CN111167455B - 一种石墨烯负载钴掺杂二氧化钛光催化剂及其制备方法 - Google Patents
一种石墨烯负载钴掺杂二氧化钛光催化剂及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种石墨烯负载钴掺杂二氧化钛光催化剂及其制备方法。本发明首先以钛酸四正丁酯和硝酸钴分别作为钛源和钴源制备前驱体溶液,以无水乙醇、冰醋酸和和PVP作为助剂,按比例将前驱体和助剂混合均匀得到纺丝液;接着进行高压静电纺丝得到初始PVP/Co‑TiO2纤维;然后在马弗炉中煅烧得到Co‑TiO2纳米纤维;最后使用真空冷冻干燥法将Co‑TiO2纳米纤维负载到石墨烯上,得到Co‑TiO2/RGO光催化剂。本发明制备方法简单、生产成本低,制备的复合光催化剂形貌可控、比表面积高、光学性能优良、绿色环保、有较好的光催化降解有机污染物效果,在VOCs治理领域有广泛应用前景。
Description
技术领域
本发明涉及光催化材料技术领域,尤其涉及一种石墨烯负载钴掺杂二氧化钛光催化剂及其制备方法。
背景技术
TiO2具有无毒、催化活性高、稳定性好以及抗氧化能力强、成本低等优点,广泛用于降解有机污染物、废水处理等领域。虽然TiO2在光催化技术中有诸多优势,但是也存在禁带宽(3.2eV)、对自然光的利用率低、吸收光阈值高等缺点,因此对二氧化钛纳米材料进行改性成为必然。
利用金属元素掺杂是一种很有前景的方法,将金属离子引入到TiO2晶格内部,可以减小TiO2纳米粒径改变晶相结构引起的晶格缺陷,在禁带中引入新的杂质能级,减小禁带宽度,降低光电子跃迁所需能量进而提高TiO2光催化活性。
发明内容
针对现有技术的不足,本发明的目的在于提供一种新型石墨烯负载钴掺杂二氧化钛光催化剂及其制备方法;本发明通过静电纺丝法制备光催化剂,制备方法简单;制得的光催化剂具有可在常温常压下进行光催化反应,反应速度快,催化效率高,应用范围广等优点。
本发明首先以钛酸四正丁酯和硝酸钴分别作为钛源和钴源制备前驱体溶液,以无水乙醇、冰醋酸和和PVP作为助剂,按比例将前驱体和助剂混合均匀得到纺丝液;接着进行高压静电纺丝得到初始 PVP/Co-TiO2纤维;然后在马弗炉中煅烧得到 Co-TiO2纳米纤维;最后使用真空冷冻干燥法将Co-TiO2纳米纤维负载到石墨烯上,得到石墨烯负载钴掺杂二氧化钛光Co-TiO2/RGO光催化剂。制得。本发明的技术方案具体介绍如下。
一种石墨烯负载钴掺杂二氧化钛光催化剂的制备方法,具体步骤如下:
(1)前驱体的制备
将钛酸四正丁酯、冰醋酸和无水乙醇混合后,按照Co/Ti的摩尔比=0.005~0.02加入硝酸钴,再在室温下搅拌得聚醋酸氧钛前驱体;
(2)纺丝液的制备
按聚乙烯吡咯烷酮PVP:无水乙醇=1:4~1:6的质量比,量取无水乙醇,边搅拌边加入PVP调节溶液至一定黏度,再继续搅拌0.5~1小时,直至排除气泡,然后向其中加入步骤(1)中所得的聚醋酸氧钛前驱体,搅拌2~4小时,静置,得到均一稳定的橙黄色PVP/Co-TiO2纺丝液;
(3)PVP/Co-TiO2复合纤维的制备
将步骤(2)中的PVP/Co-TiO2纺丝液灌入注射器内,选择不锈钢针头,将注射器倒置排出管内气泡;然后利用静电纺丝装置进行电纺,将正极连接针头,负极连接铁片板,调节固化距离、电压及设定相关参数,纺丝结束后,在负极铁片板上得到PVP/Co-TiO2复合纤维;
(4)Co-TiO2纳米纤维的制备
将步骤(3)得到的PVP/Co-TiO2复合纤维置于马弗炉中,在500℃~800℃的温度下煅烧4~5小时,煅烧结束后,自然冷却至室温,取出样品研磨,得到Co-TiO2纳米纤维;
(5)Co-TiO2/RGO气凝胶的制备
将Co-TiO2纳米纤维加入到石墨烯水凝胶中搅拌均匀后,真空冷冻干燥,得到 Co-TiO2/RGO气凝胶,即石墨烯负载钴掺杂二氧化钛光催化剂。
本发明中,步骤(1)中, 钛酸四正丁酯、冰醋酸和乙醇摩尔比为1:1:(1~4)。
本发明中,步骤(1)中, Co/Ti的摩尔比0.010~0.015。
本发明中,步骤(2)中, PVP溶液黏度2000~3000mPa·S之间。
本发明中,步骤(3)中,调节固化距离为10~15cm,电压选择为12~20kV,推进速度为1.2~2mL/h。
本发明中,步骤(3)中,纺丝时间为3~5小时。
本发明中,步骤(4)中,煅烧温度为550~650℃。
本发明中,步骤(5)中,石墨烯水凝胶通过下述步骤制得:
1)将氧化石墨烯分散液、乙二胺和硼酸钠混合后,在95~105℃的温度下反应10~20h;
2)取出步骤1)得到的样品放入体积比为1:1的乙醇和水的混合溶液中浸泡2~4h,
得到洁净的石墨烯凝胶。
本发明中,步骤(5)中,真空冷冻干燥程序如下:抽真空后降温到-50℃并保温8~10小时,升温到-40℃并保温5~7小时,升温到-30℃并保温5~7小时,升温到-20℃并保温5~7小时,升温到-10℃并保温5~7小时,升温到0℃并保温2~4小时,升温到10℃并保温2~4小时,最后升至常温。
本发明进一步提供一种上述制备方法制得的石墨烯负载钴掺杂二氧化钛光催化剂。
和现有技术相比,本发明的有益效果在于:
1. 本发明制备方法简单、生产成本低,制备的复合光催化剂形貌可控、比表面积高、光学性能优良、绿色环保;光催化剂具有较好的光催化降解有机污染物效果,在模拟太阳光下,掺杂改性的光催化剂对甲苯的降解比普通的光催化剂具有更高的催化降解效果,在VOCs治理领域有应用前景;
2. 本发明采用静电纺丝技术制备Co-TiO2纳米纤维,原料易得,制备过程简便易操作,产品中纳米颗粒分散均匀,能有效的解决纳米颗粒的团聚钝化问题;
3. 本发明利用钴掺杂二氧化钛使电子结构发生改变,从而提高了二氧化钛光吸收性能和可见光的吸收能力;
4. 本发明采用石墨烯作为光催化剂Co-TiO2的载体,使其本身增加了吸附性能和稳定性,从而提高了去污效果;
5. 本发明采用真空冷冻干燥法使Co-TiO2负载到RGO,增加了其比表面积,固定了其内部结构,从而进一步提高了二氧化钛的催化性能;同时催化剂的光生电子空穴对的复合率明显降低,也促进了二氧化钛的光吸收性能的提高。
附图说明
图1为本发明不同煅烧温度和钴掺杂量制备的Co-TiO2/RGO光催化剂降解甲苯效果。
图2为本发明实施例1提供的Co-TiO2光催化剂高分辨电镜图(SEM)。
图3为本发明实施例1提供的Co-TiO2/RGO光催化剂高分辨电镜图(SEM)。
图4为本发明实施例1提供的Co-TiO2/RGO光催化剂扫描电镜中的能谱(EDX)。
图5为本发明制备的不同钴掺杂比的Co-TiO2光催化剂X射线衍射图(XRD)。
具体实施方式
以下结合附图对本发明的原理和特征进行描述,对本发明实施例中的技术方案进行清楚、完整地描述。显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例,基于本发明中的实施例,只用于解释本发明,并非用于限定本发明的范围。
实施例1
步骤一,量取15mL无水乙醇于烧杯,然后分别取15mL冰醋酸和15mL钛酸四正丁酯(0.044mol)边搅拌便加入到乙醇中,再加入0.128g(0.00044mol)硝酸钴,最后室温下经磁力搅拌1h,制得Co-TiO2前驱体溶液;
步骤二,纺丝液的制备:称取20g无水乙醇于烧杯中,再称取5g聚乙烯吡咯烷酮(PVP,Mw=1300000),边搅拌边加入PVP,搅拌速度为400rpm速率,搅拌时间为30min,使PVP溶液黏度2000~3000mPa·S;之后进一步磁力搅拌1h至气泡排出,再加入步骤一中所得的Co-TiO2前驱体溶液,搅拌2小时,静置得到均一稳定的橙黄色PVP/Co-TiO2纺丝液;
步骤三,PVP/Co-TiO2复合纤维的制备:将步骤二中的PVP/Co-TiO2纺丝液灌入10mL注射器内,选择内径为0.7mm的不锈钢针头,将注射器倒置排出管内气泡;然后安装静电纺丝装置,连接时将正极连接针头,负极连接铁片板进行电纺。调节固化距离(针头与收集装置距离) 12cm、电压为15 kV,推进速度为1.8mL/h,通过纺丝5小时,在负极铁片板上得到PVP/Co-TiO2复合纤维。
步骤四,Co-TiO2纳米纤维的制备:将步骤三中得到的PVP/Co-TiO2复合纤维在600℃的马弗炉煅烧4小时得到Co-TiO2纳米纤维。
步骤五,石墨烯水凝胶的制备:取60mL氧化石墨烯分散液(6mg/mL)于烧杯中,边搅拌边加入0.36mL乙二胺和0.003g硼酸钠。将混合液经过10min超声后倒入反应釜,在烘箱中继续进行反应,控制反应温度100℃,反应时间14h,然后将样品取出放入50%VOL乙醇的水溶液中浸泡3h得到洁净的石墨烯水凝胶待用。
步骤六,Co-TiO2/RGO气凝胶的制备:按照Co-TiO2纳米纤维和石墨烯的质量比为5:100,将Co-TiO2纳米纤维充分研磨后与石墨烯凝胶混匀,再放入真空冷冻干燥机中35小时,得到干燥的Co-TiO2/RGO气凝胶。真空冷冻干燥机内进行干燥处理时设定程序:抽真空后降温到-50℃并保温8小时,升温到-40℃并保温7小时,升温到-30℃并保温7小时,升温到-20℃并保温6小时,升温到-10℃并保温6小时,升温到0℃并保温3小时,升温到10℃并保温4小时,最后至常温,打开真空阀,取出样品。
如图1所示,本发明采用静电纺丝法制备的Co-TiO2光催化剂微观形貌呈规则的纳米棒状结构,每根纳米棒由大量细小的TiO2颗粒累积,其表面粗糙有钴在面层生长且有空洞结构,这种微观形貌利于对有机物的吸附。
图2为本发明实施例1步骤四提供的未在石墨烯上负载的Co-TiO2光催化剂高分辨电镜图(SEM)。
图3为本发明实施例1提供的Co-TiO2/RGO光催化剂高分辨电镜图(SEM)。从图3可看出,利用静电纺丝所制备的催化剂具有较好的形貌特征,具有纳米结构的棒状体,可以更好增大接触面积。
图4为本发明实施例1提供的Co-TiO2/RGO光催化剂扫描电镜中的能谱(EDX)。从图4可看出,该复合材料Co:Ti约等于1:100,与掺杂定的标准基本一致。
图5为本发明制备的不同钴掺杂比的Co-TiO2光催化剂X射线衍射图(XRD),结果显示本发明采用静电纺丝法制备的Co-TiO2光催化剂中包含有锐钛矿和金红石两种晶型。
催化剂性能测试:
经实施例1制备的Co-TiO2/RGO光催化剂催化剂,在模拟可见光下进行催化降解甲苯反应,在一个0.5m³的石英容器中,甲苯的初始浓度为200ppm,催化剂的投加量为0.05g,反应温度为30℃,反应时间为45min时,降解率达94.7%。
在上述相同的催化降解条件下,本发明实施例1步骤四提供的未在石墨烯上负载的Co-TiO2光催化剂的甲苯降解率为68%。
实施例2
其余步骤与实施例1相同,所不同的是步骤四中,煅烧温度为500℃。
制备的催化剂在实施例1中的相同催化降解条件下,降解率达82.1%。
实施例3
其余步骤与实施例1相同,所不同的是步骤四中,煅烧温度为700℃。
制备的催化剂在实施例1中的相同催化降解条件下,降解率达86.9%。
实施例4
其余步骤与实施例1相同,所不同的是步骤四中,煅烧温度为800℃。
制备的催化剂在实施例1中的相同催化降解条件下,降解率达82.7%。
以上不同热处理温度条件下制得的Co-TiO2/ACF复合光催化剂降解甲苯的效果如图1所示。
实施例5
其余步骤与实施例1相同,所不同的是步骤一中,硝酸钴改为0g。
制备的催化剂在实施例1中的相同催化降解条件下,其降解率达82.6%。
实施例6
其余步骤与实施例1相同,所不同的是步骤一中,硝酸钴改为0.064g。
制备的催化剂在实施例1中的相同催化降解条件下,其降解率达86.3%。
实施例7
其余步骤与实施例1相同,所不同的是步骤一中,硝酸钴改为0.192g。
制备的催化剂在实施例1中的相同催化降解条件下,其降解率达88.3%。
实施例8
其余步骤与实施例1相同,所不同的是步骤一中,硝酸钴改为0.256g。
制备的催化剂在实施例1中的相同催化降解条件下,其降解率达85.1%。
以上不同钴掺杂比条件下制得的Co-TiO2/ACF复合光催化剂降解甲苯的效果如图1所示。
以上对本发明的具体实施例进行了描述。需要理解的是,本发明并不局限于上述特定实施方式,本领域技术人员可以在权利要求的范围内做出各种变形或修改,这并不影响本发明的实质内容。
Claims (9)
1.一种石墨烯负载钴掺杂二氧化钛光催化剂在可见光下催化降解甲苯中的应用,其特征在于,所述催化剂的制备方法包括以下步骤:
(1)前驱体的制备
将钛酸四正丁酯、冰醋酸和无水乙醇混合后,按照Co/Ti的摩尔比=0.005~0.02加入硝酸钴,再在室温下搅拌得聚醋酸氧钛前驱体;
(2)纺丝液的制备
按聚乙烯吡咯烷酮PVP:无水乙醇=1:4~1:6的质量比,量取无水乙醇,边搅拌边加入PVP调节溶液至一定黏度,再继续搅拌0.5~1小时,直至排除气泡,然后向其中加入步骤(1)中所得的聚醋酸氧钛前驱体,搅拌2~4小时,静置,得到均一稳定的橙黄色PVP/Co-TiO2纺丝液;
(3)PVP/Co-TiO2复合纤维的制备
将步骤(2)中的PVP/Co-TiO2纺丝液灌入注射器内,选择不锈钢针头,将注射器倒置排出管内气泡;然后利用静电纺丝装置进行电纺,将正极连接针头,负极连接铁片板,调节固化距离、电压及设定相关参数,纺丝结束后,在负极铁片板上得到PVP/Co-TiO2复合纤维;
(4)Co-TiO2纳米纤维的制备
将步骤(3)得到的PVP/Co-TiO2复合纤维置于马弗炉中,在500℃~800℃的温度下煅烧4~5小时,煅烧结束后,自然冷却至室温,取出样品研磨,得到Co-TiO2纳米纤维;
(5)Co-TiO2/RGO气凝胶的制备
将Co-TiO2纳米纤维加入到石墨烯水凝胶中搅拌均匀后,真空冷冻干燥,得到 Co-TiO2/RGO气凝胶,即石墨烯负载钴掺杂二氧化钛光催化剂。
2.根据权利要求1所述的应用,其特征在于,步骤(1)中, 钛酸四正丁酯、冰醋酸和无水乙醇摩尔比为1:1:(1~4)。
3.根据权利要求1所述的应用,其特征在于,步骤(1)中, Co/Ti的摩尔比0.01:1~0.015:1。
4.根据权利要求1所述的应用,其特征在于,步骤(2)中,PVP溶液黏度2000~3000mPa·S之间。
5.根据权利要求1所述的应用,其特征在于,步骤(3)中,调节固化距离为10~15cm,电压选择为12~20kV,推进速度为1.2~2mL/h。
6.根据权利要求1所述的应用,其特征在于,步骤(3)中,纺丝时间为3~5小时。
7.根据权利要求1所述的应用,其特征在于,步骤(4)中,煅烧温度为550~650℃。
8.根据权利要求1所述的应用,其特征在于,步骤(5)中,石墨烯水凝胶通过下述步骤制得:
1)将氧化石墨烯分散液、乙二胺和硼酸钠混合后,在95~105℃的温度下反应10~20h;
2)取出步骤1)得到的样品放入体积比为1:1的乙醇和水的混合溶液中浸泡2~4h,得到洁净的石墨烯水凝胶。
9.根据权利要求1所述的应用,其特征在于,步骤(5)中,真空冷冻干燥程序如下:抽真空后降温到-50℃并保温8~10小时,升温到-40℃并保温5~7小时,升温到-30℃并保温5~7小时,升温到-20℃并保温5~7小时,升温到-10℃并保温5~7小时,升温到0℃并保温2~4小时,升温到10℃并保温2~4小时,最后升至常温。
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