CN114702670B - 一种聚萘二酰亚胺硫酮缩聚物光催化剂及其制备方法和应用 - Google Patents
一种聚萘二酰亚胺硫酮缩聚物光催化剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种聚萘二酰亚胺硫酮缩聚物光催化剂及其制备方法和应用,其中制备方法包括步骤:将硫脲、1,4,5,8‑萘四甲酸二酐、醋酸锌和咪唑混合,反应,冷却后加入盐酸,进行真空过滤,清洗,干燥,获得固体聚萘二酰亚胺硫酮缩聚物;向盛放聚萘二酰亚胺硫酮缩聚物的容器中依次加入浓硫酸和去离子水,生成不溶性沉淀后静置,过滤,烘干,获得聚萘二酰亚胺硫酮缩聚物光催化剂。本发明提供的制备方法简单易行,所制备的聚萘二酰亚胺硫酮缩聚物光催化剂具有卓越的光催化降解性能,能够显著提高染料废水污染物的降解率。
Description
技术领域
本发明属于光催化污水处理技术领域,具体涉及一种聚萘二酰亚胺硫酮缩聚物光催化剂及其制备方法和应用。
背景技术
水是生命之源,但是水污染对生态环境和人们的健康带来巨大的威胁,特别是水中的有机污染物,如多氯联苯、抗生素、染料及其中间体等。目前主要治理方法为物理吸附、化学转化和生物降解,但是效果并不十分理想。近年来,光催化氧化降解作为一种高级氧化技术,可将毒性大、难生物降解的有机污染物彻底矿化,然而,目前具有高活性和强矿化能力的光催化剂主要为TiO2等紫外光活性的催化剂,紫外光只占太阳光的4~6%,太阳光利用率低,且现有的光催化剂成本高,难以普遍推广应用。
发明内容
本发明的目的在于克服现有技术中的不足,提供一种聚萘二酰亚胺硫酮缩聚物光催化剂及其制备方法和应用,制备方法简单易行,所制备的聚萘二酰亚胺硫酮缩聚物光催化剂具有卓越的光催化降解性能,能够显著提高染料废水污染物的降解率。
本发明提供了如下的技术方案:
第一方面,提供一种聚萘二酰亚胺硫酮缩聚物光催化剂的制备方法,包括以下步骤:
将硫脲、1,4,5,8-萘四甲酸二酐、醋酸锌和咪唑混合,反应,冷却后加入盐酸,进行真空过滤,清洗,干燥,获得固体聚萘二酰亚胺硫酮缩聚物;
向盛放聚萘二酰亚胺硫酮缩聚物的容器中依次加入浓硫酸和去离子水,生成不溶性沉淀后静置,过滤,烘干,获得聚萘二酰亚胺硫酮缩聚物光催化剂。
进一步的,所述硫脲、1,4,5,8-萘四甲酸二酐和醋酸锌的物质的量之比为1:1:1。
进一步的,所述硫脲、1,4,5,8-萘四甲酸二酐、醋酸锌和咪唑的混合反应在氩气保护下进行,反应温度为140℃,反应时间为5~10h。
进一步的,反应结束冷却至室温后加入盐酸,进行真空过滤,用去离子水洗涤沉淀至无氯离子,然后在真空箱中干燥,收集的黑褐色固体即为聚萘二酰亚胺硫酮缩聚物。
进一步的,所述盐酸的浓度为0.9-1.1mol/L。
进一步的,所述浓硫酸的浓度为98%,所述聚萘二酰亚胺硫酮缩聚物与98%浓硫酸的质量体积比为0.01~0.1:1。
进一步的,所述聚萘二酰亚胺硫酮缩聚物与去离子水的质量体积比为 0.01~0.1:5~15。
进一步的,生成的不溶性沉淀静置30~40min。
第二方面,提供一种采用第一方面所述的制备方法制备获得的聚萘二酰亚胺硫酮缩聚物光催化剂。
第三方面,提供一种第二方面所述的聚萘二酰亚胺硫酮缩聚物光催化剂在催化降解染料废水中的应用。
与现有技术相比,本发明的有益效果是:
(1)本发明以硫脲、1,4,5,8-萘四甲酸二酐、醋酸锌和咪唑为原料,原料易得,成本低,制备的固体聚萘二酰亚胺硫酮缩聚物具有一定的光催化降解能力;
(2)本发明采用浓硫酸对聚萘二酰亚胺硫酮缩聚物进行酸化,制备得到的聚萘二酰亚胺硫酮缩聚物光催化剂,具有卓越的光催化降解性能,显著提高了染料废水污染物的降解率,也为快速降解染料废水提供了可靠的技术支持;
(3)本发明提供的制备方法简单,实施性强,实施成本低,便于推广应用,且制备过程中无其它污染物产生,符合环境友好理念,具有良好的市场应用前景。
附图说明
图1是实施例1步骤(1)所制备的Thiourea-NDI的XRD衍射图;
图2是实施例1步骤(1)所制备的Thiourea-NDI–AT的扫描电镜图;
图3是实验例1中Thiourea-NDI–AT对亚甲基蓝的吸附降解曲线图;
图4是实验例2中光反应瓶A和B对亚甲基蓝的光催化降解曲线图;
图5是实验例2中光反应瓶B和E对亚甲基蓝的光催化降解曲线图。
具体实施方式
下面结合附图对本发明作进一步描述。以下实施例仅用于更加清楚地说明本发明的技术方案,而不能以此来限制本发明的保护范围。
实施例1
本实施例提供一种聚萘二酰亚胺硫酮缩聚物光催化剂的制备方法,包括以下步骤:
(1)在500mL单颈烧瓶中加入硫脲(0.15g,2mmol)、萘-1,4,5,8-四甲酸二酐(0.54g,2mmol)、醋酸锌(0.37g,2mmol)和5.00g咪唑(溶剂),在140℃高温以及氩气保护下反应5h,待反应冷却到室温后加入盐酸 (250mL,0.9mol/L),搅拌混合至无进一步沉淀,然后对反应体系进行真空过滤,并用蒸馏水洗涤沉淀直至无氯离子(用硝酸银检测是否有白色沉淀),在真空箱中干燥后用DMSO进行洗涤,随后加入蒸馏水,对析出的产物进行烘干处理,最后收集到黑褐色固体0.49g,即为聚萘二酰亚胺硫酮缩聚物,产率为70.8%,化学反应式如下:
(2)称量0.10g聚萘二酰亚胺甲酮线形缩聚物(Thiourea-NDI)至200mL 的烧杯中,向其中加入10mL 98%浓硫酸后进行超声5min,再向其中加入 150mL的去离子水,待生成不溶性沉淀后静置30min,然后过滤烘干,得到的黑褐色固体为酸处理过的聚萘二酰亚胺甲酮线形缩聚物,即聚萘二酰亚胺甲酮线形缩聚物光催化剂(Thiourea-NDI-AT)。
如图1所示为步骤(1)所制备的黑褐色固体的XRD衍射图,由图可知,Thiourea-NDI-AT具有很高的结晶度,有助于形成一个坚固的内置电场,促进光生载流子的分离和传输。
如图2所示为步骤(1)所制备的黑褐色固体的扫描电镜图,由图可知, Thiourea-NDI加酸酸化之后,材料的形貌发生改变,材料自组装形成纳米化结构增大了其表面积,佐证了材料光催化性能得到了提升。
实施例2
本实施例提供一种聚萘二酰亚胺硫酮缩聚物光催化剂的制备方法,包括以下步骤:
(1)在500mL单颈烧瓶中加入硫脲(0.15g,2mmol)、萘-1,4,5,8-四甲酸二酐(0.54g,2mmol)、醋酸锌(0.37g,2mmol)和5.00g咪唑(溶剂),在140℃高温以及氩气保护下反应10h,待反应冷却到室温后加入盐酸 (250mL,1.1mol/L),搅拌混合至无进一步沉淀,然后对反应体系进行真空过滤,并用蒸馏水洗涤沉淀直至无氯离子(用硝酸银检测是否有白色沉淀),在真空箱中干燥后用DMSO进行洗涤,随后加入蒸馏水,对析出的产物进行烘干处理,最后收集到黑褐色固体0.498g,即为Thiourea-NDI,产率为72.2%。
(2)称量0.10g Thiourea-NDI至200mL的烧杯中,向其中加入3mL 98%浓硫酸后进行超声10min,再向其中加入50mL的去离子水,待生成不溶性沉淀后静置40min,然后过滤烘干,得到的黑褐色固体为酸处理过的聚萘二酰亚胺甲酮线形缩聚物,即Thiourea-NDI-AT。
实施例3
本实施例提供一种聚萘二酰亚胺硫酮缩聚物光催化剂的制备方法,包括以下步骤:
(1)在500mL单颈烧瓶中加入硫脲(0.15g,2mmol)、萘-1,4,5,8-四甲酸二酐(0.54g,2mmol)、醋酸锌(0.37g,2mmol)和5.00g咪唑(溶剂),在140℃高温以及氩气保护下反应5h,待反应冷却到室温后加入盐酸 (250mL,1mol/L),搅拌混合至无进一步沉淀,然后对反应体系进行真空过滤,并用蒸馏水洗涤沉淀直至无氯离子(用硝酸银检测是否有白色沉淀),在真空箱中干燥后用DMSO进行洗涤,随后加入蒸馏水,对析出的产物进行烘干处理,最后收集到黑褐色固体0.492g,即为Thiourea-NDI,产率为 71.3%。
(2)称量0.10g Thiourea-NDI至200mL的烧杯中,向其中加入7mL 98%浓硫酸后进行超声5min,再向其中加入100mL的去离子水,待生成不溶性沉淀后静置35min,然后过滤烘干,得到的黑褐色固体为酸处理过的聚萘二酰亚胺甲酮线形缩聚物,即Thiourea-NDI-AT。
实验例1
取25.0mg实施例1中获得的Thiourea-NDI–AT至200mL的烧杯中,向其中加入50mL浓度为10ppm的亚甲基蓝(MB)溶液,超声5min后置于黑暗处搅拌吸附2h。观察吸附反应之后的溶液颜色变化,并在紫外分光光度仪上进行吸光度测定,所得数据绘制如图3所示,由图3可以看出吸附2h后MB溶液的吸光度明显降低,表明本发明制备的Thiourea-NDI–AT 对MB溶液具有很好的降解效果。
实验例2
(1)取5支盛有MB溶液的光反应瓶,分别编号A、B、C、D、E,反应瓶A加入10mg实施例1步骤(1)中获得的Thiourea-NDI,反应瓶B 加入10mg实施例1步骤(2)中获得的Thiourea-NDI–AT,反应瓶C加入 10mg实施例2中获得的Thiourea-NDI–AT,反应瓶D加入10mg实施例3中获得的Thiourea-NDI–AT,反应瓶E加入10mg传统光催化剂TiO2。
(2)将步骤(1)中的5个光反应瓶置于暗处,同时打开循环冷凝水,保持在室温的条件,搅拌保持1h,取样离心后打开光源,进行光催化降解,并开启光化学反应器计时,每隔1h取一次溶液进行离心抽样。
(3)取5支100mL的容量瓶编号1-5,向其中分别加入5、10、15、 20、25mL的MB溶液(10mg/L)并定容至25mL,获得标曲溶液。
(4)对配制好的标曲溶液进行吸光度测定并绘制标准曲线,由标准曲线测定样品浓度,绘制光催化降解曲线图,并通过公式r=(c0-c)/c0计算降解效率r,式中c0表示目标污染物MB溶液起始浓度,c表示反应结束后的 MB溶液浓度,计算后获得的5支光反应瓶内的降解效率数据见下表1。
表1 5支光反应瓶内的降解效率数据
由表1可知,同等实验条件下,光反应瓶A中的Thiourea-NDI的光催化降解效率为47.5%,而在光反应瓶B中经过硫酸酸化后的Thiourea-NDI –AT的光催化降解速率翻倍。而在不同硫酸添加量的条件下光催化降解速率有所不同,原因可能在于酸化程度不同,材料表面面积增加量也不同。
图4为光反应瓶A和B的光催化降解曲线图,由图可知,前2h两组光反应瓶都处于黑暗条件下达到吸附平衡,之后打开350W氙灯进行光催化降解,降解效率达到97%。
图5为光反应瓶B和E的光催化降解曲线图,由图可知,同等条件下 Thiourea-NDI-AT的光催化降解效率是经典光催化剂TiO2的15倍,具有卓越的光催化降解性能。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明技术原理的前提下,还可以做出若干改进和变形,这些改进和变形也应视为本发明的保护范围。
Claims (8)
1.一种聚萘二酰亚胺硫酮缩聚物光催化剂的制备方法,其特征在于,包括以下步骤:
将硫脲、1,4,5,8-萘四甲酸二酐、醋酸锌和咪唑混合,反应,冷却后加入盐酸,进行真空过滤,清洗,干燥,获得固体聚萘二酰亚胺硫酮缩聚物;
向盛放聚萘二酰亚胺硫酮缩聚物的容器中依次加入浓硫酸和去离子水,生成不溶性沉淀后静置,过滤,烘干,获得聚萘二酰亚胺硫酮缩聚物光催化剂;
所述浓硫酸的浓度为98%,所述聚萘二酰亚胺硫酮缩聚物与98%浓硫酸的质量体积比为0.1g:7mL,所述聚萘二酰亚胺硫酮缩聚物与去离子水的质量体积比为0.1g:100mL。
2.根据权利要求1所述的聚萘二酰亚胺硫酮缩聚物光催化剂的制备方法,其特征在于,所述硫脲、1,4,5,8-萘四甲酸二酐和醋酸锌的物质的量之比为1:1:1。
3.根据权利要求1所述的聚萘二酰亚胺硫酮缩聚物光催化剂的制备方法,其特征在于,所述硫脲、1,4,5,8-萘四甲酸二酐、醋酸锌和咪唑的混合反应在氩气保护下进行,反应温度为140℃,反应时间为5~10h。
4.根据权利要求1所述的聚萘二酰亚胺硫酮缩聚物光催化剂的制备方法,其特征在于,反应结束冷却至室温后加入盐酸,进行真空过滤,用去离子水洗涤沉淀至无氯离子,然后在真空箱中干燥,收集的黑褐色固体即为聚萘二酰亚胺硫酮缩聚物。
5.根据权利要求1所述的聚萘二酰亚胺硫酮缩聚物光催化剂的制备方法,其特征在于,所述盐酸的浓度为0.9-1.1mol/L。
6.根据权利要求1所述的聚萘二酰亚胺硫酮缩聚物光催化剂的制备方法,其特征在于,生成的不溶性沉淀静置30~40min。
7.一种采用权利要求1~6任一项所述的制备方法制备获得的聚萘二酰亚胺硫酮缩聚物光催化剂。
8.一种权利要求7所述的聚萘二酰亚胺硫酮缩聚物光催化剂在催化降解染料废水中的应用。
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