CN106268960B - 一种聚丙烯腈纤维-hemin仿生催化剂及其制备方法 - Google Patents
一种聚丙烯腈纤维-hemin仿生催化剂及其制备方法 Download PDFInfo
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- 229940025294 hemin Drugs 0.000 title claims abstract description 51
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- BTIJJDXEELBZFS-QDUVMHSLSA-K hemin Chemical compound CC1=C(CCC(O)=O)C(C=C2C(CCC(O)=O)=C(C)\C(N2[Fe](Cl)N23)=C\4)=N\C1=C/C2=C(C)C(C=C)=C3\C=C/1C(C)=C(C=C)C/4=N\1 BTIJJDXEELBZFS-QDUVMHSLSA-K 0.000 claims abstract description 34
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- GLNHIAPTFHWQKY-UHFFFAOYSA-L disodium 4-amino-3-[[4-[[4-[(2,4-diaminophenyl)diazenyl]phenyl]sulfonylamino]phenyl]diazenyl]-5-oxido-6-phenyldiazenyl-7-sulfonaphthalene-2-sulfonate Chemical compound [Na+].[Na+].Nc1ccc(N=Nc2ccc(cc2)S(=O)(=O)Nc2ccc(cc2)N=Nc2c(N)c3c(O)c(N=Nc4ccccc4)c(cc3cc2S([O-])(=O)=O)S([O-])(=O)=O)c(N)c1 GLNHIAPTFHWQKY-UHFFFAOYSA-L 0.000 description 1
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- 150000002825 nitriles Chemical class 0.000 description 1
- GCFAQSYBSUQUPL-UHFFFAOYSA-I pentasodium 5-[[4-chloro-6-[3-(2-sulfonatooxyethylsulfonyl)anilino]-1,3,5-triazin-2-yl]amino]-3-[(1,5-disulfonatonaphthalen-2-yl)diazenyl]-4-hydroxynaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].Oc1c(N=Nc2ccc3c(cccc3c2S([O-])(=O)=O)S([O-])(=O)=O)c(cc2cc(cc(Nc3nc(Cl)nc(Nc4cccc(c4)S(=O)(=O)CCOS([O-])(=O)=O)n3)c12)S([O-])(=O)=O)S([O-])(=O)=O GCFAQSYBSUQUPL-UHFFFAOYSA-I 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
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- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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Abstract
本发明公开一种聚丙烯腈纤维‑hemin仿生催化剂及其制备方法,该仿生催化剂呈纤维状,由2‑氨基咪唑改性的聚丙烯腈纤维与一种天然铁卟啉化合物hemin反应后形成。制备方法为:首先使用2‑氨基咪唑在pH=9.5和温度95℃条件下对聚丙烯腈纤维进行改性反应,使其获得含有咪唑环结构的活性基团,然后将所得改性聚丙烯腈纤维与hemin的DMF溶液进行配位反应,得到模拟辣根过氧化氢酶结构的聚丙烯腈纤维‑hemin仿生催化剂。本发明仿生催化剂适用于染料等水中有机污染物的氧化降解反应,与处理的hemin相比,聚丙烯腈纤维载体的引入不仅明显增强了其催化活性,而且极大改善了其pH适用性和使用稳定性。
Description
技术领域
本发明属于仿生催化技术领域,具体为一种用于废水中染料等有机污染物氧化降解领域的聚丙烯腈纤维-hemin仿生催化剂及其制备方法。
背景技术
近年来,仿生催化技术在染料等水中难降解有机污染物的处理中受到广泛关注。其中,金属卟啉具有可变价态的金属离子和共轭大π电子结构,从而具有氧化还原特性,被认为是一种潜在的高效仿生催化剂。然而在处理水中有机污染物时,金属卟啉催化剂易发生自聚而导致活性明显降低,而且还存在pH适用范围窄、稳定性差以及分离回收困难等不足。将金属卟啉负载于固体材料表面上制备催化剂,是克服其上述缺点的一种重要途径。TiO2薄膜、石墨烯以及活性碳纤维等材料均能够被用于负载金属卟啉制备催化剂,他们可有效活化H2O2氧化降解有机污染物,但仍存在制备过程复杂、能耗高或催化活性不理想等问题,这些不足限制了其进一步的应用。
发明内容
本发明的目的在于提供一种可用于水中染料等有机污染物处理的高效仿生催化剂,该催化剂具有制备方法简单、成本低、催化效率高以及使用稳定性强等特点。
本发明所采用的技术方案,是使用2-氨基咪唑对聚丙烯腈纤维侧基氰基进行改性,制备含有咪唑环结构的纤维载体材料。然后再将一种天然铁卟啉化合物hemin(氯化血红素)通过轴向配位作用与改性纤维上的咪唑环进行结合,制备模拟辣根过氧化氢酶结构的聚丙烯腈负载铁卟啉催化剂,具体步骤为:
1)按重量比1:(0.83-4.165)取聚丙烯腈纤维和2-氨基咪唑,将聚丙烯腈纤维加入到2-氨基咪唑水溶液中,用氢氧化钠调节pH值至9.5,在95℃和搅拌条件下反应2-6h,然后取出并用蒸馏水反复清洗烘干后得到改性聚丙烯腈纤维。
2)按重量比1:(0.1-0.5)取改性聚丙烯腈纤维和hemin,将改性聚丙烯腈纤维置于hemin的DMF溶液中,在40-60℃和搅拌条件下反应1-2.5h后取出,并用DMF和蒸馏水反复洗涤后烘干,得到聚丙烯腈纤维-hemin仿生催化剂。
所述2-氨基咪唑水溶液的浓度为16.6-83.3g/L。
所述hemin的DMF溶液的浓度为1.0-5.0g/L。
聚丙烯腈纤维通过侧基氰基的改性反应,能够引入可与金属离子发生配位作用的活性基团,从而作为载体材料负载金属离子制备催化剂。与其他载体材料相比,聚丙烯腈纤维具有价格低廉、物化性能优异和应用方式灵活等独特优势,使其成为负载金属卟啉制备仿生催化剂的潜在材料。
以辣根过氧化氢酶(Horseradish peroxidase,HRP)为代表的过氧化氢酶,具有极高的催化H2O2分解生成羟基自由基的效率,所得强氧化性自由基能够进攻有机污染物并使其发生降解反应。在辣根过氧化氢酶分子中,Fe3+与平面卟啉的四个N原子配合物形成高铁血红素,轴向下方与铁配位的是组胺His170残基中咪唑环中的N原子,轴向上方则能够与H2O2进行结合。在活化H2O2反应时,与铁中心相连的咪唑环能够通过推电子作用促进铁和氧之间的电子传递,从而大幅度提高反应体系的催化效率。通过对辣根过氧化氢酶结构的模拟,将铁卟啉负载于含有咪唑环结构的固体材料上,制备的催化剂有望获得接近过氧化氢酶的催化活性。
与现有技术相比,本发明的有益效果在于:使用含有咪唑环结构的改性聚丙烯腈纤维作为载体材料,通过轴向配位作用负载铁卟啉制备出模拟辣根过氧化酶结构的催化剂。聚丙烯腈纤维材料作为载体不仅具有优异的柔软性、结构稳定性和机械性能,而且对染料等水中有机污染物表现出较强的吸附性,大大的增强了铁卟啉作为催化材料的实用性。所述的催化剂特征在于采用简单浸渍反应的制备方法,不需要昂贵的设备,工艺流程简单,材料制备过程中能耗低。所述的催化剂活化H2O2催化降解水中污染物的效率高,因为纤维载体上咪唑环能够通过轴向配位作用促进活性中心铁和氧之间的电子传递,以类似辣根过氧化氢酶的方式提升铁卟啉的催化活性。所述的催化剂还具有pH适用范围宽和重复利用性能优异等特点。
附图说明
图1为本发明仿生催化剂的实施例一至三所得的仿生催化剂与未处理的hemin的催化活性比较(测试条件:罗丹明B染料:0.02mmol/L,H2O2:5.0mmol/L,催化剂:5.0g/L,pH=6.0,温度:50℃)。
图2为本发明仿生催化剂的实施例一所得的仿生催化剂和未处理的hemin在不同pH值条件下对染料降解的催化活性比较(测试条件:罗丹明B染料:0.02mmol/L,H2O2:5.0mmol/L,催化剂:5.0g/L,温度:50℃,反应时间:60min)。
图3为本发明仿生催化剂的实施例一所得的仿生催化剂和未处理的hemin对不同结构的染料降解催化活性比较(测试条件:染料浓度:0.02mmol/L,H2O2:5.0mmol/L,催化剂:5.0g/L,pH=6.0,温度:50℃,反应时间:60min)。
图4为本发明仿生催化剂的实施例二所得的仿生催化剂在染料降解中的重复使用性能(测试条件:罗丹明B染料:0.02mmol/L,H2O2:5.0mmol/L,催化剂:5.0g/L,pH=6.0,温度:50℃)。
具体实施方式
下面将结合实施例及附图进一步阐明本发明的内容,但这些实施例并不限制本发明的保护范围。
本发明提供一种聚丙烯腈纤维-hemin仿生催化剂(简称仿生催化剂),该仿生催化剂呈纤维状,由含有咪唑环结构活性基团的改性聚丙烯腈纤维与hemin构成,其中铁离子含量为1.5-18.9mg/g。
本发明还提供一种聚丙烯腈纤维-hemin仿生催化剂制备方法,具体步骤为:
1)按重量比1:(0.83-4.165)取聚丙烯腈纤维和2-氨基咪唑,将聚丙烯腈纤维加入到2-氨基咪唑水溶液中,用氢氧化钠调节pH值至9.5,在95℃和搅拌条件下反应2-6h,然后取出并用蒸馏水反复清洗烘干后得到改性聚丙烯腈纤维。
2)按重量比1:(0.1-0.5)取改性聚丙烯腈纤维和hemin,将改性聚丙烯腈纤维置于hemin的DMF溶液中,在40-60℃和搅拌条件下反应1-2.5h后取出,并用DMF和蒸馏水反复洗涤后烘干,得到聚丙烯腈纤维-hemin仿生催化剂。
所述2-氨基咪唑水溶液的浓度为16.6-83.3g/L。
所述hemin的DMF溶液的浓度为1.0-5.0g/L。
实施例一
1)将精确称量的1.0g聚丙烯腈纤维放入50ml浓度为83.3g/L的2-氨基咪唑水溶液中,用氢氧化钠调节pH值至9.5,在95℃和搅拌条件下反应4h,然后取出并用蒸馏水反复清洗烘干后得到改性聚丙烯腈纤维。
2)称取1.0g改性聚丙烯腈纤维置于100ml浓度为4.0g/L的hemin的DMF溶液中,在60℃和搅拌条件下反应2.5h后取出,并用DMF和蒸馏水反复洗涤后烘干,得到第一种聚丙烯腈纤维-hemin仿生催化剂。
使用元素分析仪测定负载hemin前改性聚丙烯腈纤维的氮含量为34.5%,以此评价其咪唑环基团含量。催化剂铁离子含量的测定:准确称量0.1g催化剂,溶于V(HNO3):V(H2O2)=7:3的溶液中,使用原子吸收法测定溶液中的铁离子浓度,并依此计算出催化剂上铁离子含量为15.6mg/g。
实施例二
将实施例一步骤1中2-氨基咪唑浓度调整为66.7g/L,步骤2中hemin浓度调整为2.0g/L,其余同实施例一,得到第二种聚丙烯腈纤维-hemin仿生催化剂。经测定和计算,其纤维载体材料中氮含量为30.1%,催化剂铁离子含量为10.2mg/g。
实施例三、四
将实施例一步骤2中hemin浓度分别调整为1.5g/L和3.0g/L,其余同实施例一,得到第三种和第四种聚丙烯腈纤维-hemin仿生催化剂。其纤维载体材料氮含量均为34.5%,铁离子含量分别为9.9mg/g和12.3mg/g。
实施例五、六
将实施例二步骤2中hemin浓度分别调整为3.0g/L和5.0g/L,其余同实施例二,得到第五种和第六种聚丙烯腈纤维-hemin仿生催化剂。其纤维载体材料氮含量均为30.1%,铁离子含量分别为11.5mg/g和15.3mg/g。。
实施例七、八、九
将实施例一步骤1中2-氨基咪唑浓度调整为33.2g/L,步骤2中hemin浓度分别设定为1.0g/L、3.0g/L和5.0g/L,其余同实施例1,得到第七种、第八种和第九种聚丙烯腈纤维-hemin仿生催化剂。经测定和计算,其纤维载体材料中氮含量均为26.5%,催化剂铁离子含量分别为2.8mg/g、6.7mg/g和8.5mg/g。
选取实施例一至三所得的聚丙烯腈纤维-hemin仿生催化剂进行催化活性考察,利用其对废水中染料降解率来进行测定。本发明仿生催化剂活性考察的具体方法是:首先将仿生催化剂置于染料的水溶液中,使其在一定温度和pH值条件下处理60min,此时染料在仿生催化剂上的吸附达到平衡,然后添加H2O2开始氧化降解反应,根据染料浓度的变化计算其降解率,并以染料降解率数值评价该仿生催化剂的催化活性。图1显示,当单纯只有hemin存在时,反应60min后染料降解率为34.6%,这是由于hemin能够通过其Fe离子价态之间的转变(Fe3+/Fe2+),催化H2O2发生分解并生成氧化性极强的羟基自由基,后者通过氧化作用使染料发生降解反应。而本发明所述实施例一、实施例二或实施例三所得仿生催化剂存在时,反应60min后染料降解率均接近100%,说明与未负载的hemin相比,三种实施例所得的仿生催化剂催化活性都有大幅度的提高。这是由于本发明催化剂中聚丙烯腈纤维中咪唑环能够通过轴向配位作用与hemin中Fe离子进行结合,并通过推电子作用促进催化体系中铁和氧之间的电子传递,从而提高催化剂活化H2O2的效率,使体系中产生更多的羟基自由基,最终导致更多的染料分子发生氧化降解反应。
图2显示,未负载hemin的催化活性随着pH值的升高明显降低,尤其在碱性(pH=9.0)条件下反应60min后,染料降解率只有不足10%。然而实施例一所得的仿生催化剂的催化活性受pH值的影响并不显著,pH值升高至9.0时仍有超过90%的染料发生了降解反应。这说明聚丙烯腈纤维-hemin仿生催化剂不仅大幅度提高了hemin的催化活性,而且极大地改善了其pH适用范围,使其在较宽的pH范围内均具有很高的催化活性。
从图3可以看出,本发明仿生催化剂能够适用于多种不同结构染料的氧化降解反应中。在酸性黑234、阳离子黄19、活性红195和直接蓝14四种染料的氧化降解反应中,实施例一所得的仿生催化剂均显示出远高于hemin的催化活性,反应60min后染料降解率均接近100%。这是由于本发明催化剂能够通过催化H2O2分解产生强氧化性的羟基自由基,后者几乎能够氧化所有的有机物,这使得本发明催化剂在不同结构染料的氧化降解反应中具有通用性。此外,本发明催化剂还具有良好的重复使用性能。图4表明,本发明催化剂实施例二所得的仿生催化剂在连续5次对染料罗丹明B的氧化降解过程中,其催化活性没有发生降低现象,说明其可以多次应用于染料废水的氧化降解处理中,具有良好的实用性,工业化应用具有明显的经济效益。
Claims (3)
1.一种聚丙烯腈纤维-hemin仿生催化剂,其特征在于,该仿生催化剂呈纤维状,由含有咪唑环结构活性基团的改性聚丙烯腈纤维与hemin构成,其中铁离子含量为1.5-18.9mg/g,其制备步骤为:
1)按重量比1:(0.83-4.165)取聚丙烯腈纤维和2-氨基咪唑,将聚丙烯腈纤维加入到2-氨基咪唑水溶液中,用氢氧化钠调节pH值至9.5,在95℃和搅拌条件下反应2-6h,然后取出并用蒸馏水反复清洗烘干后得到改性聚丙烯腈纤维;
2)按重量比1:(0.1-0.5)取改性聚丙烯腈纤维和hemin,将改性聚丙烯腈纤维置于hemin的DMF溶液中,在40-60℃和搅拌条件下反应1-2.5h后取出,并用DMF和蒸馏水反复洗涤后烘干,得到聚丙烯腈纤维-hemin仿生催化剂。
2.根据权利要求1所述的聚丙烯腈纤维-hemin仿生催化剂,其特征在于,所述2-氨基咪唑水溶液的浓度为16.6-83.3g/L。
3.根据权利要求1所述的聚丙烯腈纤维-hemin仿生催化剂,其特征在于,所述hemin的DMF溶液的浓度为1.0-5.0g/L。
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