CN105944763B - 具有还原Cr(VI)离子性质的硒醚亚铜簇负载型可见光催化剂 - Google Patents
具有还原Cr(VI)离子性质的硒醚亚铜簇负载型可见光催化剂 Download PDFInfo
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Abstract
本发明公开了一种具有还原Cr(VI)离子性质的硒醚亚铜簇负载型可见光催化剂，该催化剂原理为设计含硒醚的芳香环配体，以它的亚铜簇配合物作为敏化剂，通过物理吸附分步负载到TiO2，然后以这类化合物作为催化剂，表征它们的光学性质；并使用二本氨基脲显色剂方法进行分析验证。本发明还公开了该催化剂的制备方法。该催化剂只在可见光光源照射下进行催化；化学转化污染物迅速，可减少水体净化的周期；选用的化合物自身稳定，不会因为分解或难以回收而造成二次污染；用于污水处理的化学材料丰富存在、价格低廉、自身无毒性，对环境友好。
Description
技术领域
本发明涉及金属有机光催化材料技术领域，特别是涉及一种具有还原Cr(VI)离子性质的硒醚亚铜簇负载型可见光催化剂。
背景技术
水体中的重金属离子是常见的一种污染源，它们通常具有高毒性、强致癌性等特点严重威胁着人们的健康安全。有研究表明，特别是Cr(VI)离子具有很高的毒性，吸入人体可导致过敏、中毒和对人产生基因缺陷；同时，Cr(VI)还有很强的致癌性，过量的，特别是超过10ppm的Cr(VI)对水生物具有致死作用。而被还原后的三价铬离子则不具备这些毒性。
在过去的几年中，传统的生物和物理处理的方法，包括吸附、超滤、凝结等已经成为从废水和各种水体中去除污染物的主流技术。尽管如此，许多新兴的人为有机或无机污染物，特别是那些仅仅在非常低的浓度就具有高毒性的Cr(VI)，需要通过新的化学方法转化为安全无毒的化合物以达到去污净水的效果。自二十世纪八十年代以来，光催化在污染物治理方面取得了很大的进展。研究并设计光敏性好、光化学性能稳定的催化剂，将会进一步提高太阳光能到化学能的转化效率，在实际污染物处理方面获得更大的应用前景。综合以上这些特点考虑，以光能为初始能量，通过光催化剂转化为化学能，最终达到还原水中Cr(VI)的光催化途径是更加理想的选择，目前未见任何报道。
发明内容
发明目的：为了解决水体中Cr(VI)离子带来的污染问题，本发明公开了一种具有还原Cr(VI)离子的硒醚亚铜簇负载型可见光光催化剂。
技术方案：为了达到上述目的，本发明公开了一种具有还原Cr(VI)离子性质的硒醚亚铜簇负载型可见光催化剂。该催化剂以Se作为结合位点，与亚铜形成配位化合物，以芳香环作为光信号基团，对光照产生吸收响应。其结构式C如下：
光催化剂在光的照射下，会产生类似光合作用的光催化反应，产生出氧化能力极强的自由氢氧基和活性氧，具有很强的光氧化还原功能。多芳香环类硒醚铜簇具有良好的可见光光学活性、光催化还原活性、光化学稳定性和重复性，芳香环化合物还能与TiO2以物理吸附的形式形成电荷转移配合物，本发明设计含硒醚的芳香环配体，以它的亚铜簇配合物作为敏化剂，通过物理吸附分步负载到TiO2，然后以这类化合物作为催化剂，表征它们的光学性质。并验证其在光催化下还原水中Cr(VI)离子的能力。
本发明还公开了上述对Cr(VI)具有还原催化效应的硒醚亚铜簇负载型可见光催化剂的制备方法，包括如下步骤：
(1)含芳香环硒醚配体L的合成：
取100mL三口烧瓶，反复抽真空通氮气3次，量取60mL乙醇，无水硫酸镁干燥，加入到三口烧瓶中。称取0.156g二苯基二硒(0.5mmol)加入到充满氮气的三口瓶中，反复除气，冰浴3-8分钟，称取20当量的硼氢化钠0.378g加入到三口烧瓶中，溶液立即变为白色乳浊液，继续冰浴15min后，撤去冰浴，室温下继续反应2h，溶液逐渐变为澄清透明的无色溶液，2h之后，称取0.098g(0.25mmol)9-(3-溴-2-溴甲基丙基)蒽溶于少许回流过的四氢呋喃中，待其完全溶解之后，用注射器加入到三口烧瓶中，溶液变为淡黄绿色，室温下反应5h之后，停止反应，减压蒸馏旋干，并用二氯甲烷和水进行萃取，取下层白色浑浊溶液，用无水硫酸镁干燥得几乎无色的澄清溶液，向所得溶液中加入200-300目硅胶，旋干，得到淡黄色沙状固体；将合成的粗产品进行过柱子处理，用正己烷溶解适量的200-300目硅胶，装填柱子并压实，用正己烷与二氯甲烷以5:1的混合液作淋洗剂，取第二段旋干得到黄绿色的油状物L。
产率42.63％(0.0486g,0.0865mmol)。1H-NMR(400MHz,CDCl3)(δ,ppm):8.38(C14H9,H10,s.1H),8.21(C14H9,H1+8,d,2H),8.00(C14H9,H4+5,d,2H),7.46-7.35(C14H9,m,4H),7.13(C6H5,d,4H),7.06(C6H5,d,2H),6.98(C6H5,t,4H),3.87(ArCH2C,d,2H),3.18(CCH2Se,m,2H),2.99(CCH2Se,m,2H),2.54(CCHCSe,m,1H).ES MS:562.03([M+1]+).Elemental AnalysisCalcd(％):C 66.18,H 4.81；found:C 66.17,H 4.83.m.p.217-218℃.
(2)浸制法合成亚铜簇负载型催化剂C：0.080g(1mmol)称量好的TiO2加入到40mL乙腈溶液中超声30分钟，使TiO2充分分散在乙腈溶液中。然后称取0.544g(1mmol)配体L加入到白色的TiO2乙腈悬浊液，用锡箔纸包裹反应的烧杯，黑暗条件下开启磁力搅拌24h。24h后混合悬浊液呈淡黄色，然后称取0.190g(1mmol)CuI避光条件下继续搅拌24h。停止反应后将黄色悬浊液分批加入离心管离心，用乙腈溶液洗涤沉淀以除去未配位的配体L和CuI。在60℃烘箱干燥沉淀最终得到淡黄色粉末产物C。
FT-IR:νAR(C-H)cm-1 3050,2965；(C＝C)cm-1 1580,1518,1435,1350.
光催化还原Cr(VI)试验：配制30ml 1×10-4mol/L重铬酸钾水溶液，加入到50mL玻璃试管，用硫酸调节溶液PH到2。催化剂C投入量10-40mg不等，加入后搅拌确保均匀分散在水溶液中。用锡箔纸包裹试管表面，在黑暗条件下搅拌30分钟保证催化剂在非均相体系中的吸-脱附平衡。30分钟后，撤去锡箔纸开启300W金属卤素灯和风扇。此时玻璃试管用支架固定置于1mol/L亚硝酸钠水溶液内，以过滤掉波长小于400nm的发射光。开启磁力搅拌，同时用气泵往溶液中鼓入空气。每隔30min用滴管汲取3ml样品于离心管内，收集完所有样品后停止反应。将每组离心管内的样品在10000转/分钟的离心机中离心1h，汲取上清液用于滴加显色剂紫外检测Cr(VI)离子，收集催化剂沉淀用于下一步的重复实验。
光催化还原Cr(VI)到Cr(III)离子实验分析使用二本氨基脲(DPC)显色剂方法，Cr(VI)能与显色剂形成络合物而显红色，紫外-可见吸收光谱在540nm出现特征吸收峰。
有益效果：本发明公开的具有还原Cr(VI)离子性质的硒醚亚铜簇负载型可见光催化剂化学转化污染物迅速，可减少水体净化的周期；选用的化合物自身稳定，不会因为分解或难以回收而造成二次污染；用于污水处理的化学材料丰富存在、价格低廉、自身无毒性，对环境友好。
附图说明
图1显色剂下Cr(VI)离子紫外吸收光谱；
图2不同催化剂及空白实验光催化还原水中Cr(VI)离子速率图；
图3不同催化剂C投入量对可见光光催化还原Cr(VI)离子影响；
图4催化剂C随重复使用次数光催化还原效率影响。
具体实施方式
下面结合实施例对本发明做出详细说明。
实验试剂：
硼氢化钠(CP)、碘化亚铜(CP)购自国药集团化学试剂有限公司；二氯甲烷(AR)、乙醇(AR)购自无锡市亚盛化工有限公司；二苯基二硒醚(CP)购自东京化成工业株式会社；重铬酸钾(AR)、硫酸镁(AR)购自上海凌峰化学试剂有限公司；四氢呋喃(AR)、正己烷(AR)购自上海试四赫维化工有限公司；硅胶(试剂级)购自青岛海洋化工厂分厂；二氧化钛、DegussaP25、二苯氨基脲(DPC)购自天津市化学试剂研究所。
实验仪器：
旋转蒸发仪购自上海申胜生物技术有限公司；数显恒温水浴锅、磁力加热搅拌器购自国华电器有限公司；真空泵购自上海仪表供销公司；S42-D(Ⅲ)循环水式真空泵购自巩义市英峪予华仪器厂；电热真空干燥箱购自上海实验仪器有限公司；标准Schleck管线、BRUKER DRX500型核磁共振仪、电喷雾质谱仪、傅里叶红外光谱仪、Thermo ScientificNicolet IS10、TG16-WS台式高速离心机购自长沙湘仪离心机仪器有限公司。
实施例1
具有还原Cr(VI)离子性质的硒醚亚铜簇负载型可见光催化剂C的制备：
(1)含芳香环硒醚配体L的合成：取100mL三口烧瓶，反复抽真空通氮气3次，量取60mL乙醇，无水硫酸镁干燥，加入到三口烧瓶中。称取0.156g二苯基二硒(0.5mmol)加入到充满氮气的三口瓶中，反复除气，冰浴3-8分钟，称取20当量的硼氢化钠0.378g加入到三口烧瓶中，溶液立即变为白色乳浊液，继续冰浴15min后，撤去冰浴，室温下继续反应2h，溶液逐渐变为澄清透明的无色溶液，2h之后，称取0.098g(0.25mmol)9-(3-溴-2-溴甲基丙基)蒽溶于少许回流过的四氢呋喃中，待其完全溶解之后，用注射器加入到三口烧瓶中，溶液变为淡黄绿色，室温下反应5h之后，停止反应，减压蒸馏旋干，并用二氯甲烷和水进行萃取，取下层白色浑浊溶液，用无水硫酸镁干燥得几乎无色的澄清溶液，向所得溶液中加入少许200-300目硅胶，旋干，得到淡黄色沙状固体；将合成的粗产品进行过柱子处理，用正己烷溶解适量的200-300目硅胶，装填柱子并压实，用正己烷与二氯甲烷以5:1的混合液作淋洗剂，取第二段旋干得到黄绿色的油状物L。
(2)浸制法合成亚铜簇负载型催化剂C：0.080g(1mmol)称量好的TiO2加入到40mL乙腈溶液中超声30分钟，使TiO2充分分散在乙腈溶液中。然后称取0.544g(1mmol)配体L加入到白色的TiO2乙腈悬浊液，用锡箔纸包裹反应的烧杯，黑暗条件下开启磁力搅拌24h。24h后混合悬浊液呈淡黄色，然后称取0.190g(1mmol)CuI避光条件下继续搅拌24h。停止反应后将黄色悬浊液分批加入离心管离心，用乙腈溶液洗涤沉淀以除去未配位的配体L和CuI。在60℃烘箱干燥沉淀最终得到淡黄色粉末产物，即催化剂C。
光催化还原Cr(VI)试验：
配制30ml 1×10-4mol/L重铬酸钾水溶液，加入到50mL玻璃试管，用硫酸调节溶液PH到2。催化剂C投入量10-40mg不等，加入后搅拌确保均匀分散在水溶液中。用锡箔纸包裹试管表面，在黑暗条件下搅拌30分钟保证催化剂在非均相体系中的吸-脱附平衡。30分钟后，撤去锡箔纸开启300W金属卤素灯和风扇。此时玻璃试管用支架固定置于1mol/L亚硝酸钠水溶液内，以过滤掉波长小于400nm的发射光。开启磁力搅拌，同时用气泵往溶液中鼓入空气。每隔30min用滴管汲取3ml样品于离心管内，收集完所有样品后停止反应。将每组离心管内的样品在10000转/分钟的离心机中离心1h，汲取上清液用于滴加显色剂紫外检测Cr(VI)离子，收集催化剂沉淀用于下一步的重复实验。
如图1所示，为显色剂下Cr(VI)离子紫外吸收光谱。光催化还原Cr(VI)到Cr(III)离子实验分析使用的是二本氨基脲(DPC)显色剂方法，Cr(VI)能与显色剂形成络合物而显红色，紫外-可见吸收光谱在540nm出现特征吸收峰，由图示可见，随着时间递增，吸光度逐渐降低，特征吸收峰显示最佳时间为0-60min。
实施例2
配制4组30ml 1×10-4mol/L重铬酸钾水溶液，分别加入20mg实施例1制备所得催化剂C、TiO2、配体L和一组空白实验，在暗处搅拌30min后开启光源继续反应。每隔30min收集3ml反应液样品，按照上述操作测每组样品紫外。如图2所示，λ>400nm，C0为初始Cr(VI)浓度，Ct为Cr(VI)随时间变化浓度，由分析紫外吸收光谱可以看出投入催化剂C后，波长为540nm处Cr(VI)离子吸收峰随反应时间进行不断减弱最后消失，而其它几组并没发生较大变化，由此可见只有催化剂C具有可见光催化还原活性。
实施例3
配制4组30ml 1×10-4mol/L重铬酸钾水溶液，分别加入10-40mg实施例1制备所得催化剂C，在暗处搅拌30min后开启光源继续反应。每隔30min收集3ml反应液样品，按照上述操作测每组样品紫外。结果如图3所示，其中初始浓度为1×10-4mol/L，分析紫外吸收光谱可以看出随着催化剂投入量从10mg-20mg增长，催化转化率明显的提高。当继续增加催化剂投入量到40mg催化还原时间并没缩短，当投入催化剂量在20mg时有最佳的催化转化效率。
实施例4
投入20mg实施例1所得催化剂C到配制好的重铬酸钾水溶液中，按照实施例1所述方法进行光催化还原实验，实验结束后回收每组样品，再离心得到催化剂沉淀，烘干并回收，称量后重复相同条件的光催化还原实验，反复重复5次并记录每次催化转化效率对比。结果如图4所示，可见催化剂C随重复使用次数光催化还原效率影响，在经过五次的重复光催化还原Cr(VI)实验后，催化剂仍然保持着78％的催化效率。催化效率如下表：
Claims (3)
1.一种具有还原Cr(VI)离子性质的硒醚亚铜簇负载型可见光催化剂，其特征在于：所述催化剂以Se作为结合位点，与亚铜形成配位化合物，以芳香环作为光信号基团，对光照产生吸收响应，其结构式C如下：
2.权利要求1所述具有还原Cr(VI)离子性质的硒醚亚铜簇负载型可见光催化剂的制备方法，其特征在于包括以下步骤：
(1)含芳香环硒醚配体L的合成：
取100mL三口烧瓶，反复抽真空通氮气3-5次，量取60mL乙醇，无水硫酸镁干燥，加入到三口烧瓶中；称取0.156g二苯基二硒(0.5mmol)加入到充满氮气的三口烧瓶中，反复除气，冰浴3-8分钟，称取20当量的硼氢化钠0.378g加入到三口烧瓶中，溶液立即变为白色乳浊液，继续冰浴15min后，撤去冰浴，室温下继续反应2h，溶液逐渐变为澄清透明的无色溶液；称取0.098g(0.25mmol)9-(3-溴-2-溴甲基丙基)蒽溶于少许回流过的四氢呋喃中，待其完全溶解之后，用注射器加入到三口烧瓶中，溶液变为淡黄绿色，室温下反应5h之后，停止反应，减压蒸馏旋干，并用二氯甲烷和水进行萃取，取下层白色浑浊溶液，用无水硫酸镁干燥得几乎无色的澄清溶液，向所得溶液中加入200-300目硅胶，旋干，得到淡黄色沙状固体；将合成的粗产品进行过柱子处理，用正己烷溶解200-300目硅胶，装填柱子并压实，用正己烷与二氯甲烷以5:1的混合液作淋洗剂，取第二段旋干得到黄绿色的油状物，即为含芳香环硒醚配体L；
(2)浸制法合成亚铜簇负载型催化剂C：
将0.080g(1mmol)称量好的TiO2加入到40mL乙腈溶液中超声30分钟，使TiO2充分分散在乙腈溶液中，然后称取0.544g(1mmol)配体L加入到白色的TiO2乙腈悬浊液，用锡箔纸包裹反应的烧杯，黑暗条件下开启磁力搅拌24h后，混合悬浊液呈淡黄色，然后称取0.190g(1mmol)CuI避光条件下继续搅拌24h，停止反应后将黄色悬浊液分批加入离心管离心，用乙腈溶液洗涤沉淀以除去未配位的配体L和CuI，在60℃烘箱干燥沉淀最终得到淡黄色粉末产物，即光催化剂C。
3.权利要求1所述具有还原Cr(VI)离子性质的硒醚亚铜簇负载型可见光催化剂在催化还原水中Cr(VI)离子中的应用。
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