种钨酸钴/铋/溴氧铋三元异质结复合材料及其制备方法和应用 - Google Patents
一种钨酸钴/铋/溴氧铋三元异质结复合材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明属于复合声催化剂制备领域，具体涉及一种钨酸钴/铋/溴氧铋三元异质结复合材料及其制备方法和应用。将NaPO2H2·H2O溶于去离子水中，搅拌后，加入C4H6O6和NaOH,继续搅拌，加入CoWO4超声处理，得到溶液，将溶于HNO3的Bi(NO3)3·5H2O溶液缓慢加入到上述溶液中搅拌均匀，进行水热反应，抽滤，洗涤，烘干得到钨酸钴/铋纳米颗粒；将钨酸钴/铋纳米颗粒加入到装有硝酸铋溶液、乙二醇和溴化钾的容器中，混合均匀后搅拌、超声抽滤烘干、得到钨酸钴/铋/溴氧铋粉末。制得的复合材料具有更小的禁带宽度，降低了电子和空穴的传输距离从而改善其声催化活性。在超声条件下，对四环素具有良好的降解效果。
Description
技术领域
本发明属于复合声催化剂制备领域，具体涉及一种钨酸钴/铋/溴氧铋三元异质结复合材料的制备方法及应用。
背景技术
钨酸钴(CoWO4)是一种p型半导体，带隙能约为3.00eV，适合于可见光吸收和声催化降解。因此，CoWO4被用作声催化剂，然而CoWO4分离效率很低，在许多应用中不能满足实际需要。因此克服上述缺陷具有十分重要的现实意义。
声催化活性与声催化材料的形貌和电荷分离效率密切相关。大量研究表明声催化复合材料的合成，可以改善半导体前驱体与适当带隙的耦合，从而实现了声催化载体的分离效果，大大提高了声催化效率。如Jang等合成CoWO4/g-C3N4纳米复合材料并研究了其对诺氟沙星的降解。Cui等构建了CoWO4/CdS光催化剂，用于H2生成和染料降解。将CoWO4纳米粒子的窄带隙与BiOBr的宽带隙相结合，构建CoWO4/BiOBr异质结构，也是促进电子空穴对分离的一种很有前途的方法。人们利用多种金属钨酸盐纳米颗粒与BiOBr偶联形成异质结构，如Bi2WO6/BiOBr、FeWO4/BiOBr、CdWO4/BiOBr、ZnWO4/BiOBr等。
受这些研究的启发，为了提高CoWO4的活性，我们制备了CoWO4/Bi/BiOBr异质结构纳米复合声催化剂，并研究了其在超声条件下对四环素溶液的声催化活性。与母体化合物相比，所制备的异质结构CoWO4/Bi/BiOBr声催化剂具有更强的电荷分离效率和声催化活性。
发明内容
本发明目的是提供一种钨酸钴/铋/溴氧铋三元异质结复合材料及其制备方法，利用钨酸钴与铋和溴氧铋形成异质结，提高了电子空穴分离效率，从而提高其声催化活性。且本发明制备的声催化剂活性位点多，稳定性好，可应用于药物废水降解领域。
本发明采用的技术方案为：一种钨酸钴/铋/溴氧铋三元异质结复合材料，制备方法包括如下步骤：
1)将NaPO2H2·H2O溶于去离子水中，搅拌后，加入C4H6O6和NaOH,继续搅拌，加入CoWO4超声处理，得到溶液，将溶于HNO3的Bi(NO3)3·5H2O溶液缓慢加入到上述溶液中搅拌均匀，进行水热反应，抽滤，洗涤，烘干得到钨酸钴/铋纳米颗粒；
2)将钨酸钴/铋纳米颗粒加入到装有硝酸铋溶液、乙二醇和溴化钾的容器中，混合均匀后搅拌、超声、抽滤，烘干、得到钨酸钴/铋/溴氧铋粉末。
上述的一种钨酸钴/铋/溴氧铋三元异质结复合材料，按摩尔比，钨酸钴：硝酸铋＝2：5。
上述的一种钨酸钴/铋复合声催化剂，步骤1)中，按摩尔比，NaPO2H2.H2O：Bi(NO3)3·5H2O＝100:3。
上述的一种钨酸钴/铋/溴氧铋三元异质结复合材料，步骤1)中，水热反应的反应温度为60℃，反应时间为6h。
上述的一种钨酸钴/铋/溴氧铋三元异质结复合材料，按质量比，溴化钾：钨酸钴/铋纳米颗粒：硝酸铋＝4：5：4。
上述的一种钨酸钴/铋/溴氧铋三元异质结复合材料，步骤2)中，烘干温度为70-90℃，烘干时间为2h。
上述的任一种钨酸钴/铋/溴氧铋三元异质结复合材料在超声下催化降解有机污染物中的应用。
上述的应用，所述的有机污染物是四环素。
上述的应用，方法如下，将权利要求1-6所述的一种钨酸钴/铋/溴氧铋三元异质结复合材料加入到含有四环素的废水中，超声2h。
上述的应用，向含有四环素的溶液中加入钨酸钴/铋复合声催化剂，声催化剂的加入量为1g/L，所述四环素的溶液的浓度为20mg/L。
本发明的有益效果是：
本发明的钨酸钴/铋/溴氧铋三元异质结复合声催化剂可以为声催化过程提供更多的活性位点，抑制电子空穴对重组，显著提高钨酸钴的声催化活性。制备工艺简单，安全环保，在降解药物废水领域具有良好的应用前景。
附图说明
图1为所制备的CoWO4(a),CoWO4/Bi(b)和CoWO4/Bi/BiOBr(c)复合声催化剂的扫描电镜照片。
图2为所制备的CoWO4，CoWO4/Bi和CoWO4/Bi/BiOBr复合声催化剂的XPS图谱。
图3为所制备的CoWO4，CoWO4/Bi和CoWO4/Bi/BiOBr复合声催化剂的UV-DRS光谱图。
图4为不同复合比制备的CoWO4/Bi/BiOBr复合声催化剂对四环素溶液降解效果影响图。
具体实施方式
实施例1钨酸钴的制备
将1.4551g Co(NO3)2·6H2O和1.6493g Na2WO4·2H2O分别溶于装有30mL去离子水的100mL锥形瓶中；将二者混合，混合物磁力搅拌30min；再超声反应30min后倒入聚四氟乙烯反应釜中，放入鼓风干燥箱中180℃反应24h；反应结束后抽滤，在80℃条件下烘干2h，用玛瑙研钵研成细粉，得到CoWO4粉末。
实施例2钨酸钴/铋复合材料的制备
将10.5993g NaPO2H2.H2O溶于50ml去离子水中，磁力搅拌20min后，加入0.45027gC4H4O6和0.08g NaOH NaOH,继续磁力搅拌30min后,加入1.5g CoWO4超声处理,得到A溶液得到溶液。将1.2127Bi(NO3)3·5H2O溶于5ml HNO3中，磁力搅拌后得到溶液B。在磁力搅拌的条件下，将B溶液逐滴加入到A溶液中，放入烘箱中60℃下反应6h进行水热反应，抽滤，用去离子水清洗得到样品，将样品后在70-90℃烘干2h，得到钨酸钴/铋纳米粒子。
实施例3钨酸钴/铋/溴氧铋三元异质结复合材料的制备
将0.16245g溴化钾均匀分散到20ml乙二醇中，将0.16245g硝酸铋均匀分散到100ml去离子水中配置成硝酸铋溶液，将0.2g钨酸钴/铋纳米粒子加入到硝酸铋溶液中，再将上述这两种溶液混合，磁力搅拌30min，超声30min。抽滤，在70-90℃烘干2h。得到钨酸钴/铋/溴氧铋粉末(1:2)。
实施例4
将钨酸钴/铋纳米的加入量改为1.0g，溴化钾的加入量改为0.16245g，五水硝酸铋的加入量改为0.1576g，其他步骤同实施例1，得到钨酸钴/铋/溴氧铋复合声催化剂(溴氧铋：钨酸钴/铋＝1:10)。
实施例5
将钨酸钴/铋纳米的加入量改为0.4g，溴化钾的加入量改为0.16245g，五水硝酸铋的加入量改为0.1576g，其他步骤同实施例1，得到钨酸钴/铋/溴氧铋复合声催化剂(溴氧铋：钨酸钴/铋＝1:4)。
实施例6
将钨酸钴/铋纳米的加入量改为0.2g，溴化钾的加入量改为0.243675g，五水硝酸铋的加入量改为0.2364g，其他步骤同实施例1，得到钨酸钴/铋/溴氧铋复合声催化剂(溴氧铋：钨酸钴/铋＝3:4)。
实施例7
将钨酸钴/铋纳米的加入量改为0g，溴化钾的加入量改为0.243675g，五水硝酸铋的加入量改为0.2364g，其他步骤同实施例1，得到BiOBr声催化剂。
实施例8
将钨酸钴/铋纳米的加入量改为0.1g，溴化钾的加入量改为0.16245g，五水硝酸铋的加入量改为0.1576g，其他步骤同实施例1，得到钨酸钴/铋/溴氧铋复合声催化剂(溴氧铋：钨酸钴/铋＝1:1)。
实施例9钨酸钴/铋/溴氧铋三元异质结复合材料的表征分析
表1为CoWO4(实施例1制得),CoWO4/Bi(实施例2制得)和CoWO4/Bi/BiOBr(实施例3制得)复合声催化剂的BET分析，其比表面积分别为19.54nm,16.610nm,8.986nm.CoWO4/Bi/BiOBr的比表面积最小，孔径最大。
表1
从图1a中可以看出，成功合成了大量的单分散纳米颗粒，粒径约为100nm，并发现了局部团聚现象。图1b中获得的CoWO4/Bi复合材料形状规则，表面光滑，大量的球状结晶结构堆积在一起。图1c为CoWO4/Bi/BiOBr(实施例3制得)的SEM图像。从中可以清晰地观察到几个与原始CoWO4有明显差异的椭圆纳米颗粒，即BiOBr纳米颗粒。这一结果表明，在CoWO4/Bi/BiOBr纳米复合材料(实施例3制得)中，CoWO4,Bi与BiOBr纳米粒子之间可能形成异质结。
此外，还利用XPS进一步研究了样品的元素组成，如图2所示。结果表明，该复合材料由Co、Bi、Br、W、O等元素组成。表明样品中CoWO4,Bi和BiOBr共存，制备的样品为CoWO4/Bi/BiOBr相。
我们对CoWO4,CoWO4/Bi和CoWO4/Bi/BiOBr(实施例3制得)进行了UV-DRS光谱测试。测试结果表明，CoWO4,CoWO4/Bi和CoWO4/Bi/BiOBr(实施例3制得)的带隙能分别为3.00eV、2.60eV和2.20eV。制得的复合材料具有更小的禁带宽度，易于被激发。
实施例10不同复合比制备的CoWO4/Bi/BiOBr复合声催化剂对催化超声降解四环素溶液效果影响
将纯BiOBr,CoWO4/Bi和不同复合比制备的CoWO4/Bi/BiOBr(实施例3制得)复合声催化剂各20mg放于250ml锥形瓶中，各加入20ml的20mg/L四环素溶液，超声催化，2h后取样测试其吸光度。
四环素溶液的降解率公式为:降解率(％)＝[(A0-At)/A0]×100％。
A0是四环素溶液的初始吸光度，At是四环素溶液在不同实验条件下的吸光度。
结果如图3所示，在超声2h后，CoWO4/Bi催化剂将四环素降解了72％，而三元异质结构CoWO4/Bi/BiOBr(实施例3制得)将四环素降解了88％左右，体现出三元异质结构CoWO4/Bi/BiOBr具有更高的催化能力。CoWO4/Bi/BiOBr的不同比例对四环素均具有良好的降解效果，CoWO4/Bi/BiOBr复合材料中BiOBr的比例逐渐增加时，MLX的分解率先逐渐升高再下降。推测其原因可能是当BiOBr含量不足时，BiOBr与CoWO4/Bi有限的接触面积不能更有效地抑制声致发光与空穴电子对的复合。但当BiOBr的含量过多时,CoWO4/Bi复合材料表面活性位点部分被BiOBr覆盖，从而降低了CoWO4/Bi/BiOBr复合材料的声催化性能。
Claims (10)
1.一种钨酸钴/铋/溴氧铋三元异质结复合材料，其特征在于，制备方法包括如下步骤：
1)将NaPO2H2·H2O溶于去离子水中，搅拌后，加入C4H6O6和NaOH,继续搅拌，加入CoWO4超声处理，得到溶液，将溶于HNO3的Bi(NO3)3·5H2O溶液缓慢加入到上述溶液中搅拌均匀，进行水热反应，抽滤，洗涤，烘干得到钨酸钴/铋纳米颗粒；
2)将钨酸钴/铋纳米颗粒加入到装有硝酸铋溶液、乙二醇和溴化钾的容器中，混合均匀后搅拌、超声、抽滤，烘干、得到钨酸钴/铋/溴氧铋粉末。
2.根据权利要求1所述的一种钨酸钴/铋/溴氧铋三元异质结复合材料，其特征在于，按摩尔比，钨酸钴：硝酸铋＝2：5。
3.根据权利要求2所述的一种钨酸钴/铋复合声催化剂，其特征在于，步骤1)中，按摩尔比，NaPO2H2.H2O：Bi(NO3)3·5H2O＝100:3。
4.根据权利要求3所述的一种钨酸钴/铋/溴氧铋三元异质结复合材料，其特征在于，步骤1)中，水热反应的反应温度为60℃，反应时间为6h。
5.根据权利要求4所述的一种钨酸钴/铋/溴氧铋三元异质结复合材料，其特征在于，按质量比，溴化钾：钨酸钴/铋纳米颗粒：硝酸铋＝4：5：4。
6.根据权利要求5所述的一种钨酸钴/铋/溴氧铋三元异质结复合材料，其特征在于，步骤2)中，烘干温度为70-90℃，烘干时间为2h。
7.权利要求1-6所述的任一种钨酸钴/铋/溴氧铋三元异质结复合材料在超声下催化降解有机污染物中的应用。
8.根据权利要求7所述的应用，其特征在于，所述的有机污染物是四环素。
9.根据权利要求8所述的应用，其特征在于，方法如下，将权利要求1-6所述的一种钨酸钴/铋/溴氧铋三元异质结复合材料加入到含有四环素的废水中，超声2h。
10.根据权利要求9所述的应用，其特征在于，向含有四环素的溶液中加入钨酸钴/铋复合声催化剂，声催化剂的加入量为1g/L，所述四环素的溶液的浓度为20mg/L。
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