CN113583029A - 基于1,3,5-三(4-羰基苯基氧基)苯合成的二维超分子化合物及其方法、应用 - Google Patents
基于1,3,5-三(4-羰基苯基氧基)苯合成的二维超分子化合物及其方法、应用 Download PDFInfo
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Abstract
本发明涉及含染料废水的处理，特别涉及一种基于1,3,5‑三(4‑羰基苯基氧基)苯合成的二维超分子化合物及其方法、应用；所述的方法包括将1,3,5‑三(4‑羰基苯基氧基)苯、苯酚和Cu(NO3)2·3H2O加入到乙腈的水溶液中，搅拌混合均匀后，转入带有聚四氟乙烯内衬的反应釜中，加热至110‑130℃并保温60‑84小时，接着以3‑8℃/h的速度降温至20‑30℃，得到所述二维超分子化合物；与现有技术相比，本发明提供了一种较为简单的合成二维超分子化合物的方法，以及通过该方法合成得到的二维超分子化合物对水中染料具有较好的降解效率；此外，经测试，本发明合成得到的二维超分子化合物是一种稳定的、可回收的光催化剂。
Description
技术领域
本发明涉及含染料废水的处理，特别涉及一种基于1,3,5-三(4-羰基苯基氧基)苯合成的二维超分子化合物及其方法、以及基于该二维超分子化合物对水中染料的降解应用。
背景技术
含-N＝N-基团的偶氮染料是废水中的主要污染物，多数染料由于稳定性高，难以被微生物降解，并可能在生命***中诱发致癌效果。目前，吸附、膜分离和电化学降解等处理技术已被应用于染料废水的去除和处理，以消除和减少染料对生物***的持久影响。光催化被认为是解决环境问题最有希望的方法。自1972年TiO2的光催化特性被发现以来，为了探索光催化剂的应用，人们开发了光催化水分解和光催化降解有机污染物的技术。含有罗丹明B(Rh B)、亚甲基蓝(MB)、亚甲基橙(MO)等染料是高级氧化过程中常用的目标污染物。
众所周知，配位聚合物以其美观的网络结构和重要的潜在应用领域而得到广泛的应用。在众多的应用中，基于配位聚合物的光催化技术受到了广泛的关注和提升改进，主要是由于处理污染问题的基本需要。此外，越来越多的过渡金属配合物和配位聚合物作为光催化剂得到了广泛的研究和讨论，其中包括其多样化的网状结构和控制合成方法。
发明内容
本发明的目的在于克服现有技术中的不足，提供一种基于1,3,5-三(4-羰基苯基氧基)苯合成二维超分子化合物的方法，基于该方法合成得到的二维超分子化合物对水中染料具有较好的降解效率，是一种稳定的、可回收的光催化剂。
为了实现上述目的，本发明采用以下技术方案予以实现：
一种基于1,3,5-三(4-羰基苯基氧基)苯合成二维超分子化合物的方法，所述的方法包括将1,3,5-三(4-羰基苯基氧基)苯、苯酚和Cu(NO3)2·3H2O加入到乙腈的水溶液中，搅拌混合均匀后，转入带有聚四氟乙烯内衬的反应釜中，加热至110-130℃并保温60-84小时，接着以3-8℃/h的速度降温至20-30℃，得到所述二维超分子化合物。
在进一步的技术方案中，所述1,3,5-三(4-羰基苯基氧基)苯、苯酚和Cu(NO3)2·3H2O的质量比为1：(0.5-1)：(1.2-1.8)。
在进一步的技术方案中，所述乙腈的水溶液中，乙腈与水的体积比为1：(0.8-1.5)。
本发明另一方面提供了一种采用上述方法合成得到的二维超分子化合物。
本发明另一方面还提供了一种上述二维超分子化合物对水中染料的降解应用。
与现有技术相比，本发明提供了一种较为简单的合成二维超分子化合物的方法，以及通过该方法合成得到的二维超分子化合物对水中染料具有较好的降解效率；此外，经测试，本发明合成得到的二维超分子化合物是一种稳定的、可回收的光催化剂。
本发明的其他特征和优点将在随后的具体实施方式中予以详细说明。
附图说明
图1示出为本发明实施例1中合成得到的化合物1的结构；图1(a)化合物1中Cu(II)中心的配位几何；(b)化合物1中三维超分子网络透视图1；(c)相邻亚基的非配位羧基与配位水分子之间的氢键相互作用；(d)不同链上的苯酚连接子之间的π-π相互作用；
图2示出为本发明实施例1中合成得到的化合物1的热重分析曲线图；
图3示出为本发明实施例1中合成得到的化合物1的紫外-可见漫反射光谱(DRS)；
图4示出为本发明实施例1中合成得到的化合物1对不同染料的光催化性能；图4(a)-(c)MO,Rh B和MB溶液的各自吸附容量；(d)控制组的看法、三种染料的吸附能力和催化效能；(e)三种染料的降解效率比较；(f)ln(C0/C)和t的拟合数据；
图5示出为本发明实施例1中合成得到的化合物1在不同条件下的PXRD图；
图6示出为本发明实施例1中合成得到的化合物1的N2吸附-脱附等温线；
图7示出为本发明实施例1中合成得到的化合物1的催化反应机理的研究；图7(a)、(b)清除剂存在时的浓度变化特征及催化变化；(c)ln(C0/c)和time(t)的拟合数据；(d)4次循环运行后对MB降解的影响；
图8示出为本发明方案1中水中染料的分子骨架图。
图9示出为本发明方案2中采用LC-MS分析MB可能的转换路径。
具体实施方式
为了使本发明实现的技术手段、创作特征、达成目的与功效易于明白了解，下面结合具体实施例，进一步阐明本发明。
本发明中，通过选择一个三羧酸配体和含氮配体与Cu(NO3)2在温和条件下合成了一个新的二维化合物，即：[Cu2(HL)2(H2O)2(phen)2·H2O]n(H3L＝1,3,5-三(4-羰基苯基氧基)苯，phen＝1,10-邻二氮杂菲)(1)。
本发明的以下实施例中，所有其他试剂均购买并并未经进一步纯化地进行了使用。在Perkin-Elmer 240C分析仪上进行了C,H和N的元素分析。
FT-IR光谱是在VERTEX 70FT-IR分光光度计上在4000-600cm-1区域获得的。
在D/MAX-3C衍射仪上，在Cu-Kα辐射
和室温下，进行了粉末x射线衍射(PXRD)实验。
发光测量在室温下进行，光谱采集在Perkin-Elmer LS50B荧光光谱仪上进行。
紫外-可见光谱是在分光光度计上测量的。
固体样品的紫外-可见漫反射光谱是以BaSO4为反射标准在Cary 500分光光度计上采集的。
实施例1
本实施例提供了一种基于1,3,5-三(4-羰基苯基氧基)苯合成二维超分子化合物的方法，具体的，将1,3,5-三(4-羰基苯基氧基)苯(0.05mmol，0.024g)、苯酚(0.10mmol，0.018g)和Cu(NO3)2·3H2O(0.15mmol，0.036g)加入到10mL乙腈的水溶液(乙腈和水的体积比为1：1)；搅拌混合30分钟，然后放入到25mL规格带有聚四氟乙烯内衬的反应釜中，加热到120℃并保温反应72小时，接着以5℃/h的速度降温至25℃，得到产物。
为方便描述，将上述产物定义为化合物1。
如下表1所示为化合物1的晶体学数据：IR(cm-1):3466(v)；3060(m)；2583(m)；2132(m)；1712(v)；1589(v)；1496(vs)；1384(v)；1240(vs)；1137(m)；1004(m)；840(v)；727(m)。
表1化合物1的晶体数据
*R＝∑(Fo–Fc)/∑(Fo),**wR2＝{∑[w(Fo 2–Fc 2)2]/∑(Fo 2)2}1/2.
化合物1的结构描述：
在化合物1中，每个不对称亚基中都有一个Cu(II)正离子，一个HL2-负离子，一个配位水分子，一个苯酚分子和一个半自由水分子(如图1a所示)；
化合物1中的每个Cu(II)中心配位到两个相邻的HL2-连接体中的两个O原子、两个N原子来自phen，另一个氧原子来自一个配位水分子，形成一个{CuN2O3}的四面体几何。基面由两个羧基氧原子和两个苯酚分子的N原子固定，顶点位置被一个配位水分子(O10)占据。
在化合物1中，部分脱质子的HL2-阴离子以μ1-η1:η0:η0:η0的配位方式与两个金属离子结合在羧基侧，而其中间的COO-基未配位。两侧苯环与中间苯环之间的二面角分别为21.5°和18.1°。在这种连接中，HL2-阴离子和苯酚的单齿配位模式生成[Cu2(HL)2(H2O)2(phen)2]环(如图1a)；此外，化合物1的相邻亚单元通过O-H-O相互作用进一步连接，生成沿bc面的平行新层(图1c)。这些层被邻近的苯酚配体的相互作用扩展为3D超分子结构(图1b和图1d所示)。
化合物1的热重分析：
通过热重分析(TGA)研究了化合物1的热稳定性，如图2所示，对于化合物1来说，在25-197℃温度范围内第一步失重是由于释放了一个晶格水分子和两个配位水分子；超过240℃的失重可归因于晶格结构的崩溃和有机配体的分解。
光催化反应的测量：
把化合物1(40mg)加入100mL亚甲基蓝(MB)/亚甲基橙(MO)/罗丹明B(Rh B)溶液(10mg/L)中。在黑暗中搅拌悬液约30分钟，然后在带有紫外截止滤光片的300W Xe灯的可见光照射下连续搅拌(可见光λ>400nm)。液体表面的光强为由PL-MW2000光电辐射计测定3850W/m2。在一定的时间间隔内，定期取反应混合物的等分，并在MB、MO和RhB的吸收波长处用紫外-可见分光光度计分析。
化合物1的光催化性能：
收集化合物1的漫反射UV-vis数据，得到带隙(Eg)。由于x轴和直线之间的交叉点由吸收边的直线位置推断出来，得到了最终的计算结果，如图3所示，Eg评估约为2.78eV。
通过在紫外线照射下测量MB、MO和Rh B的分解。首先，在光催化剂存在下提取MB、MO和Rh B的产物成分，列出了其降解效率(如图4中a、b、c和e所示)；
在本发明的附图4中，图4a、b、c分别示出了化合物1作用于MO、Rh B和MB时，在不同波长条件下、每间隔10分钟光照时间的吸光度，吸光度越低，说明染料被降解的越多。图4a、b、c中，多个曲线分别对应的是不同处理时间的吸光度曲线，其中，对于MO来说，随着处理时间的延长，吸光度曲线并没有明显的下移，对应图4d中10.17％的降解率；对于MB来说，随着处理时间的延长，吸光度曲线更加贴近x轴，即吸光度出现明显降低，对应图4d中46.87％的降解率；对于Rh B来说，随着处理时间的延长，吸光度曲线的下降程度弱于MB，对应图4d中22.86％的降解率。
即从结果来看，化合物1显示了对MO、Rh B和MB的光催化性能，在100分钟内降解率分别为10.17％、22.86％和46.87％(如图4d)。
值得注意的是，化合物1对MB表现出选择性的光催化能力。并且，发明人发现，在不同催化剂用量、染料浓度、金属效应、光源和辐照时间对催化氧化反应有显著变化。
所有数据均采用准一级动力学方程拟合，得到并探索其催化反应速率情况(图4d)。动力学速率常数(k)是用通常的线性图计算的。ln(C0/C)与反应时间(t)呈较好的线性关系。MO、Rh B和MB在光催化剂存在下k值分别为0.00107min-1，0.00247min-1和0.0610min-1(图4f和表2)。此外，发明人还探索了化合物1的循环性能特征。即使经过四个循环实验，发现催化剂的催化性能并没有明显下降(图7d)。化合物1的PXRD在4个循环中没有明显变化(图5)。目前的结果表明，化合物1可以作为一种稳定的、可回收的光催化剂。
表2：拟一阶动力学方程的不同拟合参数
此外，发明人研究了化合物1的N2吸附-脱附等温线(图6)，得到化合物1的Brunauer-Emmett-Teller表面积为7.44m2 g-1。
通过分析其结构特点(0.22nm for 1)，如图8所示，MO染料的大小是1.54nm×0.48nm×0.28nm，MB染料的大小是1.38nm×0.64nm×0.21nm，和Rh B染料的大小是1.56nm×1.35nm×0.42nm(方案1)，它们都比晶体的孔隙结果大，因此不能进入化合物1的孔隙。基于上述材料通道的结构特征与染料分子大小之间的相关性，我们假设催化反应主要发生在催化剂的表面。
为了探索和监测催化反应的机理，发明人做了一系列的捕获和捕集实验。在各降解过程中分别选取苯醌(BQ)、叔丁醇(TBA)和草酸铵(AO)三种清除剂(图7a-7b)。数据表明，清除剂可以有效地诱导和减少催化反应的过程。MB的性能下降明显，从93.64％下降68.38％(图7c)。在催化过程中，OH-自由基捕获H+，并在化合物1中变为·OH。结果表明：·OH在MB光分解体系中是一个主要的活性氧化自由基。
为了进一步探索MB降解过程中可能产生的分解中间体，采用了LC-MS方法对其进行研究。基于目前的谱图分析，在方案2中推测了可能的降解机制。在第一种途径中，MB分子从胺化反应开始，在m/z 269和255处形成了中间产物。公式为227的中间体是通过中间体241的去甲基化和/或氧化生成的。基于其对·OH具有较强的氧化能力，产生了N/S杂环，并检测到许多后续分解产物。方案2(如图9所示)列出并讨论了最相似的降解途径。
以上显示和描述了本发明的基本原理、主要特征和本发明的特点。本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明精神和范围的前提下，本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明的范围内。本发明要求保护的范围由所附的权利要求书及其等效物界定。
Claims (5)
1.一种基于1,3,5-三(4-羰基苯基氧基)苯合成二维超分子化合物的方法，其特征在于，所述的方法包括将1,3,5-三(4-羰基苯基氧基)苯、苯酚和Cu(NO3)2·3H2O加入到乙腈的水溶液中，搅拌混合均匀后，转入带有聚四氟乙烯内衬的反应釜中，加热至110-130℃并保温60-84小时，接着以3-8℃/h的速度降温至20-30℃，得到所述二维超分子化合物。
2.根据权利要求1所述的方法，其特征在于，所述1,3,5-三(4-羰基苯基氧基)苯、苯酚和Cu(NO3)2·3H2O的质量比为1：(0.5-1)：(1.2-1.8)。
3.根据权利要求1所述的方法，其特征在于，所述乙腈的水溶液中，乙腈与水的体积比为1：(0.8-1.5)。
4.一种根据权利要求1-3任意一项所述的方法合成得到的二维超分子化合物。
5.一种根据权利要求4所述的二维超分子化合物对水中染料的降解应用。
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