CN114950560A - 有机罗丹明B和无机Cr(VI)双功能可见光催化降解的有机配合物及制备方法和应用 - Google Patents
有机罗丹明B和无机Cr(VI)双功能可见光催化降解的有机配合物及制备方法和应用 Download PDFInfo
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Abstract
一种有机罗丹明B和无机Cr(VI)双功能可见光催化降解的有机配合物,该有机配合物的分子式如下:[CoII(bcbpy)2(θ‑Mo8O26)0.5]·2H2O,其中,bcbpy为1‑(4‑羧基‑苯亚甲基)‑4,4’联吡啶;将HbcbpyC、CoCl2·6H2O和Na2MoO4·2H2O置于内衬聚四氟乙烯的不锈钢高压釜中,加入去离子水,水热反应,然后降至室温,洗涤、晾干,得到有机配合物。该有机配合物可以应用于在光催化还原六价铬和光降解有机染料罗丹明B中。合成方法简单,能在短时间内快速将六价铬还原为无毒三价铬和对罗丹明B的高效光降解,且具有高度的稳定性和可循环使用性,从而节约资源,降低污染。
Description
技术领域
本发明属于有机配合物光催化技术领域,特别涉及一种有机罗丹明B和无机Cr(VI)双功能可见光催化降解的有机配合物及制备方法和应用。
背景技术
随着工业的发展和经济的增长,环境污染和能源危机已经引起了全世界的广泛关注,尤其是化学污染物所带来的水污染问题一直受到人们的重视。而水污染问题,尤其是工业水污染,也一直是人们所关注的焦点。其中,重金属离子、有机染料是工业废水中主要的污染物,排放含有重金属离子和有毒染料的废水成为人类健康和生态系统的威胁。
六价铬是环境中最常见的重金属阳离子污染物之一,它被引入环境主要是因为铬酸盐和重铬酸盐在各种行业中的广泛使用,如皮革鞣制、纺织制造、电镀和钢铁制造,同时,六价铬是高度可溶的,并且对活生物体具有毒性、致癌性、突变性和致畸性,因此,对水中有害的六价铬金属离子的去除或将六价铬还原为无毒的三价铬是非常有必要的。
罗丹明B,是一种具有鲜桃红色的人工合成的染料,其危害性极大且非常难降解,可导致人皮肤、内脏红染、脑间血管轻度淤血,心肌纤维断裂。人食入罗丹明B,出现肺水肿,即肺泡腔内见大量均质红染物,肾间质血管淤血,肾小管腔内有管型,长期食入将会导致死亡,因此,开发一种能够高效降解罗丹明B催化剂是解决工业废水污染物的一种有效的途径。
作为金属-有机框架(MOFs)和多金属氧酸盐(POMs)相结合的新型功能性材料,不仅能够表现出MOFs的多孔、多笼、高比表面积、高稳定性、可裁剪性等优越的结构特征,同时也有效地结合了POMs的结构和性质的特殊性,进而能够实现材料结构和性能的双重调控的目的。
因此,设计合成一种催化速度快,效率高,且可重复利用适用于有机罗丹明B和无机Cr(VI)双功能有机配合物光催化剂具有十分重要的意义。
发明内容
本发明要解决的技术问题是提供一种有机罗丹明B和无机Cr(VI)双功能可见光催化降解的有机配合物及制备方法和应用,可在短时间内快速将六价铬还原为无毒三价铬和对罗丹明B的高效光降解,且具有高度的稳定性和可循环使用性,从而节约资源,降低污染。
本发明的技术解决方案是:
一种有机罗丹明B和无机Cr(VI)双功能可见光催化降解的有机配合物,该有机配合物的分子式如下:
[CoII(bcbpy)2(θ-Mo8O26)0.5]·2H2O
其中,bcbpy为1-(4-羧基-苯亚甲基)-4,4’联吡啶。
一种有机罗丹明B和无机Cr(VI)双功能可见光催化降解的有机配合物的制备方法,其具体步骤如下:
将HbcbpyCl(结构式为:),CoCl2·6H2O,Na2MoO4·2H2O按照摩尔比1:2:2.5称取,并置于25mL内衬聚四氟乙烯的不锈钢高压釜中,加入去离子水,然后升温至120℃,在120℃保温4天,然后降至室温,洗涤、晾干,得到有机配合物[CoII(bcbpy)2(θ-Mo8O26)0.5]·2H2O,其中,bcbpy为1-(4-羧基-苯亚甲基)-4,4’联吡啶。
进一步的,升温速率为10℃/h。
一种有机罗丹明B和无机Cr(VI)双功能可见光催化降解的有机配合物在光催化还原六价铬和光降解有机染料罗丹明B中的应用。
进一步的,所述有机配合物在光催化还原六价铬中的应用,其具体步骤如下:
(1)将有机配合物在玛瑙研钵中研磨10min~20min后,再在球磨机中研磨30min,得到有机配合物的粉末;
(2)将有机配合物粉末分散到含有六价铬离子的水溶液中,然后加入乙醇,超声10min形成分散均匀的悬浊液,在可见光的照射下,进行光催化还原30min时,将水溶液中的六价铬离子还原成三价铬离子。
进一步的,所述的有机配合物的用量为:有机配合物与重铬酸钾的摩尔比为(0.5~1.5):1。
进一步的,有机配合物与重铬酸钾的摩尔比为1:1的条件下,光催化还原六价铬的光催化还原效率为95%。
所述含有六价铬离子的水溶液与乙醇的体积比为1:1。
所述含有六价铬离子的水溶液为含有重铬酸根离子的水溶液。
进一步的,所述有机配合物在光降解有机染料罗丹明B中的应用,其具体步骤如下:(1)将有机配合物在玛瑙研钵中研磨10min~20min后,再在球磨机中研磨30min,得到有机配合物的粉末;
(2)将有机配合物粉末分散到罗丹明B的水溶液中,分散均匀形成悬浊液,在可见光的照射下,进行光催化降解罗丹明B90min。
进一步的,所述有机配合物与罗丹明B的摩尔比为(20~34):1。
进一步的,所述有机配合物与罗丹明B的摩尔比为27:1,光催化降解罗丹明B光催化降解效率达到99%。
本发明的有益效果是:
利用金属-紫精缺电子型MOFs对POMs具有吸电子效应,设计合成了一种紫精类配体构筑的多酸基MOF材料,不仅能够拓展多酸基功能配合物材料的合成途径,还显示出来较强的光催化性能。该多酸基钴MOF材料在可见光的照射下,30分钟内还原六价铬的效率可以达到95%,90分钟内可以将罗丹明B几乎完全降解,光降解效率可以达到99%,催化速度快,效率高,且可以回收再利用,是处理废水污染物的良好光催化剂。
附图说明
图1是本发明的[CoII(bcbpy)2(θ-Mo8O26)0.5]·2H2O的配位环境图;
图2是本发明的[CoII(bcbpy)2(θ-Mo8O26)0.5]·2H2O的基本单元;
图3是本发明的[CoII(bcbpy)2(θ-Mo8O26)0.5]·2H2O结构中的二维金属有机骨架;
图4是本发明的[CoII(bcbpy)2(θ-Mo8O26)0.5]·2H2O的三维堆积结构图;
图5是本发明的[CoII(bcbpy)2(θ-Mo8O26)0.5]·2H2O的红外光谱图;
图6是本发明的[CoII(bcbpy)2(θ-Mo8O26)0.5]·2H2O的粉末线衍射谱图;
图7是本发明的[CoII(bcbpy)2(θ-Mo8O26)0.5]·2H2O的热分析图;
图8是本发明的[CoII(bcbpy)2(θ-Mo8O26)0.5]·2H2O在黑暗条件下还原六价铬的吸收光谱;
图9是本发明的[CoII(bcbpy)2(θ-Mo8O26)0.5]·2H2O在没有催化剂存在下光催化还原六价铬的吸收光谱;
图10是本发明的[CoII(bcbpy)2(θ-Mo8O26)0.5]·2H2O在可见光下光催化还原六价铬的吸收光谱;
图11是本发明的[CoII(bcbpy)2(θ-Mo8O26)0.5]·2H2O在可见光下光催化还原反应后三价铬的XPS能谱;
图12是本发明的[CoII(bcbpy)2(θ-Mo8O26)0.5]·2H2O在有无催化剂条件下对六价铬的还原效率对比图;
图13是本发明的[CoII(bcbpy)2(θ-Mo8O26)0.5]·2H2O在可见光下光催化还原六价铬三次循环后的效果;
图14是本发明的[CoII(bcbpy)2(θ-Mo8O26)0.5]·2H2O在黑暗条件下吸附罗丹明B的吸收光谱;
图15是本发明的[CoII(bcbpy)2(θ-Mo8O26)0.5]·2H2O在没有催化剂存在下光催化降解罗丹明B吸收光谱;
图16是本发明的[CoII(bcbpy)2(θ-Mo8O26)0.5]·2H2O在可见光下光催化降解罗丹明B的吸收光谱;
图17是本发明的[CoII(bcbpy)2(θ-Mo8O26)0.5]·2H2O在有无催化剂条件下对罗丹明B的降解效率对比图;
图18是本发明的[CoII(bcbpy)2(θ-Mo8O26)0.5]·2H2O在可见光下光催化降解罗丹明B三次循环后的效果;
图19是本发明的[CoII(bcbpy)2(θ-Mo8O26)0.5]·2H2O在可见光下光催化反应后的红外光谱图;
图20是本发明的[CoII(bcbpy)2(θ-Mo8O26)0.5]·2H2O在可见光下光催化反应后的粉末衍射谱图。
具体实施方式
实施例1合成[CoII(BCbpy)2(θ-Mo8O26)0.5]·2H2O
将0.50mmolHbcbpy,1.00mmolCoCl2·6H2O,1.29mmolNa2MoO4·2H2O和8mL去离子水依次加入到25mL内衬聚四氟乙烯的不锈钢高压釜中,然后以10℃/h升温速率升温至120℃条件下,恒温加热四天后缓慢降至室温,洗涤、晾干,得到粉色块状晶体[CoII(BCbpy)2(θ-Mo8O26)0.5]·2H2O(配合物1),室温下干燥,产率为42%,其配位环境图如图1所示,金属和配体形成的基本单元如图2所示,金属和配体形成的二维层如图3所示,整体结构的三维堆积结构如图4所示。
一、基于本发明实施例1的配合物1的表征
(1)红外光谱表征相成分
在FT-IR光谱仪进行测试配合物材料的红外光谱,扫描范围400~4000cm-1。如图5所示多酸的特征吸收峰在918cm-1~663cm-1,bcbpy配体中的ν(C–N)吸收峰出现在1552cm-1~1423cm-1,羧基吸收峰出现在1639cm-1~1608cm-1,表明配合物是由对应原料合成的。
(1)粉末衍射表征相纯度
在RigakuUltima IV粉末X射线衍射仪上收集完成粉末衍射数据,操作电流为40mA,电压为40kV。采用钼靶X射线。固定扫描,接收狭缝宽为0.1mm。密度数据收集扫描范围为5°到50°,扫描速度为5°/s,跨度为0.02°/次。数据拟合使用Cerius2程序,单晶结构粉末衍射谱模拟转化使用Mercury 1.4.1。
如图6所示,配合物1的粉末X射线衍射谱图与拟合的PXRD谱图基本吻合,表明该多酸基Co-MOF为纯相。
(3)热重表征材料稳定性
热稳定性采用PE-Pyris Diamond S-II热分析仪完成,加热速率10℃/min,温度范围30℃~800℃。图7表明本发明合成的配合物1的分解温度范围为25℃~520℃。
二、晶体结构测定
用显微镜选取合适大小的单晶,室温下采用Bruker SMART APEX II衍射仪(石墨单色器,Mo-Ka,)收集衍射数据。扫描方式衍射数据使用SADABS程序进行吸收校正。数据还原和结构解析分别使用SAINT和SHELXTL程序完成。最小二乘法确定全部非氢原子坐标,并用理论加氢法得到氢原子位置。采用最小二乘法对晶体结构进行精修。图1-4展示出实施例1合成的配合物1的基本配位情况和扩展结构。其晶体学衍射点数据收集与结构精修的部分参数如表1所示:
表1
三、多酸基钴金属有机骨架光催化还原六价铬的测试
对实施例1合成的配合物1[CoII(bcbpy)2(θ-Mo8O26)0.5]·2H2O进行了光催化还原六价铬的测试,结果表明配合物1对六价铬离子的还原具有良好的效果,可应用于处理废水中六价铬离子。
配合物1光催化还原六价铬离子实验的具体步骤如下:
将100mg的配合物1[CoII(bcbpy)2(θ-Mo8O26)0.5]·2H2O在玛瑙研钵中研磨10min~20min后,放入球磨机中研磨30min后成均匀的粉末,精确称取10mg固体样品分散到10mL、8.2×10-4M重铬酸钾的水溶液中,然后加入10mL乙醇,超声10min形成分散均匀的悬浊液作为实验组,先放入黑暗中搅拌半个小时,每隔15min取出3mL悬浊液进行离心,取离心后的上清液进行吸光度的测定,根据图8可见,紫外的吸光度没有明显的变化。在不加配合物1情况下,取相同体积的上述溶液作为空白对照组。实验组和空白对照组分别边搅拌边采用300W氙灯作为可见光光源进行照射。对于实验组和空白对照组,每隔15min取3mL溶液进行离心分离;得到上层溶液进行UV测试。在经过30min可见光光照后,在配合物1无催化剂情况下,对照组溶液中的Cr2O7 2-几乎无法仅仅通过光照被还原,如图9所示;在存在催化剂情况下,上述实验组溶液中的Cr2O7 2-的特征吸收发生快速显著的降低,表明Cr2O7 2-已经迅速被还原,如图10-11所示。在经过30min可见光光照射后,根据还原效率计算公式[(C0-Ct)/C0],Cr2O7 2-的还原效率可达到95%,如图12所示。
如表2所示,在乙醇与重铬酸钾水溶液的体积比为1:1的条件下,探索了配合物1与重铬酸钾摩尔比为(0.5~1.5):1对可见光光催化还原六价铬还原效率的影响:当配合物1与重铬酸钾的摩尔比为0.5:1时,在经过30min可见光光照后,光催化还原六价铬的效率为77%;当配合物1与重铬酸钾的摩尔比为1:1时,在经过30min可见光光照后,光催化还原六价铬的效率为95%;当配合物1与重铬酸钾的摩尔比为1.5:1时,在经过30min可见光光照后,光催化还原六价铬的效率为81%。因此,配合物1与重铬酸钾的摩尔比为1:1时,光催化效果最好。
表2
将光催化还原六价铬后的晶体回收后用水和乙醇的混合溶液洗涤三次,再加入同样体积和浓度的重铬酸钾溶液,然后在重复上述实验组的操作。重复3次后,光催化效果仍很好,每次的光催化效率分别为94.04%,93.85%,91.06%,如图13所示。
四、配合物1光催化降解罗丹明B的测试
对实施例1合成的配合物1[CoII(BCbpy)2(θ-Mo8O26)0.5]·2H2O进行了光催化降解罗丹明B的测试,结果表明配合物1对罗丹明B的降解效果良好,可应用于处理废水中的有机染料。
配合物1光催化降解罗丹明B实验的具体步骤如下:
将100mg的催化剂[CoII(bcbpy)2(θ-Mo8O26)0.5]·2H2O在玛瑙研钵中研磨10min~20min后,放入球磨机中研磨30min后成均匀的粉末,精确称取20mg固体样品分散到40mL、1.46×10-5M罗丹明B的水溶液中作为实验组,先放入黑暗中搅拌半个小时,以达到吸附解吸平衡,每隔15分钟取出3毫升悬浊液进行离心,取离心后的上清液进行UV测定,根据图14可见,紫外的吸光度没有明显的变化。在不加配合物1的情况下,取相同体积的上述溶液作为空白对照组。实验组和空白对照组分别边搅拌边采用300W氙灯作为可见光光源进行照射。对于实验组和空白对照组,每隔15min取3mL溶液进行离心分离;得到上层溶液进行UV测试。在经过90min可见光光照后,在无配合物1催化剂情况下,对照组溶液中的罗丹明B染料分子几乎无法仅仅通过光照而降解,如图15所示;在存在催化剂情况下,上述实验组溶液中的罗丹明B染料分子的特征吸收发生快速显著的降低,表明该染料分子已经发生迅速分解,如图16所示。在经过90min可见光光照射后,罗丹明B的降解效率可以达到99%,如图17所示。
如表3所示,探索了配合物1与罗丹明B的摩尔比为20~34:1对可见光光催化降解罗丹明B效率的影响:当配合物1与罗丹明B的摩尔比为20:1时,在经过90min可见光光照后,光催化降解罗丹明B的效率为90%;当配合物1与罗丹明B的摩尔比为27:1时,在经过30min可见光光照后,光催化降解罗丹明B的效率为99%;当配合物1与罗丹明B的摩尔比为34:1时,在经过30min可见光光照后,光催化降解罗丹明B的效率为94%。因此,配合物1与罗丹明B的摩尔比为27:1时光催化效果最好。
表3
将光催化降解罗丹明B后的晶体回收后用水洗涤三次,再加入同样体积和浓度的罗丹明B溶液,然后重复上述光降解实验。重复3次后,每次的光催化降解率分别为96.74%,96.23%,95.15%,如图18所示。
如图19-20所示,将重复三次后的样品回收,进行红外和粉末衍射表征测试,与原始红外光谱和粉末衍射吻合较好,表明该多酸基金属有机配合物材料在催化过程中,具有良好的稳定性。
以上实验结果表明配合物1可作为可见光下光催化还原六价铬和降解罗丹明B的高效催化剂,且可以循环使用,是处理废水中污染物的良好催化剂。
以上仅为本发明的具体实施例而已,并不用于限制本发明,对于本领域的技术人员来说,本发明可以有各种更改和变化。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种有机罗丹明B和无机Cr(VI)双功能可见光催化降解的有机配合物,其特征是:
该有机配合物的分子式如下:
[CoII(bcbpy)2(θ-Mo8O26)0.5]·2H2O
其中,bcbpy为1-(4-羧基-苯亚甲基)-4,4’联吡啶。
3.根据权利要求2所述的有机罗丹明B和无机Cr(VI)双功能可见光催化降解的有机配合物的制备方法,其特征是:升温速率为10℃/h。
4.一种如权利要求1所述的有机配合物在光催化还原六价铬和光降解有机染料罗丹明B中的应用。
5.根据权利要求4所述的有机配合物在光催化还原六价铬中的应用,其特征是:
具体步骤如下:
(1)将有机配合物在玛瑙研钵中研磨10min~20min后,再在球磨机中研磨30min,得到有机配合物的粉末;
(2)将有机配合物粉末分散到含有六价铬离子的水溶液中,然后加入乙醇,超声10min形成分散均匀的悬浊液,在可见光的照射下,进行光催化还原30min时,将水溶液中的六价铬离子还原成三价铬离子。
6.根据权利要求5所述的有机配合物在光催化还原六价铬中的应用,其特征是:所述有机配合物与重铬酸钾的摩尔比为(0.5~1.5):1;所述含有六价铬离子的水溶液与乙醇的体积比为1:1。
7.根据权利要求5所述的有机配合物在光催化还原六价铬中的应用,其特征是:所述含有六价铬离子的水溶液为含有重铬酸根离子的水溶液,有机配合物与重铬酸根离子的摩尔比为1:1的条件下,光催化还原六价铬的光催化还原效率为95%。
8.根据权利要求4所述的有机配合物在光降解有机染料罗丹明B中的应用,其特征是:
具体步骤如下:
(1)将有机配合物在玛瑙研钵中研磨10min~20min后,再在球磨机中研磨30min,得到有机配合物的粉末;
(2)将有机配合物粉末分散到罗丹明B的水溶液中,分散均匀形成悬浊液,在可见光的照射下,进行光催化降解罗丹明B 90min。
9.根据权利要求8所述的有机配合物在光降解有机染料罗丹明B中的应用,其特征是:所述有机配合物与罗丹明B的摩尔比为(20~34):1。
10.根据权利要求8所述的有机配合物在光降解有机染料罗丹明B中的应用,其特征是:所述有机配合物与罗丹明B的摩尔比为27:1,光催化降解罗丹明B光催化降解效率达到99%。
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