CN111732138B - 一种氮掺杂碳点/钛酸纳米管复合材料及其制备方法 - Google Patents
一种氮掺杂碳点/钛酸纳米管复合材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种氮掺杂碳点/钛酸纳米管复合材料,所述复合材料为钛酸纳米管上负载有氮掺杂碳点。本发明还公开了上述氮掺杂碳点/钛酸纳米管复合材料的制备方法,具体为:将钛酸纳米管粉末超声分散于溶剂中,然后将氮掺杂碳点粉末投加到上述溶液中持续超声分散;将得到的混合液进行水热反应,对反应后的初始产物进行清洗、烘干处理得到氮掺杂碳点/钛酸纳米管复合材料。本发明复合材料能够同时高效去除水体中的抗生素和重金属。
Description
技术领域
本发明涉及一种氮掺杂碳点/钛酸纳米管复合材料,还涉及上述复合材料的制备方法。
背景技术
随着经济的快速发展,人们对物质需求不断提高,尤其对畜禽产品的需求量也越来越大。20世纪80年代后期,我国的畜牧业从最初的粗放型逐步转变为集约型。与传统的粗放型饲养方式相比,集约型和规模化的饲养方式使生产效率得到了很大的提升,并且有效增加了经济效益。与此同时,一些具有促进生长和疾病预防的物质,如铜(Cu)、锌(Zn)等重金属以及四环素类和氟喹诺酮类等抗生素,被广泛添加于畜禽养殖业的饲料中。由于畜禽对重金属和抗生素的吸收率较低,因此会将其排泄掉,大量畜禽粪便的排放,给生态环境构成了极大的威胁。现有技术中,几乎没有能够同时高效环保地去除水体中抗生素和重金属的材料,都是专门针对抗生素或重金属的处理材料。
发明内容
发明目的:本发明所要解决的技术问题是提供一种氮掺杂碳点/钛酸纳米管复合材料,该复合材料能够同时高效去除水体中的抗生素和重金属,并且反应后材料还可以回收再利用。
本发明还要解决的技术问题是提供上述氮掺杂碳点/钛酸纳米管复合材料的制备方法,该制备方法工艺简单、制备成本低。
为解决上述技术问题,本发明所采用的技术方案为:
一种氮掺杂碳点/钛酸纳米管复合材料,所述复合材料为钛酸纳米管上负载有氮掺杂碳点。
其中,每克钛酸纳米管上负载有0.1~0.15克氮掺杂碳点。
下述内容中,氮掺杂碳点标记为NCDs,钛酸纳米管标记为TNTs。
上述氮掺杂碳点/钛酸纳米管复合材料的制备方法,具体为:将钛酸纳米管超声分散于溶剂中,然后将氮掺杂碳点投加到上述溶液中持续超声分散;将得到的混合液进行水热反应,对反应后的初始产物进行清洗、烘干处理后得到氮掺杂碳点/钛酸纳米管复合材料。
其中,所述水热反应的温度为120~130℃,水热反应的时间为4~5h。
其中,烘干温度为60~70℃,烘干时间为10~12h。
其中,溶剂中,钛酸纳米管粉末与氮掺杂碳点粉末的加入质量比为1∶0.1~0.15。
有益效果:单独的钛酸纳米管利用层级之间的Na+和H+与金属阳离子进行离子交换从而实现对水体中重金属离子的吸附去除,但是单独的钛酸纳米管在可见光下没有光催化活性;单独的氮掺杂碳点有较低的光催化活性和对重金属离子的吸附去除能力;将两者组成复合材料后,复合材料中,利用NCDs的上转换光致发光特性,将TNTs的吸收带由紫外光拓宽到可见光区域,从而复合材料(中的TNTs)可以利用太阳光(即可见光)高效光催化降解抗生素的同时还能通过离子交换快速吸附去除重金属(并且吸附去除重金属的能力也大大提高,原因是复合材料具有等电点低和大的比表面积,通过离子交换和配位作用能够高效地吸附大量的二价铜离子),而且吸附重金属的过程还可以进一步提高TNTs对抗生素的降解速率(在吸附水体中重金属Cu(II)后,Cu(II)进入复合材料的层间,可以窄化其禁带宽度并拓宽对可见光的吸收带,从而进一步提高复合材料的光催化性能);另外,本发明方法工艺简单,原材料易获得,制备成本低,制得的复合材料具有化学稳定性好以及易于从溶液中分离出来的优点。
附图说明
图1为TNTs的TEM和HRTEM表征图;
图2为NCDs的TEM和HRTEM表征图;
图3为复合材料NCDs/TNTs的TEM和HRTEM表征图;
图4为复合材料NCDs/TNTs和TNTs的N2吸附-脱附等温线;
图5为复合材料NCDs/TNTs和TNTs的孔径分布图;
图6为复合材料NCDs/TNTs、TNTs和NCDs在不同pH的zeta电势;
图7为复合材料NCDs/TNTs和TNTs的紫外-可见漫反射光谱(UV-vis DRS);
图8为复合材料NCDs/TNTs和TNTs同步去除Cu(II)和抗生素诺氟沙星效果图。
具体实施方式
以下结合附图和具体实施例对本发明技术方案作进一步说明。
实施例1
钛酸纳米管(TNTs)的制备方法,具体包括如下步骤:
将1.2g TiO2投加到66.7mL浓度为10.0mol·L-1的NaOH溶液中,室温下用磁力器搅拌12h至混合均匀;然后将混合液转移到聚四氟乙烯内衬的不锈钢反应釜中(有效容积为100mL),于130℃下水热反应48h;反应后自然冷却到室温,将生成的白色固体用去离子水洗涤至上清液为中性,最后用无水乙醇分散,再于80℃下烘干12h,研细得到TNTs白色粉末。
实施例2
氮掺杂碳点(NCDs)的制备方法,具体包括如下步骤:
将2g一水合柠檬酸和1g尿素溶解在10mL去离子水中,室温下用磁力器搅拌30min至混合均匀;将混合液转移到聚四氟乙烯内衬的不锈钢反应釜中(有效容积为25mL),于180℃下水热反应4.5h;最后将得到的墨绿色液体通过透析袋过滤12h,然后冷冻干燥研磨得到NCDs墨绿色粉末。
实施例3
本发明氮掺杂碳点/钛酸纳米管复合材料(NCDs/TNTs)的制备方法,具体包括如下步骤:
步骤1,通过水热法合成白色粉末状钛酸纳米管(TNTs):
将1.2g TiO2投加到66.7mL浓度为10.0mol·L-1的NaOH溶液中,室温下用磁力器搅拌12h至混合均匀;然后将混合液转移到聚四氟乙烯内衬的不锈钢反应釜中(有效容积为100mL),于130℃下水热反应48h;反应后自然冷却到室温,将生成的白色固体用去离子水洗涤至上清液为中性,最后用无水乙醇分散,再于80℃下烘干12h,研细得到TNTs白色粉末;
步骤2,通过水热法合成氮掺杂碳点(NCDs):
将2g一水合柠檬酸和1g尿素溶解在10mL去离子水中,室温下用磁力器搅拌30min至混合均匀;将混合液转移到聚四氟乙烯内衬的不锈钢反应釜中(有效容积为25mL),于180℃下水热反应4.5h;最后将得到的墨绿色液体通过透析袋过滤12h,然后冷冻干燥研磨得到NCDs墨绿色粉末;
步骤3,将NCDs负载到TNTs上:
将1g TNTs固体粉末通过超声分散到30mL乙醇溶液中,然后将0.125g NCDs投加到上述溶液中持续超声分散30min;将得到的混合液转移到聚四氟乙烯内衬的不锈钢反应釜中(有效容积为25mL),于120℃下水热反应4h;反应后自然冷却到室温,将生成的淡绿色固体用无水乙醇洗涤两次并分散,最后在60℃下烘干10h,研细得到NCDs/TNTs淡绿色粉末。
实施例4
本发明氮掺杂碳点/钛酸纳米管复合材料的制备方法,具体包括如下步骤:
步骤1同实施例3;
步骤2同实施例3;
步骤3,将NCDs负载到TNTs上:
将1g TNTs固体粉末通过超声分散到30mL乙醇溶液中,然后将0.1g NCDs投加到上述溶液中持续超声分散30min;将得到的混合液转移到聚四氟乙烯内衬的不锈钢反应釜中(有效容积为25mL),于120℃下水热反应4h;反应后自然冷却到室温,将生成的淡绿色固体用无水乙醇洗涤两次并分散,最后在60℃下烘干10h,研细得到NCDs/TNTs淡绿色粉末。
实施例5
本发明氮掺杂碳点/钛酸纳米管复合材料的制备方法,具体包括如下步骤:
步骤1同实施例3;
步骤2同实施例3;
步骤3,将NCDs负载到TNTs上:
将1g TNTs固体粉末通过超声分散到30mL乙醇溶液中,然后将0.15g NCDs投加到上述溶液中持续超声分散30min;将得到的混合液转移到聚四氟乙烯内衬的不锈钢反应釜中(有效容积为25mL),于120℃下水热反应4h;反应后自然冷却到室温,将生成的淡绿色固体用无水乙醇洗涤两次并分散,最后在60℃下烘干10h,研细得到NCDs/TNTs淡绿色粉末。
实施例1~5制得的材料在可见光下同时光催化降解溶液中的诺氟沙星和吸附重金属Cu(II):
取五组诺氟沙星初始浓度为5mg/L、Cu(II)初始浓度为60mg/L的溶液100mL(即溶液中同时含有诺氟沙星和二价铜离子),分别放入用于进行光催化反应的烧杯中,调节溶液的pH=5±0.1,每组溶液中分别投加等量的实施例1~5制得的材料,材料的投加浓度均为0.5g/L,通过磁力搅拌进行暗反应60min达到吸附解吸平衡,然后放置于光催化反应的可见光源下继续磁力搅拌120min后,取上清液过0.22μm的水系膜后通过紫外可见分光光度计于272.5nm的波长下测定溶液中诺氟沙星的含量和通过ICP-OES来测定溶液中Cu(II)的浓度。
表1为实施例1~5制得的材料在去除水体中共存的诺氟沙星的结果:
溶液中诺氟沙星残余浓度(mg/L) | 去除率(%) | |
实施例1的光催化剂 | 5 | 0 |
实施例2的光催化剂 | 4.76 | 4.8 |
实施例3的光催化剂 | 0.09 | 98.2 |
实施例4的光催化剂 | 1.03 | 79.4 |
实施例5的光催化剂 | 0.88 | 82.4 |
表2为实施例1~5制得的材料在去除水体中共存的Cu(II)的结果:
溶液中Cu(II)残余浓度(mg/L) | 去除率(%) | |
实施例1的光催化剂 | 10.05 | 83.3 |
实施例2的光催化剂 | 58.21 | 3.0 |
实施例3的光催化剂 | 0.035 | 99.94 |
实施例4的光催化剂 | 0.096 | 99.84 |
实施例5的光催化剂 | 0.072 | 99.8 |
由表1可以得出,实施例3得到的NCDs/TNTs复合材料对诺氟沙星的去除能力最好,较实施例1和2分别提高了98.2%和93.4%。较实施例4和5也是效果最好的,说明复合材料在制备过程中NCDs投加量会影响NCDs/TNTs的表面性能,即复合材料表面官能团的数量和表面电势的变化,进而影响异质结构的稳定性及其光催化性能。
由表2可以得出,实施例3得到的NCDs/TNTs复合材料对Cu(II)的去吸附最好,较实施例1和2分别提高了16.6%和96.9%。说明复合材料在同步去除溶液中诺氟沙星和Cu(II)时,均取得了很好的效果。有以下几方面原因:1、NCDs表面的氨基和TNTs表面的羟基构成异质结(Ti-N-H),使得复合材料表面带负电,有利于对带正电荷的诺氟沙星的吸附(在pH=5的条件下),进而促进了其对诺氟沙星的光降解;2、NCDs的上转换光学性能使得TNTs可以吸收可见光,进而可以在可见光下光降解诺氟沙星;3、NCDs中掺杂N的亲电子性能,促进了复合材料光催化过程中光生载流子的分离,提高了其光催化性能;4、复合材料的比表面积增大和表面电势的变化(表面电势降低,更利于吸附金属阳离子),使得其对Cu(II)的吸附能力增大,而且吸附的Cu(II)进入TNTs的层间,会窄化其禁带宽度和拓宽其对可见光的吸收,并且Cu(II)还能捕获电子和促进光生载流子的分离,进一步提高了对共存的诺氟沙星的光降解率。
通过图1~3可知,TNTs是中空、两端开口、粗细均匀的多层纳米管,NCDs/TNTs是由钛酸纳米管(TNTs)和氮掺杂碳点(NCDs)构成的复合材料。
通过图4可知,NCDs/TNTs复合材料的比表面积为265.87m2/g,高于TNTs(245.32m2/g)。此外,两个样品的等温线与典型的H3滞后环的IV型一致,表明材料中存在介孔结构。此外,还利用Barrett-Joyner-Halenda(BJH)的测量结果进一步分析了样品的孔径分布。从图5中可以看出,TNTs的平均孔径和孔隙体积12.334nm和0.983cm3/g;NCDs-TNTs复合材料的平均孔径约为11.674nm,孔隙体积约为1.026cm3/g。
通过图6可知,NCDs/TNTs、TNTs和NCDs的表面zeta电势的变化,在pH=5时,NCDs-TNTs、TNTs和NCDs表面电势分别为-31.5,-4.8,-5.0mV。
通过图7可知,纯TNTs能够对约375nm处的紫外光产生响应。与纯TNTs相比,NCDs/TNTs复合材料的光学响应范围有明显的红移。可见,NCDs/TNTs复合材料在400-500nm可见光波段表现出增强的吸附作用,说明负载NCDs可以提高NCDs/TNTs复合材料在可见光区域的吸附强度。
通过图8可知,Cu(II)很快就被NCDs/TNTs吸附完,即使和诺氟沙星共处时,Cu(II)去除效率仍然很高,在60分钟达到95%。NCDs/TNTs光降解诺氟沙星的效率在与Cu(II)共存时,相比单独只有诺氟沙星时的去除率提高了1.6倍,这是由于吸附二价铜离子到TNTs的层间,引入了新的杂质能级,使得TNTs的禁带宽度变窄,进一步增加了对光的吸收,导致其光催化活性进一步增强。
Claims (3)
1.一种用于去除水体中抗生素和重金属的氮掺杂碳点/钛酸纳米管复合材料,其特征在于:所述复合材料为钛酸纳米管上负载有氮掺杂碳点,每克钛酸纳米管上负载有0.1~0.15克氮掺杂碳点;NCDs表面的氨基和TNTs表面的羟基构成异质结;NCDs和TNTs通过键Ti-N-H连接;
上述氮掺杂碳点/钛酸纳米管复合材料的制备方法,具体为:将钛酸纳米管超声分散于溶剂中,然后将氮掺杂碳点投加到上述溶液中持续超声分散;将得到的混合液进行水热反应,水热反应的温度为120~130°C,水热反应的时间为4~5h;对反应后的初始产物进行清洗、烘干处理得到氮掺杂碳点/钛酸纳米管复合材料。
2.根据权利要求1所述的用于去除水体中抗生素和重金属的氮掺杂碳点/钛酸纳米管复合材料,其特征在于:烘干温度为60~70°C,烘干时间为10~12h。
3.根据权利要求1所述的用于去除水体中抗生素和重金属的氮掺杂碳点/钛酸纳米管复合材料,其特征在于:溶剂中,钛酸纳米管粉末与氮掺杂碳点粉末的加入质量比为1:0.1~0.15。
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