CN107175132B - 一种可回收的磁性壳聚糖酞菁催化剂及应用 - Google Patents
一种可回收的磁性壳聚糖酞菁催化剂及应用 Download PDFInfo
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Abstract
本发明提供了一种可回收的磁性壳聚糖酞菁催化剂,包括包覆有壳聚糖的四氧化三铁磁性载体,和负载在载体表面具有平滑球状结构的四羧基钴酞菁。本发明还提供了上述的可回收的磁性壳聚糖酞菁催化剂的制备方法,包括一个制备包覆有壳聚糖的四氧化三铁磁性载体的步骤;一个制备四酰胺基酞菁钴的步骤;一个制备四羧基酞菁钴的步骤;将四羧基酞菁钴加入盛有二甲基甲酰胺的反应容器中,搅拌使其充分溶解,随后加入包覆有壳聚糖的四氧化三铁磁性载体粉末超声分散,搅拌,抽出二甲基甲酰胺溶剂,然后洗涤、干燥得可回收的磁性壳聚糖酞菁催化剂。本发明作为催化剂催化水溶液中的染料分子降解反应,降解效率高,无需借助氧化剂,并且可以使用外磁场进行回收。
Description
技术领域
本发明属于化工领域,涉及一种催化剂,具体来说是一种可回收的磁性壳聚糖酞菁催化剂及应用。
背景技术
相对均相催化剂酸而言,非均相催化剂具有分离回收、不需要使用助催化剂的优点而备受瞩目。多年来,人们一直在开发研究非均相催化剂,酞菁是人们发现最早的仿生催化材料之一,因为它的光学活性,热稳定性和高催化活性而得到广泛关注。而且在许多有机合成催化中已经得到应用。然而,它的较低的表面积在和对过氧化氢等氧化源物质的需求,以及在回收方面上的困难,限制了酞菁催化剂在工业上的广泛应用。
为了克服这些缺点,研究人员尝试将酞菁负载在不同的载体上,比如用金属氧化物支撑磺化酞菁铁,将酞菁固载在不同孔径的微孔径载体上,或将酞菁负载到纳米载体上,或是制备不同形貌的金属酞菁颗粒等。但是,从实际应用角度来看,仍存在着需要氧化剂助氧化剂,活性低,难回收的缺陷。近些年,人们对于提高酞菁催化剂催化效率的研究做出了大量的努力。中国石油大学Zhao Chaocheng研究组成功地制备出酞菁钴/MCM41催化剂,实验证实该系列催化剂在氙灯的照射下,可以利用分子氧氧化降解亚甲基橙,通过沉淀回收利用,多次循环后使用寿命较长的优点。
但是合成该类催化剂同样也存在合成过程复杂等问题,降解需要使用额外光源,并且不易回收,制约其在工业上的广泛应用。磁性催化剂对有些催化反应研究了多年,但现已开发出的各种磁性催化剂,也存在较多不足,活性差、酸碱环境下稳定性差、对反应温度要求高,因此,需要研发一种可以高效利用分子氧,便于回收利用,使用条件广泛的磁性酞菁催化剂。
发明内容
针对现有技术中的上述技术问题,本发明提供了一种可回收的磁性壳聚糖酞菁催化剂及应用,所述的这种可回收的磁性壳聚糖酞菁催化剂及应用要解决现有技术中的合成过程复杂、降解需要使用额外光源,并且不易回收的技术问题。
本发明提供了一种可回收的磁性壳聚糖酞菁催化剂,包括包覆有壳聚糖的四氧化三铁磁性载体,和负载在载体表面具有平滑球状结构的四羧基钴酞菁,记为CoTcPc-Chitosan/Fe3O4。
进一步的,所述四羧基酞菁钴的负载量为每10mg催化剂含5 mg四羧基酞菁钴。
进一步的,所述的四氧化三铁磁性载体为直径1至3μm的微球结构。
本发明还提供了上述的一种可回收的磁性壳聚糖酞菁催化剂的制备方法,包括以下步骤:
1)一个制备包覆有壳聚糖的四氧化三铁磁性载体的步骤:
将FeCl3·6H2O与FeCl2·4H2O加入到含有壳聚糖的乙酸溶液中并充分搅拌使其溶解,60~80℃下通入氮气保护并反应4~8h,滴加氨水,获得包覆有壳聚糖的四氧化三铁磁性载体;
2)一个制备四酰胺基酞菁钴的步骤:
将偏苯三酸酐、六水合氯化亚钴、四水合钼酸铵、氯化铵、尿素研磨混合后置于一个第一容器中,冷凝回流条件下将混合物加热至170~190℃并搅拌,反应6~10小时,将所得产物在浓度为1mol/L的盐酸溶液中浸泡3~8小时,抽滤混合液保留滤饼,将滤饼洗至中性并且滤液无色后烘干并研磨细得到四酰胺基酞菁钴;
3)一个制备四羧基酞菁钴的步骤:
将步骤2)所得四酰胺基酞菁钴置于第二反应容器中,倒入氢氧化钠饱和氯化钠溶液。在95-100℃下冷凝回流6~10小时,所得溶液加入盐酸调至pH=2,收集所得沉淀,用去离子水洗至中性后,使用真空干燥箱烘干沉淀,所得产物使用乙醇洗至洗液无色,在50~65℃真空干燥箱中干燥10~14小时后得到四羧基酞菁钴;
4)将步骤3)制备的四羧基酞菁钴加入盛有二甲基甲酰胺的第三反应容器中,搅拌使其充分溶解,随后加入步骤1)制备的包覆有壳聚糖的四氧化三铁磁性载体粉末超声分散,将以上混合液转移至第四反应容器中常温下机械搅拌60~80小时,随后使用油泵连接的旋转蒸发仪,抽出二甲基甲酰胺溶剂,然后采用清水充分洗涤,干燥后即得可回收的磁性壳聚糖酞菁催化剂。
进一步的,所述的步骤1)中,FeCl3·6H2O:FeCl2·4H2O:壳聚糖:乙酸的物料比为6.75g:2.4759g:3g:100mL;所述的步骤(2)中,苯三酸酐:六水合氯化亚钴:四水合钼酸铵:氯化铵:尿素的的物料比为27.5g:8.3g:0.574g:3.75g:50g;所述的步骤4)中,包覆有壳聚糖的四氧化三铁磁性载体:四羧基酞菁钴:二甲基甲酰胺的物料比为0.3g:0.3g:100mL。
进一步的,所述步骤1)反应完成后的产物用去离子水和无水乙醇分别洗涤三次,在60℃真空干燥箱中干燥12小时后收集待用;
所述的步骤2)反应完成后待反应釜自然冷却至室温,产物用去离子水、无水乙醇分别洗涤三次,所得样品在60℃真空干燥箱中干燥12小时后收集待用;
所述步骤3)反应完毕后,黑绿色粉末四羧基酞菁钴用少量去离子水和无水乙醇分别洗涤三次,于60℃真空干燥箱中干燥12小时后收集。
本发明还提供了上述的可回收的磁性壳聚糖酞菁催化剂在染料污染物降解反应中的应用。将催化剂和染料溶液混合,在光照接触空气的条件下持续搅拌,通过降解染料分子从而降低溶液的色度。
按照上述方案所述的染料污染物为亚甲基蓝和曙红Y。
按上述方案,上述应用方法具体步骤为:将CoTcPc-Chitosan/Fe3O4催化剂加入到亚甲基蓝的水溶液和曙红Y的水溶液中,超声分散,随后使用光照射并接触空气,反应开始计时,每隔一段时间,使用磁铁分离催化剂并收集反应溶液,采用紫外可见吸收光谱仪进行吸光度检测:以去离子水为参比样,检测反应液在200-800nm范围内的吸光度,记录亚甲基蓝在662nm处的吸光度数值,记录曙红Y在515nm处的吸光度数值。
按照上述方案,所述CoTcPc-Chitosan/Fe3O4催化剂用量为0.1g,所述体系中亚甲基蓝和曙红Y的浓度是50 ppm。
按照上述方案,CoTcPc-Chitosan/Fe3O4催化剂经回收纯化后再次使用,方法如下:使用磁铁将CoTcPc-Chitosan/Fe3O4吸附至烧杯内壁,将剩余的降解后溶液小心倾倒出,再向空烧杯内加入去离子水,超声分散CoTcPc-Chitosan/Fe3O4后使用磁铁再次吸附并倾倒溶液,如此反复直至水溶液呈无色,最后在0℃真空干燥箱中干燥6小时后收集待用。
本发明采用高温熔融、碱性水解的方法制备了一种水溶性酞菁衍生物,一锅法制备了磁性壳聚糖粉末,并使用溶剂浸渍的方法制得四羧基酞菁钴-磁性壳聚糖粉末。所得催化剂催化活性高,易分离回收,能重复利用,利于工业催化应用。
本发明提供的磁性壳聚糖酞菁催化剂,特点是以壳聚糖包裹四氧化三铁,制备的磁粉表面具有氨基和羟基官能团。制备的酞菁衍生物四羧基酞菁钴,表面富含大量的羧基,在水溶液中具有良好的溶解性。以溶剂占位方式,溶解酞菁催化剂,浸渍壳聚糖包覆修饰磁性纳米粒子搅拌,之后形成的磁性酞菁催化剂材料。本发明提供的磁性壳聚糖酞菁催化剂中作为磁性核的纳米粒子是超顺磁性铁的氧化物。
本发明的催化剂不仅具有稳定的物理性质,而且集化学催化和磁性回收两功能于一身,可反复多次使用。本发明作为催化剂催化水溶液中的染料分子降解反应,降解效率高,无需借助氧化剂,并且可以使用外磁场进行回收。在室温下快速发生反应,催化反应过程绿色安全、易于控制。
本发明和已有技术相比,其技术进步是显著的。本发明的合成步骤简单,易操作,产率高,重复效果好,利于大规模工业化生产。本发明的催化剂催化活性高,可以使用外磁场分离回收,能重复利用,利于实际废水处理应用。本发明催化剂适用条件温和,可以在常温太阳光照下利用分子氧降解有机染料,降低废水色度。
附图说明
图1是(a) CoTcPc、(b) chitosan、(c) Chitosan/Fe3O4、(d) CoTcPc-Chitosan/Fe3O4的傅立叶变换红外光谱图。
图2是(a) CoTcPc、(b) CoTcPc-Chitosan/Fe3O4的SEM照片
图3是经CoTcPc-Chitosan/Fe3O4催化的亚甲基蓝降解的紫外-可见吸收光谱图。
图4是经CoTcPc-Chitosan/Fe3O4催化的亚甲基蓝和曙红Y降解的效率图和效果图。
图5是经多次回收循环的CoTcPc-Chitosan/Fe3O4催化的亚甲基蓝效率图。
图6是经多次回收循环的CoTcPc-Chitosan/Fe3O4催化的曙红Y的效率图。
具体实施方式
以下结合附图和实施例进一步对本发明进行说明。
实施例1
步骤1.称取7.4 g偏苯三酸酐,1.363 g氯化亚钴,15.015 g尿素,0.148 g钼酸铵,1.15g氯化铵装入三颈烧瓶,升温至120 ℃回流2小时,随后升温至180 ℃保温6小时。
步骤2.冷却至室温后将所得固体使用1mol/L盐酸浸泡5小时,随后将溶液倒入水中,过滤,用去离子水洗涤滤出的固体2~3次,烘干,收集。
步骤3.称取5 g步骤2中收集的样品溶于200 ml 2 mol/L氢氧化钠饱和氯化钠溶液,完全溶解后将溶液加热至98 ℃,回流加热8小时。
步骤4.将水解后的反应液抽滤,往滤液中加入盐酸调至pH=2,静置分离所得沉淀。水洗沉淀至中性,将沉淀置于60 ℃真空干燥箱中干燥6小时后收集,得到四羧基酞菁钴粉末。四羧基酞菁钴的红外光谱如图1(a)所示,其中1715 cm-1和3465 cm-1是羧基的和羟基的特征峰;形貌如图2(a)扫描电镜照片所示。
步骤5.称取1.35 g六水合氯化铁,0.495 g四水合氯化亚铁,0.6 g壳聚糖溶解到20 mL乙酸溶液中。通入N2保护并且机械搅拌,反应6小时。随后滴加氨水滴至pH=11,水洗沉淀至中性,将沉淀置于40 ℃真空干燥箱中干燥8小时后收集,得包覆有壳聚糖的四氧化三铁磁性载体,改磁性载体的红外谱图如图1(c)所示,壳聚糖的红外光谱如图1(b)所示。
步骤6.取1g步骤4产物四羧基酞菁钴粉末溶解到20 mL二甲基甲酰胺中,随后加入步骤5制备的包覆有壳聚糖的四氧化三铁磁性载体粉末超声分散,将以上混合液转移至三颈烧瓶中常温下机械搅拌72小时,随后使用油泵连接的旋转蒸发仪,抽出二甲基甲酰胺溶剂,然后采用清水充分洗涤,干燥后即得可回收的四羧基酞菁钴-壳聚糖磁性粉末催化剂,负载型催化剂的红外谱图如图1(d)所示,催化剂的形貌如图2(b)所示,为均匀分散的球状颗粒。
实施例2
将0.1 g四羧基酞菁钴-壳聚糖磁性粉末加入到200 mL 50 ppm的亚甲基蓝溶液中,室温下避光搅拌他使催化剂和溶液达到吸附平衡。之后往溶液鼓入空气,在日光灯照射下持续搅拌。测定溶液在最大吸收波长(662nm处)吸光度变化,计算降解效率。溶液降解1小时内紫外-可见光吸收光谱变化如图3所示,当反应4小时,溶液中亚甲基蓝的吸光度降低到原来的10 %,染料降解率达到90 %。反应6小时,亚甲基蓝的降解率达到99.8 %,亚甲基蓝降解率随时间变化关系如附图4所示。使用外磁场将磁性催化剂吸出分离,重新加入相同浓度相同量的亚甲基蓝溶液,相同条件下重复4次试验。每一次循环对亚甲基蓝的降解率分别是:99%、94%、92.3%、90%(如图5所示)。
实施例3
将200mL 50ppm的亚甲基蓝溶液中滴入10mL H2O2,在避光的条件下搅拌均匀,然后加入HCl调至pH=2,之后加入0.05g的四羧基酞菁钴-壳聚糖磁性粉末。在避光通入空气的情况下搅拌,发现5分钟亚甲基蓝降解率达到98.6%。
实施例4
将0. 1g四羧基酞菁钴-壳聚糖磁性粉末加入到200mL 50ppm的曙红Y溶液中,室温下避光搅拌他使催化剂和溶液达到吸附平衡。加入盐酸将溶液pH调至5,之后往溶液鼓入空气,在日光灯照射下持续搅拌。测定溶液在最大吸收波长(515nm处)吸光度变化,计算降解效率。发现在2小时,曙红降解率达到99%,曙红的降解率随时间变化关系如附图4所示。使用外磁场将磁性催化剂吸出分离,重新加入入相同浓度相同量的曙红溶液,相同条件下重复4次试验。每一次循环对曙红降解率分别是:98%、96%、93%、91.2%,降解率变化如图6所示,。
实施例5
将0. 1g四羧基酞菁钴-壳聚糖磁性粉末加入到200mL 50ppm的曙红Y溶液中,室温下避光搅拌他使催化剂和溶液达到吸附平衡,保持溶液pH=7。在太阳光的照射下直接与空气接触,使用磁力搅拌器进行搅拌。如图4所示,4小时之后,曙红的降解率达到了94%。
Claims (3)
1.一种可回收的磁性壳聚糖酞菁催化剂的制备方法,其特征在于包括以下步骤:
1)一个制备包覆有壳聚糖的四氧化三铁磁性载体的步骤:
将FeCl3·6H2O与FeCl2·4H2O加入到含有壳聚糖的乙酸溶液中并充分搅拌使其溶解,60~80℃下通入氮气保护并反应4~8h,滴加氨水,获得包覆有壳聚糖的四氧化三铁磁性载体;
2)一个制备四酰胺基酞菁钴的步骤:
将偏苯三酸酐、六水合氯化亚钴、四水合钼酸铵、氯化铵、尿素研磨混合后置于一个第一容器中,冷凝回流条件下将混合物加热至170~190℃并搅拌,反应6~10小时,将所得产物在浓度为1mol/L的盐酸溶液中浸泡3~8小时,抽滤混合液保留滤饼,将滤饼洗至中性并且滤液无色后烘干并研磨细得到四酰胺基酞菁钴;
3)一个制备四羧基酞菁钴的步骤:
将步骤2)所得四酰胺基酞菁钴置于第二反应容器中,倒入氢氧化钠饱和氯化钠溶液;在95-100℃下冷凝回流6~10小时,所得溶液加入盐酸调至pH=2,收集所得沉淀,用去离子水洗至中性后,使用真空干燥箱烘干沉淀,所得产物使用乙醇洗至洗液无色,在50~65℃真空干燥箱中干燥10~14小时后得到四羧基酞菁钴;
4)将步骤3)制备的四羧基酞菁钴加入盛有二甲基甲酰胺的第三反应容器中,搅拌使其充分溶解,随后加入步骤1)制备的包覆有壳聚糖的四氧化三铁磁性载体粉末超声分散,将以上混合液转移至第四反应容器中常温下机械搅拌60~80小时,随后使用油泵连接的旋转蒸发仪,抽出二甲基甲酰胺溶剂,然后采用清水充分洗涤,干燥后即得可回收的磁性壳聚糖酞菁催化剂。
2.根据权利要求1所述的一种可回收的磁性壳聚糖酞菁催化剂的制备方法,其特征在于:所述的步骤1)中,FeCl3·6H2O:FeCl2·4H2O:壳聚糖:乙酸的物料比为6.75g:2.4759g:3g:100mL;所述的步骤2)中,苯三酸酐:六水合氯化亚钴:四水合钼酸铵:氯化铵:尿素的的物料比是27.5g:8.3g:0.574g:3.75g:50g;所述的步骤4)中,包覆有壳聚糖的四氧化三铁磁性载体:四羧基酞菁钴:二甲基甲酰胺的物料比为0.3g:0.3g:100mL。
3.根据权利要求1所述的一种可回收的磁性壳聚糖酞菁催化剂的制备方法,其特征在于:所述步骤1)反应完成后的产物用去离子水和无水乙醇分别洗涤三次,在60℃真空干燥箱中干燥12小时后收集待用;
所述的步骤2)反应完成后待反应釜自然冷却至室温,产物用去离子水、无水乙醇分别洗涤三次,所得样品在60℃真空干燥箱中干燥12小时后收集待用;
所述步骤3)反应完毕后,黑绿色粉末四羧基酞菁钴用少量去离子水和无水乙醇分别洗涤三次,于60℃真空干燥箱中干燥12小时后收集。
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