CN108686333B - 一种基于微/纳米配位聚合物的光催化降解磷酸酯类化合物的方法 - Google Patents
一种基于微/纳米配位聚合物的光催化降解磷酸酯类化合物的方法 Download PDFInfo
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Abstract
本发明属于环境催化领域，特别涉及一种以微/纳米配位聚合物为催化剂的光催化降解磷酸酯类化合物的方法。本发明中使用吡啶羧酸类配体(结构如附图所示)和过渡金属离子制备了一系列颗粒尺寸在微/纳米范围的配位聚合物作为光催化剂。光催化降解过程中，将磷酸酯类化合物溶解在水中，分别加入氧化剂H2O2和微/纳米配位聚合物构成反应体系，用光源照射反应体系，并使反应在空气气氛下进行。反应后磷酸酯类化合物基本降解(转化率大于90％)并深度矿化。
Description
技术领域：
本发明属于环境催化领域，特别涉及一种以微/纳米配位聚合物为催化剂的光催化降解磷酸酯类化合物的方法。
背景技术：
磷酸酯类化合物，是指分子结构中具有磷酸基的一类有机化合物。该类化合物可以作为乙酰胆碱酯酶的抑制剂，致使乙酰胆碱在有机体的生理作用部位积聚导致神经过度兴奋等症状，从而破坏有机体的神经系统。水体中的磷酸酯类化合物主要来源于农业及工业废水的排放，具有毒性大，浓度高，致癌，致畸，对光、热、氧等较稳定，可生化降解性差等特点，通过食物链的富集作用后，可能给人、畜的健康带来重大的隐患。因此，开发针对磷酸酯类化合物的降解方法对于环境治理具有重要意义。
光催化技术因为能够利用丰富的太阳能资源实现对污染物的有效降解，而受到普遍关注。目前国际上光催化领域的研究主要集中在两类光催化体系：以二氧化钛为代表的无机半导体异相光催化体系和以含铁配合物为代表的过渡金属配合物均相光催化体系。前者虽然具有较高的稳定性和光催化活性，但通常只能利用占太阳光比例很小的紫外光，并且无机半导体组成以及晶相的调节只能在非常小的范围内进行。过渡金属配合物类光催化剂往往具有很高的可见光吸收，且有机配体的多样性使得对其性能的调控十分容易，但其均相催化的本质使这类光催化剂难以回收利用，由此增加处理成本。以上因素都极大地限制了它们的实际应用。
配位聚合物是由有机配体和金属离子通过配位作用连接形成的一大类晶态或非晶态材料。由于有大量的有机配体和金属离子可供选择，使配位聚合物的组成和骨架结构具有多样性，这就方便了对其激发以及催化性能的调控。配位聚合物中有机配体和金属离子的密集有序排列，使得吸收的光能可以在结构单元间相互传递，因此可表现出类似无机半导体的光激发特性。因此配位聚合物兼具无机半导体的高电荷分离效率及易分离回收的优点和过渡金属配合物的高可见光吸收及组成结构易于调控的特点，有望发展成为一类新型可见光光催化剂。目前将配位聚合物应用于降解磷酸酯类化合物只有少量报道(J.E.Mondloch，M.J.Katz，W.C.Isley Iii，P.Ghosh，P.Liao，W.Bury，G.W.Wagner，M.G.Hall，J.B.DeCoste，G.W.Peterson，R.Q.Snurr，C.J.Cramer，J.T.Hupp，O.K.Farha，Nat.Mater.2015，14，512-516；M.J.Katz，J.E.Mondloch，R.K.Totten，J.K.Park，S.T.Nguyen，O.K.Farha，J.T.Hupp，Angew.Chem.Int.Ed.2014，53，497-501)，但在这些研究中都只是催化磷酸酯类化合物的水解，难以实现对底物的深度降解。
在本发明中，申请人以吡啶羧酸类配体和非贵过渡金属离子构筑了一系列颗粒尺寸在微/纳米范围内的配位聚合物光催化剂，利用该类光催化剂稳定性高、颗粒尺寸小的特点，通过活化H2O2成功实现对磷酸酯类化合物的高效降解。
发明内容
本发明的目的是提供一种降解磷酸酯类化合物的光催化氧化方法。
本发明的降解磷酸酯类化合物的光催化氧化方法：将磷酸酯类化合物溶解在水中，加入氧化剂H2O2和微/纳米配位聚合物构成反应体系，用光源照射反应体系，并使反应在空气气氛下进行，反应后磷酸酯类化合物基本降解并深度矿化。
所述的微/纳米配位聚合物是由吡啶羧酸类配体和过渡金属离子构筑的，颗粒尺寸在微米或纳米范围内的配位聚合物。
所述的吡啶羧酸类配体为在吡啶环上连接有羧基取代基的配体(图1)。
所述的微/纳米配位聚合物的合成方法为将吡啶羧酸类配体和含过渡金属离子的盐在水、有机溶剂或两者所组成的混合溶剂中进行反应制备，反应温度为0摄氏度至150摄氏度。
所述的微米配位聚合物催化剂在反应体系中的浓度为5毫克/升～50毫克/升。
所述的磷酸酯类化合物是分子结构中具有磷酸基团的有机分子。
所述的分子结构中具有磷酸基团的有机分子可以为磷酸单酯、磷酸双酯或磷酸三酯。
所述的光源是紫外光、可见光或者太阳光。
本发明的技术核心是磷酸酯类化合物在紫外光或可见光照射下，在微/纳米配位聚合物和H2O2的作用下，在水溶液中发生降解并深度矿化。
附图说明
图1 吡啶羧酸类配体的结构图
图2 [Fe(py-3，5-dc)(H2O)2](H2O)0.5的配位结构图。
图3 [Fe(py-3，5-dc)(H2O)2](H2O)0.5的扫描电镜照片。
图4 [Fe(py-2，5-dc)(H2O)3](H2O)0.5的配位结构图。
图5 [Fe(py-2，5-dc)(H2O)3](H2O)0.5的扫描电镜照片。
图6 [Zn(py-3，5-dc)(H2O)2]的配位结构图。
图7 [Zn(py-3，5-dc)(H2O)2]的扫描电镜照片。
图8 双(4-硝基苯基)磷酸酯的结构图。
图9 乙基对氧磷的结构图。
图10 三(4-硝基苯基)磷酸酯的结构图。
具体实施方式
实施例1
[Fe(py-3，5-dc)(H2O)2](H2O)0.5的合成
将1毫摩尔硫酸亚铁和1毫摩尔吡啶-3，5-二羧酸(H2py-3，5-dc)分散于200毫升由水和N，N’-二甲基甲酰胺所组成的混合溶剂(体积比为1∶1)中，在130摄氏度加热搅拌条件下反应4小时。反应结束后，冷却致室温，将橘黄色沉淀物离心分离，分别用蒸馏水、N，N’-二甲基甲酰胺和无水乙醇各洗涤三遍，在60℃真空干燥箱中干燥6小时。最后所得产物为[Fe(py-3，5-dc)(H2O)2](H2O)0.5。元素分析：31.4％碳，2.49％氢，5.28％氮；计算值为31.61％碳，3.03％氢，5.27％氮。配位结构和形貌分别如图2和图3所示。
实施例2
[Fe(py-2，5-dc)(H2O)3](H2O)0.5的合成
将0.5毫摩尔硫酸亚铁和0.5毫摩尔吡啶-2，5-二羧酸(H2py-2，5-dc)分散于12毫升由水和N，N’-二甲基甲酰胺所组成的混合溶剂(体积比为1∶1)中，装入25毫升水热反应釜在120摄氏度加热12小时。反应结束后，冷却致室温，将棕色沉淀物离心分离，分别用蒸馏水、N，N’-二甲基甲酰胺和无水乙醇各洗涤三遍，在60℃真空干燥箱中干燥6小时。最后所得产物为[Fe(py-2，5-dc)(H2O)3](H2O)0.5。元素分析：29.26％碳，3.92％氢，5.28％氮；计算值为29.60％碳，3.55％氢，4.93％氮。配位结构和形貌分别如图4和图5所示。
实施例3
[Zn(py-3，5-dc)(H2O)2]的合成
0.1毫摩尔吡啶-3，5-二羧酸(H2py-3，5-dc)和0.2毫摩尔氢氧化钠溶解在7.5毫升四氢呋喃和6.5毫升水配制的混合溶剂中。向该溶液中逐滴加入1毫升浓度为0.1毫摩尔/升的硝酸锌溶液，搅拌反应10分钟。反应结束后，将白色沉淀物离心分离，分别用蒸馏水和无水乙醇洗涤三遍，在60℃真空干燥箱中干燥6小时。最后所得产物为[Zn(py-3，5-dc)(H2O)2]。元素分析：31.16％碳，3.05％氢，5.14％氮；计算值为31.31％碳，3.38％氢，5.22％氮。配位结构和形貌分别如图6和图7所示。
实施例4
以[Fe(py-3，5-dc)(H2O)2](H2O)0.5为催化剂降解双(4-硝基苯基)磷酸酯(图8)
使用上述双(4-硝基苯基)磷酸酯作为初始反应物，将双(4-硝基苯基)磷酸酯溶解在水溶液中，加入[Fe(py-3，5-dc)(H2O)2](H2O)0.5和H2O2构成反应体系。其中，反应体系中的双(4-硝基苯基)磷酸酯的浓度为0.05毫摩尔/升，[Fe(py-3，5-dc)(H2O)2](H2O)0.5的浓度为0.01克/升，H2O2浓度为1.25毫摩尔/升；用可见光(300瓦氙灯用滤光片滤除420纳米以下部分)照射反应体系，并使反应在空气中进行90分钟。在可见光及微米配位聚合物的作用下，双(4-硝基苯基)磷酸酯的转化率为95％，总有机碳去除率为66％，磷、氮的释放率(分别转化为磷酸根离子和硝酸根离子)分别为74％和94％。
实施例5
以[Fe(py-3，5-dc)(H2O)2](H2O)0.5为催化剂降解乙基对氧磷(图9)
使用上述乙基对氧磷作为初始反应物，将乙基对氧磷溶解在水溶液中，加入[Fe(py-3，5-dc)(H2O)2](H2O)0.5和H2O2构成反应体系。其中，反应体系中的乙基对氧磷的浓度为0.05毫摩尔/升，[Fe(py-3，5-dc)(H2O)2](H2O)0.5的浓度为0.03克/升，H2O2浓度为1.25毫摩尔/升；用可见光(300瓦氙灯用滤光片滤除420纳米以下部分)照射反应体系，并使反应在空气中进行180分钟。在可见光及微米配位聚合物的作用下，乙基对氧磷的转化率为90％。
实施例6
以[Fe(py-3，5-dc)(H2O)2](H2O)0.5为催化剂降解三(4-硝基苯基)磷酸酯(图10)
使用上述三(4-硝基苯基)磷酸酯作为初始反应物，将三(4-硝基苯基)磷酸酯溶解在水溶液中，加入[Fe(py-3，5-dc)(H2O)2](H2O)0.5和H2O2构成反应体系。其中，反应体系中的三(4-硝基苯基)磷酸酯的浓度为0.05毫摩尔/升，[Fe(py-3，5-dc)(H2O)2](H2O)0.5的浓度为0.03克/升，H2O2浓度为1.25毫摩尔/升；用可见光(300瓦氙灯用滤光片滤除420纳米以下部分)照射反应体系，并使反应在空气中进行300分钟。在可见光及微米配位聚合物的作用下，三(4-硝基苯基)磷酸酯的转化率为93％。
对比例1
光照降解双(4-硝基苯基)磷酸酯(图8)
使用上述双(4-硝基苯基)磷酸酯作为初始反应物，将双(4-硝基苯基)磷酸酯溶解在水溶液中，加入H2O2构成反应体系。其中，反应体系中的双(4-硝基苯基)磷酸酯的浓度为0.05毫摩尔/升，H2O2浓度为1.25毫摩尔/升，反应体系中没有任何催化剂存在；用可见光(300瓦氙灯用滤光片滤除420纳米以下部分)照射反应体系，并使反应在空气中进行90分钟。在可见光的作用下反应90分钟后，双(4-硝基苯基)磷酸酯的转化率为1％。
对比例2
以[Fe(py-3，5-dc)(H2O)2](H2O)0.5为催化剂降解双(4-硝基苯基)磷酸酯(图8)
使用上述双(4-硝基苯基)磷酸酯作为初始反应物，将双(4-硝基苯基)磷酸酯溶解在水溶液中，加入[Fe(py-3，5-dc)(H2O)2](H2O)1.5和H2O2构成反应体系。其中，反应体系中的双(4-硝基苯基)磷酸酯的浓度为0.05毫摩尔/升，微米配位聚合物的浓度为0.01克/升，H2O2浓度为1.25毫摩尔/升；使反应在空气中及没有光照射的暗反应条件下进行90分钟。在微米配位聚合物的作用下，双(4-硝基苯基)磷酸酯的转化率为58％。
对比例3
以[Fe(py-3，5-dc)(H2O)2](H2O)0.5为催化剂降解双(4-硝基苯基)磷酸酯(图8)
使用上述双(4-硝基苯基)磷酸酯作为初始反应物，将双(4-硝基苯基)磷酸酯溶解在水溶液中，加入[Fe(py-3，5-dc)(H2O)2](H2O)1.5构成反应体系。其中，反应体系中的双(4-硝基苯基)磷酸酯的浓度为0.05毫摩尔/升，[Fe(py-3，5-dc)(H2O)2](H2O)1.5的浓度为0.01克/升，反应体系中没有H2O2存在；用可见光(300瓦氙灯用滤光片滤除420纳米以下部分)照射反应体系，并使反应在空气中进行90分钟。在可见光及微米配位聚合物的作用下，双(4-硝基苯基)磷酸酯的转化率为3％。
Claims (6)
1.一种基于微/纳米配位聚合物的光催化降解磷酸酯类化合物的方法，其特征是：将磷酸酯类化合物溶解在水溶液中，加入氧化剂H2O2和微/纳米配位聚合物构成反应体系，用光源照射反应体系，并使反应在空气气氛下进行，反应后磷酸酯类化合物基本降解并深度矿化；
所述的微/纳米配位聚合物由吡啶羧酸类配体和亚铁离子或锌离子所构筑，颗粒尺寸在微米或纳米范围内的配位聚合物；
所述的吡啶羧酸类配体为在吡啶环上连接有羧基取代基的配体，其结构式如下：
2.根据权利要求1所述的方法，其特征是：所述的微/纳米配位聚合物的合成方法为将吡啶羧酸类配体和含亚铁离子或锌离子的盐在水、有机溶剂或两者所组成的混合溶剂中进行反应制备，反应温度为0摄氏度至150摄氏度。
3.根据权利要求1所述的方法，其特征是：所述的微/纳米配位聚合物在反应体系中的浓度为5毫克/升～500毫克/升。
4.根据权利要求1所述的方法，其特征是：所述的磷酸酯类化合物是分子结构中具有磷酸基团的有机分子。
5.根据权利要求4所述的方法，其特征是：所述的分子结构中具有磷酸基团的有机分子为磷酸单酯、磷酸双酯或磷酸三酯。
6.根据权利要求1所述的方法，其特征是：所述的光源是紫外光、可见光或者太阳光。
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