CN113976049A - 一种cof/cs气凝胶及其制备方法和应用 - Google Patents
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Abstract
本发明公开了一种COF/CS气凝胶及其制备方法和应用。本发明的一种COF/CS气凝胶,所述COF/CS气凝胶包括通过1,3,5‑三醛基‑2,4,6‑间苯三酚交联在一起的COF纳米粒子和壳聚糖气凝胶网络,所述COF纳米粒子为TpPa‑SO3H纳米粒子。一种COF/CS气凝胶在含有磺胺类药物废水处理中的应用。制备的COF/CS气凝胶水稳定性好,含有与磺胺甲基嘧啶(SMR)亲和力强的磺酸基,因此可去除水体中的多种磺胺类药物,在废水处理领域具有很好的应用前景。
Description
技术领域
本发明涉及废水处理技术领域,尤其涉及一种COF/CS气凝胶及其制备方法和应用。
背景技术
磺胺类药物,作为抗生素中最具代表性的药物种类之一,是近年来产量最多,用量最大的药物之一,具有高效、毒性较低、抗菌谱广等优点。但是因其在生产中、使用中的违规排放以及不恰当的使用等都会将其引入到水环境中。磺胺类药物,因其固有属性,致使其在自然环境下降解速率慢,迁移快,在生命体中不易代谢,可以通过食物链的途径,最终在人体富集,造成人体消化道功能紊乱、中毒效应等不良反应,进一步导致细菌耐药性增强,甚至产生无法抑制的超级细菌,引起细胞癌变。同时,为了响应当前高效率且可持续发展的需求。因此发展一种简单高效的技术去除水体中的磺胺类药物具有十分重要的意义。
目前,对于水体中的磺胺类药物进行去除的方法主要有化学氧化法、生物降解法、物理吸附法等,其中吸附因操作简单、分离快速、成本低、回收率高等优点,已得到广泛应用。虽然目前已有多种材料作为吸附剂被应用于水体中磺胺类药物的去除,如活性碳、石墨烯、金属有机骨架、共价有机骨架等,但这些材料相对较差的选择性及较低的吸附容量、分离较为困难等缺点,限制其广泛应用。因此,开发对目标污染物磺胺甲基嘧啶具有高选择性、高吸附容量的易于分离的新型吸附剂具有十分重要的现实意义。
发明内容
本发明的目的在于,针对现有技术的上述不足,提出一种操作简单、能耗低、快速且易于批量生产的可压缩、自漂浮的COF/CS气凝胶及其制备方法和应用。
本发明的一种COF/CS气凝胶,所述COF/CS气凝胶包括通过1,3,5-三醛基-2,4,6-间苯三酚交联在一起的COF纳米粒子和壳聚糖气凝胶网络,所述COF纳米粒子为TpPa-SO3H纳米粒子。
进一步的,所述COF纳米粒子采用机械研磨法制备。
一种如上述的COF/CS气凝胶的制备方法,包括如下步骤:
S1:采用机械研磨法制备COF纳米粒子;
S2:以乙酸为酸性条件溶解壳聚糖形成均匀透明的壳聚糖乙酸水溶液;
S3:将一定量的步骤S1制得的COF纳米粒子添加到步骤S2中得到的壳聚糖乙酸水溶液中,超声使其分散均匀,再添加交联剂Tp,即1,3,5-三醛基-2,4,6-间苯三酚,反应得COF/CS水凝胶;
S4:将步骤S3得到的COF/CS水凝胶,经冷冻干燥后得COF/CS气凝胶。
进一步的,步骤S1的具体步骤为:将Pa-SO3H和PTSA充分研磨,混合均匀后,加入Tp后,继续研磨一段时间,再加入一定量的水后继续研磨一段时间后,转移至玻璃小瓶中,170℃加热一段时间,混合物洗涤后,真空干燥后得到TpPa-SO3H。
进一步的,所述步骤S2中乙酸和水的体积比为3:320,壳聚糖乙酸水溶液的浓度为10mg/mL。
进一步的,所述步骤S3中壳聚糖和COF纳米粒子的质量比为1:4~4:1。
进一步的,所述步骤S3中,交联剂Tp和壳聚糖的质量比为0.5:5~1:5,反应条件为:20~35℃,反应时间为12~24小时。
进一步的,所述步骤S4中:冷冻干燥冷阱温度为-36~-40℃,冷冻干燥时间为24~36小时。
一种如上述的一种COF/CS气凝胶在含有磺胺类药物废水处理中的应用。
进一步的,所述磺胺类药物为磺胺甲基嘧啶。
本发明选择1,3,5-三甲酰基间苯三酚(Tp)作为交联剂合成COF/CS气凝胶,并且COF为TpPa-SO3H,通过改变CS和COF的进料比,可以合成具有不同COF负载量的COF/CS气凝胶,当COF负载量达到75wt%时,复合气凝胶材料仍具有良好的完整性和稳定性。此外,通过增加CS和COF的进料量,可以实现大体积COF/CS气凝胶的合成。与传统CS气凝胶的刚性形成鲜明对比的是,所得CS/COF气凝胶具有独特灵活性。更重要的是,COFs的加入可以降低CS水凝胶的密度,使其能够顺利漂浮在水面,易于回收利用。另一方面,气凝胶中交联的COF保持了其结晶度、孔隙率和优异的吸附性能。制备的COF/CS气凝胶水稳定性好,含有与磺胺甲基嘧啶(SMR)亲和力强的磺酸基,因此可去除水体中的多种磺胺类药物,在废水处理领域具有很好的应用前景。
附图说明
图1为本发明COF/CS气凝胶吸附剂的合成示意图;
图2为实施例1所制备的COF/CS气凝胶的扫描电镜图;
图3为实施例1所制备的COF/CS气凝胶的FT-IR谱图;
图4为实施例1所制备的COF/CS气凝胶的XRD谱图;
图5为实施例1所制备的COF/CS气凝胶的氮气吸附-解吸谱图;
图6为实施例1所制备的COF/CS气凝胶对SMR的吸附性能对比图;
图7为实施例1所制备的TpPa-SO3H/CS气凝胶吸附剂对SMR的吸附性能关系图(时间影响);
图8为实施例1所制备的TpPa-SO3H/CS气凝胶吸附剂对SMR的吸附性能关系图(SMR初始浓度影响);
图9为实施例1所制备的TpPa-SO3H/CS气凝胶吸附剂对SMR的重复使用性能;
图10为未负载COF的纯壳聚糖气凝的SEM图像。
具体实施方式
以下是本发明的具体实施例并结合附图,对本发明的技术方案作进一步的描述,但本发明并不限于这些实施例。
实施例l
如图1所示的本发明COF/CS气凝胶吸附剂的合成示意图。
机械研磨法制备COF纳米粒子:将0.45mmol 2,5-二氨基苯磺酸(Pa-SO3H,84.7mg)和2.5mmol对甲苯磺酸(PTSA,430.5mg)充分研磨,混合均匀后,加入0.35mmol 2,4,6-三甲酰基间苯三酚(Tp,74.2mg)后,继续研磨10~15min,再加入100μL水继续研磨5min后,转移至玻璃小瓶中,170℃加热3~5min,混合物依次使用热水、N,N-二甲基乙酰胺、水、丙酮洗涤后,60℃真空干燥过夜,即可得到COF-TpPa-SO3H。
化学交联法结合冷冻干燥合成COF/CS气凝胶:称取10mg CS置于800μL乙酸水(V乙酸:V水=3:320)溶液中,超声20~30min使CS充分溶解后,称取10mg TpPa-SO3H(TpPa-1,TpPa-NH2,TpPa-CH3)加入到壳聚糖水溶液中,超声+涡旋使其分散均匀后,加入200μL分散均匀的Tp水溶液(10mg/mL),涡旋至形成稳定的凝胶后,室温反应24h,冷冻干燥后,即可得到TpPa-SO3H/CS气凝胶(TpPa-1/CS气凝胶,TpPa-NH2/CS气凝胶,TpPa-CH3/CS气凝胶)。
实施例2
CS和TpPa-SO3H的质量比为1:4,可以合成质量比分别为25%的COF/CS气凝胶,其它工艺参数与实施1相同。
实施例3
CS和TpPa-SO3H的质量比为4:1可以合成质量比分别为75%的COF/CS气凝胶,其它工艺参数与实施1相同。
对比例
将实施例中的TpPa-SO3H换成TpPa-1,TpPa-NH2或TpPa-CH3,其他工艺与实施例1相同,分别得到TpPa-1/CS气凝胶,TpPa-NH2/CS气凝胶,TpPa-CH3/CS气凝胶
应用实例
TpPa-SO3H/CS气凝胶吸附剂对SMR的吸附性能测试
本实施例选择SMR作为常见抗生素的代表,对实施例1中制备的COF/CS气凝胶吸附剂的吸附性能进行了测试。测试的操作步骤如下:
1)取50mL的100ppm SMR溶液至100mL锥形瓶中,分别加入20mg COF/CS气凝胶(TpPa-SO3H/CS气凝胶,TpPa-1/CS气凝胶,TpPa-NH2/CS气凝胶,TpPa-CH3/CS气凝胶),摇床摇4h后将COF/CS气凝胶用镊子轻轻取出,取上清液使用紫外分光光度计中测定溶液中剩余目标分析物的浓度,对比不同官能化COF材料对SMR的吸附性能,结果发现TpPa-SO3H/CS气凝胶最好(如图6示)。
2)取25mL的20ppm SMR溶液至100mL锥形瓶中,加入20mg TpPa-SO3H/CS气凝胶,在摇床摇20,40,60,90,120,180,240min时,取上清液使用紫外分光光度计中测定溶液中剩余目标分析物的浓度,确定TpPa-SO3H/CS气凝胶吸附SMR达到吸附平衡时的时间,结果发现TpPa-SO3H/CS气凝胶可在120min内达到吸附平衡(如图7示)。
3)取50mL的5,10,20,50,100,150ppm SMR溶液至100mL锥形瓶中,分别加入20mgTpPa-SO3H/CS气凝胶,摇床摇480min,取上清液使用紫外分光光度计中测定溶液中剩余目标分析物的浓度,确定TpPa-SO3H/CS气凝胶对SMR的最大吸附容量,结果发现TpPa-SO3H/CS气凝胶在25℃时最大吸附容量为102.5mg g-1(如图8示)。
4)取50mL的100ppm SMR溶液至100mL锥形瓶中,分别加入20mg TpPa-SO3H/CS气凝胶,摇床摇480min,取上清液使用紫外分光光度计中测定溶液中剩余目标分析物的浓度,确定TpPa-SO3H/CS气凝胶对SMR的最大吸附容量,将吸附后的TpPa-SO3H/CS气凝胶从吸附液中用镊子取出后,浸泡在5mL甲醇中,超声使SMR从TpPa-SO3H/CS气凝胶上洗脱,再用超纯水洗涤数次后,再重复上述步骤。可以看出,材料在重复使用三次之后对SMR仍然保留较好的吸附性能(如图9所示)。
所制备的COF/CS气凝胶吸附容量大,并可快速实现母液快速分离,吸附效果重现性良好。
从图2可以看出,本实施例1制备的COF/CS气凝胶材料形貌,图10为未负载COF的纯壳聚糖气凝胶的形貌,从图2和图10可以看出。TpPa-SO3H/CS气凝胶的表面更粗糙,表面有明显的颗粒分布,说明TpPa-SO3H/CS气凝胶负载在气凝胶的表面。
图3可以观察到,Tp/CS气凝胶、TpPa-SO3H粉末和TpPa-SO3H/CS气凝胶在1582cm-1和1280cm-1处具有强烈的伸缩振动,分别对应于Schiff碱反应后产生的C=O和C-N峰。同时,在TpPa-SO3H粉末和TpPa-SO3H/CS气凝胶上也观察到了1082cm-1和1031cm-1附近的强伸缩振动峰,对应于磺酸基的O=S=O伸缩振动,表明TpPa-SO3H成功负载到CS气凝胶上。
图4可以看出,该方法合成的TpPa-SO3H具有良好的结晶度。同时,在TpPa-SO3H/CS气凝胶上也可以观察到~5°的强衍射峰,表明虽然TpPa-SO3H负载在CS气凝胶上,但它仍然保留了TpPa-SO3H的高结晶度。
图5可以看出,TpPa-SO3H/CS气凝胶的BET表面积(30.03m2/g)与Tp/CS气凝胶(0.97m2/g)相比显着增加,但其BET表面积略低于TpPa-SO3H粉末(107.92m2/g)。原因是虽然CS具有非常均匀的网络结构,但其网络表面光滑平整(图10)。因此,负载COF后,比表面积大、孔径丰富的COF材料改善了CS的网络表面,增加了气凝胶BET表面积。
第一个是说明材料的物理性质;COF材料负载到壳聚糖网络上之后,依然保留了COF的高结晶度等理化性质。
以上未涉及之处,适用于现有技术。
虽然已经通过示例对本发明的一些特定实施例进行了详细说明,但是本领域的技术人员应该理解,以上示例仅是为了进行说明,而不是为了限制本发明的范围,本发明所属技术领域的技术人员可以对所描述的具体实施例来做出各种各样的修改或补充或采用类似的方式替代,但并不会偏离本发明的方向或者超越所附权利要求书所定义的范围。本领域的技术人员应该理解,凡是依据本发明的技术实质对以上实施方式所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围。
Claims (10)
1.一种COF/CS气凝胶,其特征在于:所述COF/CS气凝胶包括通过1,3,5-三醛基-2,4,6-间苯三酚交联在一起的COF纳米粒子和壳聚糖气凝胶网络,所述COF纳米粒子为TpPa-SO3H。
2.如权利要求1所述的一种COF/CS气凝胶,其特征在于:所述COF纳米粒子采用机械研磨法制备。
3.一种如权利要求1或2所述的COF/CS气凝胶的制备方法,其特征在于:包括如下步骤:
S1:采用机械研磨法制备COF纳米粒子;
S2:以乙酸为酸性条件溶解壳聚糖形成均匀透明的壳聚糖乙酸水溶液;
S3:将一定量的步骤S1制得的COF纳米粒子添加到步骤S2中得到的壳聚糖乙酸水溶液中,超声使其分散均匀,再添加交联剂Tp,即1,3,5-三醛基-2,4,6-间苯三酚,反应得COF/CS水凝胶;
S4:将步骤S3得到的COF/CS水凝胶,经冷冻干燥后得COF/CS气凝胶。
4.如权利要求3所述一种COF/CS气凝胶的制备方法,其特征在于:步骤S1的具体步骤为:将Pa-SO3H和PTSA充分研磨,混合均匀后,加入Tp后,继续研磨一段时间,再加入一定量的水后继续研磨一段时间后,转移至玻璃小瓶中,170℃加热一段时间,混合物洗涤后,真空干燥后得到TpPa-SO3H。
5.如权利要求3所述一种COF/CS气凝胶的制备方法,其特征在于:所述步骤S2中乙酸和水的体积比为3:320,壳聚糖乙酸水溶液的浓度为10mg/mL。
6.如权利要求3所述一种COF/CS气凝胶的制备方法,其特征在于:所述步骤S3中壳聚糖和COF纳米粒子的质量比为1:4~4:1。
7.如权利要求6所述一种COF/CS气凝胶的制备方法,其特征在于:所述步骤S3中,交联剂Tp和壳聚糖的质量比为0.5:5~1:5,反应条件为:20~35℃,反应时间为12~24小时。
8.如权利要求3所述一种COF/CS气凝胶的制备方法,其特征在于:所述步骤S4中:冷冻干燥冷阱温度为-36~-40℃,冷冻干燥时间为24~36小时。
9.一种如权利要求1或2所述的一种COF/CS气凝胶在含有磺胺类药物废水处理中的应用。
10.如权利要求9所述COF/CS气凝胶在含有磺胺类药物废水处理中的应用,其特征在于:所述磺胺类药物为磺胺甲基嘧啶。
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