CN107486213B - 一种中空BiVO4微米片光催化剂的制备方法 - Google Patents
一种中空BiVO4微米片光催化剂的制备方法 Download PDFInfo
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Abstract
本发明公开了一种中空BiVO4微米片光催化剂的制备方法,包括:合成中空BiVO4微米片及硼酸根离子掺杂与氧化钴纳米颗粒共修饰的中空BiVO4微米片。本发明的有益效果在于:所需原料来源丰富、合成方法简单、可规模制备、重复性好,材料稳定性高;本发明制备的材料可用于光催化降解有机污染物、光催化分解水产氧,具有很好的实用价值和应用前景。
Description
技术领域
本发明涉及无机功能纳米材料技术领域,具体涉及一种硼酸根离子掺杂与氧化钴纳米颗粒共修饰的中空BiVO4微米片光催化剂的制备方法。
背景技术
环境污染和能源短缺已成为制约人类社会可持续发展的重要问题。开发新型能源与环境净化材料已经成为全人类的重大课题。太阳能是最理想的可再生资源,利用绿色的太阳光驱动降解有机污染物,这种光催化技术已成为解决环境问题的重要手段。
光催化技术的核心是新型高效光催化剂的开发。商品化的P25光催化剂已被广泛应用。但是该产品存在光谱响应范围太窄之不足,只能利用太阳光谱中的紫外线部分,这大大限制了该产品的应用范围。开发新型高效的可见光响应的催化剂是当前研究的热点,也代表光催化产品开发的新方向。
BiVO4是一种可见光响应的光催化剂,已被广泛应用于光催化降解有机污染物、分解水、以及光电化学池。但是未经修饰的BiVO4的光催化活性仍不理想,难以满足实际的应用。通过合成纳米结构、贵金属修饰、掺杂、构筑异质结、助催化剂负载等手段能够有效提升BiVO4的光催化活性。但是目前的方法存在难以规模制备、操作繁杂、成本高等不足。利用地球含量丰富、价格低廉的原材料做掺杂剂和助催化剂,通过掺杂和助催化剂的共修饰,则可以进一步提升BiVO4的光催化活性。
发明内容
针对现有技术的不足,本发明旨在提供一种中空BiVO4微米片光催化剂的制备方法,实现制备硼酸根离子掺杂与氧化钴纳米颗粒共修饰的中空BiVO4微米片光催化剂。
为了实现上述目的,本发明采用如下技术方案:
一种中空BiVO4微米片光催化剂的制备方法,包括如下步骤:
S1合成中空BiVO4微米片:
1.1)将BiVO4·5H2O加入到稀硝酸溶液中,搅拌使其溶解,得到溶液A;
1.2)将NaVO3与乙二胺四乙酸加入到NaOH溶液中,搅拌使其溶解,得到溶液B;
1.3)将溶液B加入到溶液A中得到混合溶液并调节pH至4.6-5;然后加入到反应釜中,180℃反应24h,产物经水洗,烘干,即可得中空BiVO4微米片;
S2制备硼酸根离子掺杂与氧化钴纳米颗粒共修饰的中空BiVO4微米片:
2.1)将硝酸钴和硼酸钠,加入到乙醇与水的混合溶液中,搅拌使其溶解;
2.2)将步骤1.3)中制备得到的中空BiVO4微米片加入到步骤2.1) 中得到的溶解有硝酸钴和硼酸钠的乙醇与水的混合溶液中,蒸干,在氩气气氛中200℃煅烧24h,即得硼酸根离子掺杂与氧化钴纳米颗粒共修饰的中空BiVO4微米片。
需要说明的是,步骤S1具体为:
1.1)将2mL的浓硝酸加入10mL的蒸馏水中稀释后,再加入5 mmol的BiVO4·5H2O,搅拌使其溶解,得到溶液A;
1.2)将5mmol的NaVO3与1g的乙二胺四乙酸加入到8mL浓度为4mmol/L的NaOH溶液中,搅拌使其溶解,得到溶液B;
1.3)将溶液B加入到溶液A中,用4mmol/L NaOH溶液调节pH 至4.6-5,然后加入到50mL的反应釜中,180℃反应24h,产物经水洗,烘干,即可得中空BiVO4微米片。
需要说明的是,所述步骤S2具体如下:
2.1)将10mg的硝酸钴和10mg的硼酸钠,溶解于20mL体积比为1:1的乙醇与水的混合溶液中;
2.2)将500mg步骤1.3)中制备得到的中空BiVO4微米片加入步骤2.1)的混合溶液中,蒸干,在氩气气氛中200℃煅烧24h,即可得硼酸根离子掺杂与氧化钴纳米颗粒共修饰的中空BiVO4微米片。
上述中空BiVO4微米片光催化剂的制备方法制备得到的硼酸根离子掺杂与氧化钴纳米颗粒共修饰的中空BiVO4微米片可应用于降解污染物中。
需要说明的是,硼酸根离子掺杂与氧化钴纳米颗粒共修饰的中空 BiVO4微米片在光催化降解染料罗丹明B中作为光催化剂。
本发明的有益效果在于:
1、通过一锅水热合成路线得到中空BiVO4微米片,可实现规模化制备。
2、选择由高丰度、低成本的元素钴与硼作为助催化剂和掺杂剂,通过简单的浸渍法可同时实现硼酸根与氧化钴纳米颗粒对中空BiVO4微米片的共同修饰,减少了操作程序。
3、相比较中空BiVO4微米片、氧化钴纳米颗粒修饰的中空BiVO4微米片以及硼酸根掺杂的中空BiVO4微米片,本发明的硼酸根离子掺杂与氧化钴纳米颗粒共修饰的中空BiVO4微米片由于有效的载流子分离以及增强的表面催化活性而显示出最佳的光催化活性,可应用于环境净化领域。
4、本发明所需原料来源丰富、路线简单、重复性好、易于规模化生产。
附图说明
图1为中空BiVO4微米片的X-射线衍射花样。
图2中空BiVO4微米片的扫描电镜像。
图3为硼酸根离子掺杂与氧化钴纳米颗粒负载共修饰的中空 BiVO4微米片的X-射线衍射花样。
图4为硼酸根离子掺杂与氧化钴纳米颗粒负载共修饰的中空 BiVO4微米片的扫描电镜像。
图5为硼酸根离子掺杂与氧化钴纳米颗粒负载共修饰的中空 BiVO4微米片的透射电镜像。
图6为硼酸根离子掺杂与氧化钴纳米颗粒负载共修饰的中空 BiVO4微米片的元素分布。
图7为中空BiVO4微米片以及硼酸根离子掺杂与氧化钴纳米颗粒负载共修饰的中空BiVO4微米片的紫外漫反射谱图。
图8为中空BiVO4微米片以及硼酸根离子掺杂与氧化钴纳米颗粒负载共修饰的中空BiVO4微米片的荧光光谱图。
图9为中空BiVO4微米片以及硼酸根离子掺杂与氧化钴纳米颗粒负载共修饰的中空BiVO4微米片的光催化活性比较实验结果示意图。
具体实施方式
以下将结合附图对本发明作进一步的描述,需要说明的是,本实施例以本技术方案为前提,给出了详细的实施方式和具体的操作过程,但本发明的保护范围并不限于本实施例。
一种硼酸根离子掺杂与氧化钴纳米颗粒负载共修饰的中空BiVO4微米片光催化剂的制备方法,包括以下步骤:
S1合成中空BiVO4微米片:
1.1)将2mL的浓硝酸加入10mL的蒸馏水中稀释后,再加入5 mmol的BiVO4·5H2O,搅拌使其溶解,得到溶液A;
1.2)将5mmol的NaVO3与1g的乙二胺四乙酸加入到8mL浓度为4mmol/L的NaOH溶液中,搅拌使其溶解,得到溶液B;
1.3)将溶液B加入到溶液A中,用4mmol/LNaOH调节溶液的最终pH为4.6-5;将此溶液加入到50mL的反应釜中,180℃反应24h,产物经水洗,烘干,即可得中空BiVO4微米片;
S2制备硼酸根离子掺杂与氧化钴纳米颗粒共修饰的中空BiVO4微米片:
2.1)将10mg的硝酸钴和10mg的硼酸钠,溶解于20mL体积比为1:1的乙醇与水的混合溶液中。
2.2将500mg步骤1.3)中制备的中空BiVO4微米片加入该混合溶液,蒸干,在氩气气氛中200℃煅烧24h,即可得硼酸根离子掺杂与氧化钴纳米颗粒共修饰的中空BiVO4微米片。
上述制备方法制备得到的硼酸根离子掺杂与氧化钴纳米颗粒共修饰的中空BiVO4微米片在光催化降解有机污染物中的应用,具体在光催化降解水体中染料罗丹明B方面的应用。
步骤S1中所获得中空BiVO4微米片的X-射线衍射花样如图1所示。所有的衍射峰可以指标化为纯相的BiVO4。扫描电镜观察表明,产物为中空的微米片结构(图2)。
步骤S2所获得的硼酸根离子掺杂与氧化钴纳米颗粒共修饰的中空BiVO4微米片的X-射线衍射花样如图3所示。所有的衍射峰可以指标化为纯相的BiVO4,没有其它杂质相被探测到,表明产物中氧化钴的成分较少,硼酸根的掺杂不会影响BiVO4的相结构。产物的扫描电镜像(图4)显示,经过硼酸根掺杂与氧化钴负载,产物的形貌没有明显的变化。从透射电镜像能够看出,氧化钴纳米颗粒被均匀的负载在BiVO4表面(图5)。元素分布图也证实产物中含有Bi、V、Co、O、 B元素,硼酸根与氧化钴纳米颗粒均匀的分散在中空BiVO4微米片表面(图6)。
进一步地,步骤S1与S2中获得的中空BiVO4微米片与经过硼酸根掺杂与氧化钴纳米颗粒负载后的中空BiVO4微米片的紫外漫反射谱与荧光光谱分别如图7与图8所示。紫外漫反射谱分析表明,经硼酸根掺杂与氧化钴纳米颗粒修饰后的中空BiVO4微米片的光谱响应范围没有明显的变化。而荧光光谱测试显示经硼酸根掺杂与氧化钴纳米颗粒修饰后的中空BiVO4微米片的荧光性能下降,表明硼酸根掺杂与氧化钴纳米颗粒修饰促进了光生载流子的有效分离。
下面通过实验说明中空BiVO4微米片和硼酸根掺杂与氧化钴纳米颗粒共修饰的中空BiVO4微米片的光催化性能:
光催化反应光源为500W氙灯(配有400nm的滤光片),反应在室温下进行,每次催化实验催化剂的用量为0.1g,以罗丹明B(10-5 mol/L,100mL)溶液作为降解对象,对光催化剂的性能进行评价。在光照前,催化剂放入染料溶液中在暗处搅拌8h,达到吸附脱附平衡后,打开光源,在磁力搅拌下进行光照,每隔固定的时间取样,进行离心后取上层清夜进行吸光度测试。实验结果如图9所示。由图9 可知,经过硼酸根掺杂与氧化钴纳米颗粒修饰后的中空BiVO4微米片展现出了优秀的光催化活性。可见光照射下,修饰后的中空BiVO4微米片在3h内就可以将罗丹明B几乎完全降解。而可见光辐照下,在没有任何催化剂时,罗丹明B本身稳定且基本不降解。而未经修饰的中空BiVO4微米片,3h内,仅有42%的罗丹明B被降解。
对于本领域的技术人员来说,可以根据以上的技术方案和构思,作出各种相应的改变和变形,而所有的这些改变和变形都应该包括在本发明权利要求的保护范围之内。
Claims (5)
1.一种硼酸根离子掺杂与氧化钴纳米颗粒共修饰的中空BiVO4微米片的制备方法,其特征在于,包括如下步骤:
S1合成中空BiVO4微米片:
1.1)将BiVO4·5H2O加入到稀硝酸溶液中,搅拌使其溶解,得到溶液A;
1.2)将NaVO3与乙二胺四乙酸加入到NaOH溶液中,搅拌使其溶解,得到溶液B;
1.3)将溶液B加入到溶液A中得到混合溶液并调节pH至4.6-5;然后加入到反应釜中,180℃反应24h,产物经水洗,烘干,即可得中空BiVO4微米片;
S2制备硼酸根离子掺杂与氧化钴纳米颗粒共修饰的中空BiVO4微米片:
2.1)将硝酸钴和硼酸钠,加入到乙醇与水的混合溶液中,搅拌使其溶解;
2.2)将步骤1.3)中制备得到的中空BiVO4微米片加入到步骤2.1)中得到的溶解有硝酸钴和硼酸钠的乙醇与水的混合溶液中,蒸干,在氩气气氛中200℃煅烧24h,即得硼酸根离子掺杂与氧化钴纳米颗粒共修饰的中空BiVO4微米片。
2.根据权利要求1所述的硼酸根离子掺杂与氧化钴纳米颗粒共修饰的中空BiVO4微米片的制备方法,其特征在于,步骤S1具体为:
1.1)将2mL的浓硝酸加入10mL的蒸馏水中稀释后,再加入5mmol的BiVO4·5H2O,搅拌使其溶解,得到溶液A;
1.2)将5mmol的NaVO3与1g的乙二胺四乙酸加入到8mL浓度为4mmol/L的NaOH溶液中,搅拌使其溶解,得到溶液B;
1.3)将溶液B加入到溶液A中,用4mmol/L NaOH溶液调节pH至4.6-5,然后加入到50mL的反应釜中,180℃反应24h,产物经水洗,烘干,即可得中空BiVO4微米片。
3.根据权利要求1所述的硼酸根离子掺杂与氧化钴纳米颗粒共修饰的中空BiVO4微米片的制备方法,其特征在于,所述步骤S2具体如下:
2.1)将10mg的硝酸钴和10mg的硼酸钠,溶解于20mL体积比为1:1的乙醇与水的混合溶液中;
2.2)将500mg步骤1.3)中制备得到的中空BiVO4微米片加入步骤2.1)的混合溶液中,蒸干,在氩气气氛中200℃煅烧24h,即可得硼酸根离子掺杂与氧化钴纳米颗粒共修饰的中空BiVO4微米片。
4.权利要求1所述硼酸根离子掺杂与氧化钴纳米颗粒共修饰的中空BiVO4微米片的制备方法制备得到的硼酸根离子掺杂与氧化钴纳米颗粒共修饰的中空BiVO4微米片在降解污染物中的应用。
5.根据权利要求4所述的应用,其特征在于,硼酸根离子掺杂与氧化钴纳米颗粒共修饰的中空BiVO4微米片在光催化降解染料罗丹明B中作为光催化剂。
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