CN108514885B - 一种Cu（Ⅱ）修饰的BiOCl的制备方法及其应用 - Google Patents
一种Cu（Ⅱ）修饰的BiOCl的制备方法及其应用 Download PDFInfo
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Abstract
本发明公开了一种Cu(Ⅱ)修饰的BiOCl纳米材料。该材料在一步简单的水热法制备螺旋的BiOCl纳米片结构上，通过免还原剂与保护剂的原位光还原法修饰Cu(Ⅱ)，该Cu(Ⅱ)修饰的BiOCl催化剂，能够有效降低电子和空穴对的复合速率，对罗丹明B的降解有良好的可见光光催化性能。
Description
技术领域
本发明属于新型光催化材料制备技术领域，具体涉及一种Cu(Ⅱ)修饰的BiOCl的制备方法及其光催化应用。
背景技术
在过去的三十年中，环境的持续恶化，探索新的有效的污染物处理策略迫在眉睫，经济和环境友好型的太阳能光光催化***引起了科学家的广泛关注。特别地，典型的具有莫尔条纹的BiOCl光催化材料，由于合成出的这种BiOCl结构，带有周期性的螺旋形貌，同时层与层的转角在3℃，形成带有莫尔条纹的纳米片层结构，使得带隙有效的降低到(2.6eV),从而可以吸收可见光。然而，该材料的电子和空穴的复合机率仍然很高，同时，载流子寿命短，大大降低了光催化剂的降解速率。
目前，研究人员已经做了很多努力来改善BiOCl电子和空穴复合过快的缺点的属性。例如，将氧空位引入晶格缺陷，与金属物质结合形成肖特基势垒；调控尺寸、形貌或暴露晶面等方法有效降低电子和空穴的复合效率。然而，几个缺点还需要克服。例如，形貌改变不会改变BiOCl的固有光学特性；形成异质结，很难获得高度均匀的分布；相改变可能破坏分层结构，从而削弱静电场在BiOCl晶体中的贡献。掺杂是一个有效的方法，改变电子和空穴的复合速率，在不改变宿主晶体结构的情况下，形成一种掺杂能量水平。据报道，掺杂的Au、 Ag、Pt、Pd元素可以减少BiOCl纳米片的电子和空穴的复合速率，从而增强了BiOCl的光催化性能。C掺杂也能使BiOCl电子和空穴的复合速率降低。
在这里,我们采用Cu元素，有利于界面的电荷转移，使得BiOCl的电子和空穴的复合速率大大降低,提高光催化性能，同时，铜价格低廉，更易于实际应用。
发明内容
本发明的目的是克服现有技术的不足，提供一种Cu(Ⅱ)修饰的BiOCl的制备方法及其光催化应用。
本发明的目的是通过以下技术方案实现的：一种Cu(Ⅱ)修饰的BiOCl的制备方法，该方法具体为：将1mM氯化铜溶液加入到BiOCl纳米片水溶液中，其中铜的质量为BiOCl质量的1～10％；以300mW/cm2的全波段白光为光源，照射混合溶液40分钟以上，得到Cu(Ⅱ)修饰的BiOCl纳米片。
进一步地，所述BiOCl纳米片通过以下方法制备得到：
(1.1)取80ml乙二醇，加入4.8ml浓度为20wt％的PDDA(分子量400 000-500000)的水溶液，混合后加入Bi(NO3)3.5H2O，搅拌30min；
(1.2)将上述混合溶液转移到200℃的油浴中，加热回流2h。
(1.3)待上述混合溶液冷却到室温，进行离心，洗涤、烘干。离心水洗3遍，真空干燥箱中80℃烘干12h。
进一步地，所述BiOCl纳米片水溶液的浓度为0.1～1mg/mL。
Cu(Ⅱ)修饰的BiOCl纳米片在光催化中的应用。
本发明的优点是：
(1)原料廉价易得，利用原位光还原法，过程简单，回收利用率高，适合工业生产。
(2)Cu(Ⅱ)修饰的BiOCl新型光催化材料，由于铜离子掺杂进入BiOCl晶格，取代了部分Bi离子，并在表面形成了Cu(Ⅱ)氧化物纳米团簇，大幅度的扩宽了吸光范围，并且有效的抑制了电子和空穴对的复合的机率，从而提高了BiOCl的光催化性能。
附图说明
图1是本发明制备的Cu(Ⅱ)修饰的BiOCl纳米材料材料的形貌图。其中，(a)为Cu(Ⅱ)修饰的BiOCl的扫描电子显微镜图片，(b)为Cu(Ⅱ)修饰的BiOCl的透射电子显微镜图片，(c)为Cu(Ⅱ)修饰的BiOCl的高分辨透射电子显微镜图片，(d)为Cu(Ⅱ)修饰的BiOCl的透射电子显微镜暗场像图片，(e)-(h)为Cu(Ⅱ) 修饰的BiOCl新型光催化材料的能谱图片；
图2是本发明制备的Cu(Ⅱ)修饰的BiOCl纳米材料材料的X射线光电子能谱图谱。
图3是本发明制备的Cu(Ⅱ)修饰的BiOCl纳米材料的降解罗丹明B图谱。a 、b 是Cu(Ⅱ)修饰的BiOCl新型光催化材料的催化性质测试(Ⅱ)图，c 是Cu(Ⅱ) 修饰的BiOCl纳米材料的催化稳定性的催化性质测试图，d 是Cu修饰的BiOCl纳米材料与传统块体BiOCl、Ag修饰的BiOCl、Au修饰的BiOCl纳米材料对降解罗丹明B转化效率对比图。
具体实施方式
以下结合附图和实施例进一步说明本发明。
实施例1
本实施例制备Cu(Ⅱ)修饰的BiOCl纳米片纳米材料,具体包括以下步骤：
(1)一步水热合成BiOCl光催化材料,具体为:
(1.1)用100ml量筒量取80ml乙二醇溶液，然后倒入容积为250ml二颈瓶瓶中，搅拌，用移液枪取4.8ml的PDDA(分子量400000-500000)的20wt％水溶液，滴入上述二颈瓶中，继续剧烈搅拌，然后向其中加入0.0970g Bi(NO3)3.5H2O，磁力搅拌30min；
(1.2)将上述混合溶液转移到200℃的油浴中，加热回流2h。
(1.3)待上述混合溶液冷却到室温，进行离心，洗涤、烘干。用高速离心机离心15min，用去离子水洗3遍，真空干燥箱中80℃烘干12h。
(2)之后利用BiOCl自身的光催化特性，在光照条件下通过BiOCl的光生电子还原吸附在其表面的Cu(Ⅱ)，最终形成Cu(Ⅱ)修饰的BiOCl新型光催化材料，具体为：
(2.1)配制BiOCl水溶液，水溶液的浓度为0.5mg/mL，加入1mM氯化铜溶液，其中铜的质量为BiOCl质量的1％。
(2.2)以300mW/cm2的全波段白光为光源，照射上述样品，使其在BiOCl纳米片表面形成Cu(Ⅱ)氧化物纳米团簇，并且部分铜离子掺入了BiOCl纳米片，最终形成了Cu(Ⅱ)修饰的BiOCl纳米片新型光催化材料。
图1为Cu(Ⅱ)修饰的BiOCl新型光催化材料的形貌图谱，(a)为Cu(Ⅱ)修饰的BiOCl的扫描电子显微镜图片，(b)为Cu(Ⅱ)修饰的BiOCl的透射图片， (c)为Cu(Ⅱ)修饰的BiOCl的高分辨透射电子显微镜图片，从图中可以看出 Cu(Ⅱ)修饰有一个微弱的影响，几乎不改变的晶格和形貌和尺寸，(d-h)为Cu(Ⅱ) 修饰的BiOCl新型光催化材料的能谱图片，从图中可以看出EDX谱已经显示了 Cu元素的存在。相应的随机选择区域的EDX映射图呈现出Bi，O，Cl和Cu 元素的分布,同时可以看出Cu元素整体均匀分散Cu(Ⅱ)修饰的BiOCl选定区域。
图2为Cu(Ⅱ)修饰的BiOCl新型光催化材料的X射线光电子能谱图谱，从图中可以看出，Cu(Ⅱ)修饰的BiOCl样品中特征峰在934.57eV和954.44eV，分别为Cu 2p3/2和Cu 2p1/2峰，这证明了Cu以二价离子形式修饰的BiOCl材料上。
实施例2
本实施例用所制备的Cu(Ⅱ)修饰的BiOCl新型光催化材料作为光催化降解Ⅱ罗丹明B的光催化测试实验，主要步骤如下：
(1)以10mg/L的罗丹明B溶液为目标降解物，取50毫升目标降解物放入玻璃反应器中，容器外层使用冷凝水恒温，用300W氙灯(滤光片>400nm)可见光作为光源，加入Cu修饰的BiOCl的光催化剂各10毫克。暗处理30min,达到吸附解吸附平衡，分别取5min,10min,15min取样，样品进行离心处理，以10000r/min 的条件下离心10min,取上层清液，采用UV-8500紫外-可见光光度计(UV-vis)对罗丹明B浓度(C/C0)的变化进行作图。作为对比，分别在1mM氯金酸、硝酸银溶液中利用原位光还原法在具有莫氏条纹的BiOCl的纳米片上负载Au、Ag 等纳米粒子并在相同条件下检测其对罗丹明B光降解的性能。
图3a 是Cu(Ⅱ)修饰的BiOCl在可见光照射下，罗丹明B在554纳米的特征吸收峰在15分钟之内快速下降。
3b 是在催化剂存在的情况下，在可见光照射下，RhB浓度的随时间演变情况。在不加入催化剂的情况下，光降解罗丹明B是忽略不计的，然而，Cu(Ⅱ) 修饰的BiOCl催化剂展现了良好的可见光催化活性。
3c 是对Cu(Ⅱ)修饰的BiOCl的新型光催化材料进行的重复利用性进行检测。从图中可以看出该纳米催化材料具有非常优异的稳定性以及可回收利用性。
采用Au、Ag两种贵金属，按照相同的方法(以300mW/cm2的全波段白光为光源，照射混合溶液40分钟以上)对BiOCl纳米片进行修饰，结果表明，Au、 Ag均以纳米粒子形式修饰在BiOCl纳米片表面，X射线光电子能谱图谱为检测到Au、Ag离子峰。
在相同条件下，分别检测Ag修饰的BiOCl和Au修饰的BiOCl和Cu(Ⅱ) 修饰的BiOCl三种催化材料的对罗丹明B降解速度，如图3d 。从图中可以看出，本发明中的制备的非贵金属基催化材料Cu(Ⅱ)修饰的BiOCl的催化速率明显优于其他两种催化剂在相同条件下制备的贵金属基催化材料，考虑到Cu基材料相比于Au、Ag等贵金属催化材料在价格成本上的巨大优势，可以说明本发明制备的Cu(Ⅱ)修饰的BiOCl新型光催化材料在工业应用方面具有非常高的潜力。
实施例3
本实施例制备Cu(Ⅱ)修饰的BiOCl纳米片纳米材料,具体包括以下步骤：
(1)一步水热合成BiOCl光催化材料,具体为:
(1.1)用100ml量筒量取80ml乙二醇溶液，然后倒入容积为250ml二颈瓶瓶中，搅拌，用移液枪取4.8ml的PDDA(分子量400000-500000)的20wt％水溶液，滴入上述二颈瓶中，继续剧烈搅拌，然后向其中加入Bi(NO3)3.5H2O，磁力搅拌 30min；
(1.2)将上述混合溶液转移到200℃的油浴中，加热回流2h。
(1.3)待上述混合溶液冷却到室温，进行离心，洗涤、烘干。用高速离心机离心15min，用去离子水洗3遍，真空干燥箱中80℃烘干12h。
(2)之后利用BiOCl自身的光催化特性，在光照条件下通过BiOCl的光生电子还原吸附在其表面的Cu(Ⅱ)，最终形成Cu(Ⅱ)修饰的BiOCl新型光催化材料，具体为：
(2.1)配制BiOCl水溶液，水溶液的浓度分别为0.1mg/mL，0.5mg/mL， 1mg/mL，加入一定体积的1mM氯化铜溶液，其中铜的质量为BiOCl质量的5％。
(2.2)以300mW/cm2的全波段白光为光源，照射上述样品，使其在BiOCl纳米片表面形成Cu(Ⅱ)氧化物纳米团簇，并且部分铜离子掺入了BiOCl纳米片，最终形成了Cu(Ⅱ)修饰的BiOCl纳米片新型光催化材料。
通过测试表明，本实施例中，Cu(Ⅱ)修饰几乎不改变的晶格和形貌和尺寸，且Cu以二价离子形式修饰的BiOCl材料上。
实施例4
本实施例制备Cu(Ⅱ)修饰的BiOCl纳米片纳米材料,具体包括以下步骤：
(1)一步水热合成BiOCl光催化材料,具体为:
(1.1)用100ml量筒量取80ml乙二醇溶液，然后倒入容积为250ml二颈瓶瓶中，搅拌，用移液枪取4.8ml的PDDA(分子量400000-500000)的20wt％水溶液，滴入上述二颈瓶中，继续剧烈搅拌，然后向其中加入Bi(NO3)3.5H2O，磁力搅拌 30min；
(1.2)将上述混合溶液转移到200℃的油浴中，加热回流2h。
(1.3)待上述混合溶液冷却到室温，进行离心，洗涤、烘干。用高速离心机离心15min，用去离子水洗3遍，真空干燥箱中80℃烘干12h。
(2)之后利用BiOCl自身的光催化特性，在光照条件下通过BiOCl的光生电子还原吸附在其表面的Cu(Ⅱ)，最终形成Cu(Ⅱ)修饰的BiOCl新型光催化材料，具体为：
(2.1)配制BiOCl水溶液，水溶液的浓度为0.5mg/mL，加入不同体积的1mM 氯化铜溶液，其中铜的质量分别为BiOCl质量的1％,5％，10％。
(2.2)以300mW/cm2的全波段白光为光源，照射上述样品，使其在BiOCl纳米片表面形成Cu(Ⅱ)氧化物纳米团簇，并且部分铜离子掺入了BiOCl纳米片，最终形成了Cu(Ⅱ)修饰的BiOCl纳米片新型光催化材料。
通过测试表明，本实施例中，Cu(Ⅱ)修饰几乎不改变的晶格和形貌和尺寸，且Cu以二价离子形式修饰的BiOCl材料上。
Claims (4)
1.一种Cu（Ⅱ）修饰的BiOCl的制备方法，其特征在于，该方法具体为：将1mM氯化铜溶液加入到BiOCl纳米片水溶液中，其中铜的质量为BiOCl质量的1~10%；以300mW/cm2的全波段白光为光源，照射混合溶液40分钟以上，得到Cu(Ⅱ)修饰的BiOCl纳米片，其中铜离子掺杂进入BiOCl晶格，取代了部分Bi离子，并在表面形成了Cu(Ⅱ)氧化物纳米团簇；
所述BiOCl纳米片通过以下方法制备得到：
(1.1)取80ml乙二醇，加入4.8ml浓度为20wt％、分子量为400000-500000的PDDA水溶液，混合后加入Bi(NO3)3•5H2O，搅拌30min；
(1.2)将上述混合溶液转移到200℃的油浴中，加热回流2h；
(1.3)待上述混合溶液冷却到室温，进行离心，洗涤、烘干；离心水洗3遍，真空干燥箱中80℃烘干12h。
2.根据权利要求1所述的方法，其特征在于，Bi(NO3)3•5H2O的量为0.0970g。
3.根据权利要求1所述的方法，其特征在于，所述BiOCl纳米片水溶液的浓度为0.1~1mg/mL。
4.权利要求1所述方法制备的Cu(Ⅱ)修饰的BiOCl纳米片在光催化中的应用。
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