CN110204714B - 一种磁性共价三嗪骨架材料及其制备方法和应用 - Google Patents
一种磁性共价三嗪骨架材料及其制备方法和应用 Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 52
- 239000013311 covalent triazine framework Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 32
- BHXFKXOIODIUJO-UHFFFAOYSA-N benzene-1,4-dicarbonitrile Chemical compound N#CC1=CC=C(C#N)C=C1 BHXFKXOIODIUJO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000015556 catabolic process Effects 0.000 claims abstract description 8
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Abstract
本发明涉及一种磁性共价三嗪骨架材料及其制备方法和应用,磁性共价三嗪骨架材料包括共价三嗪骨架和Fe3O4。本发明的磁性共价三嗪骨架材料具有磁性,方便回收利用,能够用于废水处理中,且能够作为催化剂用于抗生素的降解中。本发明的制备方法采用微波为热源,以Fe3O4作为微波吸收传递介质,使得对苯二腈能够迅速缩合,同时由于Fe3O4的存在,使得反应过程中粉末聚集,而不易产生粉末飞溢现象,使得反应更加完全。
Description
技术领域
本发明具体涉及一种磁性共价三嗪骨架材料及其制备方法和应用。
背景技术
共价有机骨架(Covalent Organic Frameworks,COFs)是一种新型的由轻元素(H、O、C、N、B)通过结合力强大的共价键(如C-C、C-N、C-O等)构成的高性能碳质高分子材料,由于共价键的存在,促使其在不同溶剂中具备较高的化学稳定性。共价三嗪骨架(CovalentTriazine-based Frameworks,CTFs)是COFs的一类分支,是一种具有刚性疏水芳香族骨架和极性官能团的长链聚合物,通过以芳香族腈为原料,ZnCl2为催化剂,经三聚反应缩合而成,因其不需要有机溶剂,成本低、含氮量高等而备受关注。目前常用的CTF合成方法包括溶剂热合成法、离子热合成法、微波合成法等,传统的热合成方法所需条件较为苛刻,需要在高温高压(400-700℃)条件下反应较长时间(20-116h),普通的实验条件难以满足要求。而微波合成技术因其操作简便、反应时间短及能量利用率高等优势被频繁应用于材料制备领域。
但是,现有技术中的共价三嗪骨架材料的性能仍有待提高,且在应用过程中,存在共价三嗪骨架材料难以回收的问题。
发明内容
本发明所要解决的技术问题是克服现有技术的不足,提供一种磁性共价三嗪骨架材料及其制备方法和应用,该磁性共价三嗪骨架材料具有磁性,易于回收,且制备方法简单。
为解决以上技术问题,本发明采用如下技术方案:
本发明一方面提供一种磁性共价三嗪骨架材料,包括共价三嗪骨架和Fe3O4。
本发明的所述的磁性共价三嗪骨架材料呈正四面体形态。
本发明的所述的磁性共价三嗪骨架材料具有超顺磁性。根据一个优选实施方式,所述的磁性共价三嗪骨架材料的饱和磁化强度大于70emu·g-1。
本发明的所述的磁性共价三嗪骨架材料具有孔隙,进一步地,所述的磁性共价三嗪骨架材料具有较大的孔径与较小的孔体积。根据一个优选实施方式,所述的磁性共价三嗪骨架材料的孔径为6~8nm,孔体积为0.02~0.04cm3·g-1。
根据一个优选实施方式,所述的磁性共价三嗪骨架材料表面的碳原子质量百分比为46~56%,氮原子质量百分比为5.5~6.6%,氧原子质量百分比为28~36%,铁原子质量百分比为8.9~10.9%,锌原子质量百分比为1.2~1.4%。
本发明中,所述的磁性共价三嗪骨架材料为粉末状。
本发明另一方面提供一种所述的磁性共价三嗪骨架材料的制备方法,所述的磁性共价三嗪骨架材料由对苯二腈和Fe3O4在ZnCl2的作用下,在微波条件下反应制得。
本发明采用Fe3O4作为微波吸收传递介质,与微波共同使用,能够保证反应温度以使反应进行;另外,通过调节不同微波输出功率,使得生成的磁性共价三嗪骨架材料的性质有所差异,从而可以适用于不同领域。
优选地,所述的微波的输出功率为300~600W,从而能够促使反应充分进行,提高原料利用率。
优选地,所述的对苯二腈和Fe3O4的投料摩尔比为1:0.5~1.2,进一步优选为1:1~1.2。在兼顾产率的同时,采用上述投料摩尔比可以使产物的性能更优。
优选地,所述的对苯二腈和所述的ZnCl2的投料质量比为1:5~10。在兼顾产率的同时,采用上述质量比可以降低产物中锌盐的残留量。
根据一个优选且具体实施方式,所述的制备方法的具体实施方式为:将所述的对苯二腈、所述的Fe3O4和所述的ZnCl2混合后,在300~600W的微波功率下反应30~90min,然后用盐酸浸泡后,在外加磁场条件下分离沉淀物,所述的沉淀物经洗涤、干燥得到所述的磁性共价三嗪骨架材料。
本发明的第三个方面是提供所述的磁性共价三嗪骨架材料在废水处理中的应用。
特别是所述的磁性共价三嗪骨架材料吸附废水中的亚甲基蓝、染料等有害物质。
本发明的第三个方面是提供所述的磁性共价三嗪骨架材料在抗生素的降解中的应用,其中,在进行所述的抗生素的降解时,添加有所述的磁性共价三嗪骨架材料和氧化剂。
其中,所述的磁性共价三嗪骨架材料作为催化剂。
本发明中的原料可以市购获得,或者本发明中的Fe3O4采用水热法制备。
水热法制备Fe3O4的具体方法为:称取6.74g FeCl3·6H2O置于125mL乙二醇中,搅拌30min得均相溶液,加入14.37g醋酸钠,继续搅拌30min混匀,将混合溶液转移至200mL高压反应釜中,在200℃下反应8h。冷却至室温后,用磁铁收集黑色磁性微球,用水和乙醇交替洗涤三次,于60℃下真空干燥6h,研磨备用。
由于上述技术方案的实施,本发明与现有技术相比具有如下优点:
本发明的磁性共价三嗪骨架材料具有磁性,方便回收利用,能够用于废水处理中,且能够作为催化剂用于抗生素的降解中。
本发明的制备方法采用微波为热源,以Fe3O4作为微波吸收传递介质,使得对苯二腈能够迅速缩合,同时由于Fe3O4的存在,使得反应过程中粉末聚集,而不易产生粉末飞溢现象,使得反应更加完全。
附图说明
图1为实施例5制得的MCTF的SEM图(左)和TEM图(右);
图2为实施例5制得的MCTF和对苯二腈(DCB)的FTIR光谱图;
图3为实施例5制得的MCTF的XRD图;
图4为实施例5制得的MCTF的磁化曲线;
图5为实施例5制得的MCTF的XPS图;
图6为实施例5制得的MCTF的N2吸附-脱附等温线;
图7为MCTF、DCB和Fe3O4对AO7的吸附率曲线;
图8为不同体系下SMX的降解趋势;
图9为不同实施例制得的MCTF催化PMS降解SMX的趋势。
具体实施方式
下面采用具体实施方式对本发明的技术方案进一步详细说明。
下述Fe3O4购自麦克林I811693-500g;对苯二腈购自阿拉丁D111053;氯化锌购自麦克林Z820755。下述实施例采用的微波设备为上海新仪微波化学有限公司(Uwave-2000)。
实施例1
称取2g对苯二腈与2g Fe3O4,混合均匀后迅速加入16g ZnCl2,混合均匀后将粉末转移入石英坩埚,在500W功率下反应60min,得到黑色产物,将其用0.1mol·L-1HCl浸泡以去除残余物,同时防止ZnCl2水解,浸泡完成后在外加磁场条件下分离沉淀物,再用水和无水乙醇交替洗三次,60℃下真空干燥6h,取出、研磨得到0.85g MCTF粉末。
实施例2
称取2g对苯二腈与4g Fe3O4,混合均匀后迅速加入16g ZnCl2,混合均匀后将粉末转移入石英坩埚,在300W功率下反应60min,得到黑色产物,将其用0.1mol·L-1HCl浸泡以去除残余物,同时防止ZnCl2水解,浸泡完成后在外加磁场条件下分离沉淀物,再用水和无水乙醇交替洗三次,60℃下真空干燥6h,取出、研磨得到2.93g MCTF粉末。
实施例3
称取2g对苯二腈与4g Fe3O4,混合均匀后迅速加入16g ZnCl2,混合均匀后将粉末转移入石英坩埚,在400W功率下反应60min,得到黑色产物,将其用0.1mol·L-1HCl浸泡以去除残余物,同时防止ZnCl2水解,浸泡完成后在外加磁场条件下分离沉淀物,再用水和无水乙醇交替洗三次,60℃下真空干燥6h,取出、研磨得到2.68g MCTF粉末。
实施例4
称取2g对苯二腈与4g Fe3O4,混合均匀后迅速加入16g ZnCl2,混合均匀后将粉末转移入石英坩埚,在500W功率下反应60min,得到黑色产物,将其用0.1mol·L-1HCl浸泡以去除残余物,同时防止ZnCl2水解,浸泡完成后在外加磁场条件下分离沉淀物,再用水和无水乙醇交替洗三次,60℃下真空干燥6h,取出、研磨得到1.54g MCTF粉末。
实施例5
称取2g对苯二腈与4g Fe3O4,混合均匀后迅速加入16g ZnCl2,混合均匀后将粉末转移入石英坩埚,在600W功率下反应60min,得到黑色产物,将其用0.1mol·L-1HCl浸泡以去除残余物,同时防止ZnCl2水解,浸泡完成后在外加磁场条件下分离沉淀物,再用水和无水乙醇交替洗三次,60℃下真空干燥6h,取出、研磨得到1.24g MCTF粉末。
该MCTF粉末的SEM和TEM如图1所示,从图中可见,其为正四面体形态,棱角分明,能够明显看到边界痕迹。
通过FTIR对MCTF与原材料DCB的官能团进行分析,如图2所示,由于合成MCTF的原料DCB含有-C≡N键,因此在DCB图谱2232cm-1处有明显的振动峰,与之相比,MCTF在该处无明显振动峰,在1613cm-1和1411cm-1处出现C=N键与C-C键振动峰,证明三嗪环存在,三聚反应已经完成,588cm-1处为Fe-O振动峰。
为了研究铁氧化合物的组成,对MCTF的XRD进行分析,如图3,在衍射角18.3°、30.4°、35.4°、37°、43°、53.3°、56.8°、62.4°显示出强衍射峰,峰位与Fe3O4标准卡片(JCPDS75-1609)符合,其分别对应了Fe3O4的111、220、311、222、400、422、511、440面,可以确认MCTF中包含的磁性铁氧化物为Fe3O4。
通过在室温条件下测定了MCTF的饱和磁化强度,如图4,可见不存在明显滞后环,为S型磁化曲线,无磁滞现象出现,材料表现出良好的超顺磁性。MCTF的饱和磁化强度为75.14emu·g-1,具有良好的磁性能。
图5是MCTF的XPS图,在284.1eV、398.1eV、530.1eV出现了三个信号较强的峰,分别对应的是MCTF中C1s,N1s,O1s的结合键能,说明材料表面的主要元素有碳、氮、氧。同时在1021.1出现一个较弱的Zn2p峰,说明在材料合成过程中,过量的ZnCl2的加入使得即使通过盐酸的长时间洗涤,仍然残留一定量的ZnCl2。MCTF中不同原子质量百分比见表1,从表1可见,虽然材料中含有ZnCl2残留,但Zn原子质量仅为1.31%。
表1
名称 | C | N | O | Fe | Zn |
原子质量% | 50.63 | 6.05 | 32.15 | 9.85 | 1.31 |
通过在77K的吸氮实验,对MCTF的孔隙进行评价,图6为MCTF的N2吸附-脱附等温线,显示其为Ⅳ型的等温线,可看到滞后环存在,证明了该材料具有大量的微孔,其BET比表面积为93.6131m2·g-1,却拥有孔径6.93nm,孔体积0.03cm3·g-1的特殊结构,较大的孔径与较小的孔体积使得材料具有存储物质,维持物质活性的潜能。
应用例1、亚甲基蓝吸附实验
取5mL的亚甲基蓝(10mg·L-1)于离心管中,分别加入10mg实施例2至5制得的MCTF材料,涡旋30s后用紫外可见分光光度计测量残液吸光度,带入标准曲线计算残液亚甲基蓝浓度,利用如下公式计算吸附率,各实施例制得的MCTF材料的吸附率结果见表2。
吸附率(%)=(c0-ct)×100/c0
表2
实施例2 | 实施例3 | 实施例4 | 实施例5 | |
吸附率 | 57.4% | 63.3% | 96.9% | 93.1% |
应用例2、AO7吸附实验
取100mL的AO7工作溶液(10mg·L-1)于锥形瓶中,利用0.1mol·L-1的HCl和NaOH调节溶液初始pH。分别将制备好的MCTF(实施例3所得)、DCB和Fe3O4投入配置好的溶液中即开始计时,调节磁力搅拌转速大约在1000r·min-1,使得高速下MCTF被甩出而不附着在转子表面,均匀的分布在溶液中,同时分别在不同时间点取5mL溶液,经0.45μm水系滤膜滤后待测。
MCTF、DCB和Fe3O4对AO7的吸附率见图7,其中,测定时T=298K,C(AO7)=10mg·L-1,pH≈7,C(MCTF、DCB、Fe3O4)=0.4g·L-1。
20min内,对苯二腈、Fe3O4体系下AO7的吸附率分别为3.0%、3.4%。由此可知,原料对苯二腈与Fe3O4对于AO7并不具备明显的吸附作用;与之相比,20min内MCTF对AO7的吸附率达到了98.8%。
应用例3、SMX降解实验
室温条件下,注入一定量的纯水在100mL容量瓶中,同时加入一定量的过一硫酸盐(PMS),MCTF(实施例4所得)促使反应浓度分别为0.15mmol·L-1、0.3g·L-1,随后加入一定量的磺胺甲恶唑(SMX),促使反应浓度为0.5mmol·L-1,反应开始。分别在不同时间点取样,随后迅速加入过量淬灭剂Na2S2O3终止反应,猝灭后的样品经0.22μm滤膜过滤后,收集滤液利用HPLC-MS/MS分析测定。为了进行对比分析,空白样分别为单独PMS、MCTF。测定结果如图8所示,其中,测定时T=298K,C(SMX)=0.5mmol·L-1,pH≈7,C(MCTF)=0.3g·L-1,C(PMS)=0.15mmol·L-1。
从图8可见,单独PMS、MCTF无明显作用,而同时加入PMS作为氧化剂、MCTF为催化剂SMX即可在30min内降解完全。
同时考察了不同实施例制得的MCTF材料催化PMS降解SMX的效果,如图9所示,其中300W为实施例2,400W是实施例3,500W是实施例4,600W是实施例5,从图9可见,实施例5(600W)效果最佳,30min即可降解完全。
以上对本发明做了详尽的描述,其目的在于让熟悉此领域技术的人士能够了解本发明的内容并加以实施,并不能以此限制本发明的保护范围,且本发明不限于上述的实施例,凡根据本发明的精神实质所作的等效变化或修饰,都应涵盖在本发明的保护范围之内。
Claims (8)
1. 一种磁性共价三嗪骨架材料,其特征在于:包括共价三嗪骨架和Fe3O4;所述的磁性共价三嗪骨架材料由对苯二腈和Fe3O4在ZnCl2的作用下,在微波条件下反应制得,所述的磁性共价三嗪骨架材料呈正四面体形态;所述的磁性共价三嗪骨架材料具有超顺磁性,其饱和磁化强度大于70 emu•g-1;所述的磁性共价三嗪骨架材料具有孔隙,其孔径为6~8nm,孔体积为0.02~0.04 cm3•g-1。
2.一种如权利要求1所述的磁性共价三嗪骨架材料的制备方法,其特征在于:所述的磁性共价三嗪骨架材料由对苯二腈和Fe3O4在ZnCl2的作用下,在微波条件下反应制得。
3.根据权利要求2所述的制备方法,其特征在于:所述的微波的输出功率为300~600W。
4.根据权利要求2所述的制备方法,其特征在于:所述的对苯二腈和Fe3O4的投料摩尔比为1:0.5~1.2。
5.根据权利要求2所述的制备方法,其特征在于:所述的对苯二腈和所述的ZnCl2的投料质量比为1:5~10。
6.根据权利要求2所述的制备方法,其特征在于:所述的制备方法的具体实施方式为:将所述的对苯二腈、所述的Fe3O4和所述的ZnCl2混合后,在300~600W的微波功率下反应30~90min,然后用盐酸浸泡后,在外加磁场条件下分离沉淀物,所述的沉淀物经洗涤、干燥得到所述的磁性共价三嗪骨架材料。
7.如权利要求1所述的磁性共价三嗪骨架材料在废水处理中的应用。
8.如权利要求1所述的磁性共价三嗪骨架材料在抗生素的降解中的应用,其中,在进行所述的抗生素的降解时,添加有所述的磁性共价三嗪骨架材料和氧化剂。
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