CN111454283A - 一种铜配合物合成及作为光降解催化剂的应用 - Google Patents
一种铜配合物合成及作为光降解催化剂的应用 Download PDFInfo
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Abstract
本发明提供一种铜金属配合物制备及其在光降解催化剂的应用。所述配合物的化学式为[Cu(L)(AIP)(H2O)·H2O]n；其中，H2AIP＝5‑氨基间苯二甲酸，L＝3，5‑二(1H‑苯并咪唑‑1‑基)吡啶。所述铜金属配合物为铜离子通过AIP2‑、L配体自组装而成的二维结构。该铜配合物具有稳定和高效的催化光降解染料性质：60分钟内亚甲基蓝基本降解完全，且易分离并可多次循环使用。
Description
技术领域
本发明属于有机合成和金属有机化学技术领域，具体涉及到一种3，5-二(1H-苯并咪唑-1-基)吡啶(L)和5-氨基间苯二甲酸(H2AIP)为配体的铜配合物的制备及其作为降解亚甲基蓝(MB)染料的应用。
背景技术
工业的快速发展带来了日趋严峻的生态环境问题，人类的生存环境不断遭到破坏，使得水污染问题日趋严重。目前，我国水体污染的主要来源是工业废水，其中印染废水占工业废水的比重已超过35％。印染废水具有废水量大、色度高、毒性大、水质复杂等特点，属于高浓度难降解有机废水。亚甲基蓝(MB)、甲基橙(MO)等偶氮型染料在水体中的危害极大，不但严重危害河流、海洋的生态平衡，而且还会通过皮肤吸收进入人体内，导致头痛、呕吐，甚至照成多种器官不可逆的伤害乃至致癌。因此，高效处理水体中偶氮型染料污染物是一个重要课题。
传统的水处理工艺因具有易产生二次污染、耗能高、效率低等一系列弊端而不断被革新，由单纯传统处理工艺的改革逐渐转变为水处理的新材料研发。利用环境净化材料催化光降解染料废水的方法可以降解许多难生物降解的复杂大分子，在染料废水处理领域越来越引起人们的关注。
大量关于配合物应用在光降解染料领域的报道，表明具有不同分子结构的配合物在光降解染料领域具有较好的应用。与传统用于光降解的半导体材料相比，配合物在光降解染料方面具有许多优势：(1)晶体结构的精准有利于研究配合物光降解染料的结构与性质之间的关系；(2)可调谐的活性位点促进了配合物光降解染料能高效利用太阳能；(3)配合物的多孔性和较大比表面积能够允许染料分子快速的通过通道，这对提高光催化降解的效率是十分有效的；(4)配合物的金属离子和配体的相互作用可以有效分离光电电子和空缺，从而提高光催化活性。因此，配合物具有高的光催化活性和化学稳定性，且合成方法简单，是一种理想的光反应的催化剂。
3，5-二(1H-苯并咪唑-1-基)吡啶(L)是配位能力较强的桥连配体。该配体是V型苯并咪唑类配体，两端具有两个苯并咪唑，有利于配合物的合成，易合成具有不同维数的金属配合物，而合成不同维数的结构是完成器件化至关重要的一步。
本发明属于有机合成和金属有机化学技术领域，涉及具有二维铜金属荧光配合物的合成，更具体的说是3，5-二(1H-苯并咪唑-1-基)吡啶(L)和5-氨基间苯二甲酸(H2AIP)为配体的铜配合物的合成及其作为光降解催化剂的应用。本发明采用二价铜离子作为主体，以3，5-二(1H-苯并咪唑-1-基)吡啶和5-氨基间苯二甲酸作为配体来构筑配合物，探究不同金属离子对该金属配合物性能的影响，同时具有二维结构的铜配合物对于亚甲基蓝染料具有明显的光降解性质：60分钟内亚甲基蓝染料基本降解完全。
发明内容
本发明旨在提供一种有效催化降解含偶氮类有机染料亚甲基蓝的二维铜配合物及其制备方法。本发明选用3，5-二(1H-苯并咪唑-1-基)吡啶、5-氨基间苯二甲酸配体和六水合硝酸铜构筑铜配合物。该配合物能够高效降解亚甲基蓝有机染料并能保证优异的催化活性及重复性。该配合物合成工艺简单、成本低、效率高、重现性好、检测灵敏、易于分离、收益高，可应用于工业化生产，在环境监测、生命科学及污染物降解领域具有潜在的应用前景。
本发明所涉及的用作亚甲基蓝光降解催化剂的铜配合物的化学式为：[Cu(L)(AIP)(H2O)·H2O]n，其中，H2AIP＝5-氨基间苯二甲酸，L＝3，5-二(1H-苯并咪唑-1-基)吡啶。L，H2AIP的结构式如下：
本发明所涉及的用作偶氮类有机染料亚甲基蓝光降解催化剂的二维铜配合物结构如图1(a)所示，它的基本结构参数为：
本发明的铜配合物的晶体属于三斜晶系，空间群为P-1，晶胞参数为
α＝72.219(2)°，β＝84.864(3)°，γ＝88.713(2)°；所述配合物中铜(1)原子与两个来自于两个3，5-二(1H-苯并咪唑-1-基)吡啶的氮原子、两个来自于两个5-氨基间苯二甲酸的氧原子配位；铜(2)原子与两个来自于两个5-氨基间苯二甲酸的氮原子、两个来自于两个5-氨基间苯二甲酸的氧原子配位，形成无限二维网状结构，如图1(b)所示。
本发明所涉及的铜配合物的制备方法包括下述步骤：
(1)制备方法：3，5-二(1H-苯并咪唑-1-基)吡啶：5-氨基间苯二甲酸：六水合硝酸铜＝1∶1∶1，加入H2O(8mL)，混合后放入水热25mL反应釜的聚四氟乙烯内胆中混合，超声振荡5钟，得到混合液；
(2)将上述混合液在150℃下烘制72小时，取出产物后将固体分离；
(3)用水将上述固体洗涤三次，得到蓝色透明块状晶体。
进一步地，本发明提供上述铜配合物用作催化光降解去除水中亚甲基蓝染料的应用，用于治理自然水体中的亚甲基蓝染料废水。
本发明的优点是：该制备方法工艺简单，产率高、易于分离、重现性好、灵敏度高、催化效率好、收率高，可以得到单一晶型、高纯度的晶体材料，易工业化生产；该产品能够有效催化降解亚甲基蓝，且多次循环使用而催化效率基本保持不变。
附图内容
图1(a)为本发明铜配合物的晶体结构图；图1(b)为本发明铜配合物的二维结构图。
图2为本发明铜配合物对亚甲基蓝的光催化降解图。
具体实施方式
为了更好的理解本发明，下面结合实施实例进一步阐述本发明的内容，但本发明的内容不仅仅局限于下面的实施例。
实施例1：配合物的合成
将11.9mg的Cu(NO3)2·6H2O、10.5mg的H2AIP、16.5mg的L溶于8mL水中，超声振荡5min，转移至25mL水热反应釜的聚四氟乙烯内胆中，在150℃温度条件下反应72小时，所得产物用水洗涤两次(2mL/次)，得到蓝色透明块状晶体。
实施例2：配合物的结构表征
用显微镜选取合适大小的单晶，室温下采用Siemens(Bruker)SMART CCD衍射仪(石墨单色器，Mo-Ka，
)收集衍射数据。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。如图1(a)和图1(b)的展示了[Cu(L)(AIP)(H2O)·H2O]n基本配位情况和堆积方式。其晶体学衍射点数据收集与结构精修的部分参数如下表所示。
表1配合物的晶体学数据
R1＝∑||Fo|-|Fc||/∑|Fo|.ωR2＝∑[w(Fo 2-Fc 2)2]/∑[w(Fo 2)2]1/2
实施例3：配合物的光降解
称量30mg本发明合成的铜配合物加入到50mL的亚甲基蓝水溶液(10mg/L)，然后加入50uL的H2O2，黑暗下搅拌30min使配合物表面达到吸附-脱附平衡，然后边搅拌的同时边用可见灯照射，每10min取1mL的亚甲基蓝水溶液，立即测试吸光度的变化。光降解的结果显示，该配合物60min内对于亚甲基蓝的降解率分别高达91.5％，且可以多次循环使用(如图2)。
Claims (3)
1.一种有效降解亚甲基蓝染料的铜配合物，其特征在于，其化学式为[Cu(L)(AIP)(H2O)·H2O]n，其中，H2AIP＝5-氨基间苯二甲酸，L＝3，5-二(1H-苯并咪唑-1-基)吡啶；所述的铜配合物的晶体属于三斜晶系，空间群为P-1，晶胞参数为
α＝72.219(2)°，β＝84.864(3)°，γ＝88.713(2)°；铜(1)原子与两个来自于两个3，5-二(1H-苯并咪唑-1-基)吡啶的氮原子、两个来自于两个5-氨基间苯二甲酸的氧原子配位；铜(2)原子与两个来自于两个5-氨基间苯二甲酸的氮原子、两个来自于两个5-氨基间苯二甲酸的氧原子配位，形成无限二维网状结构。
2.根据权利要求1所述的铜金属的制备方法，其特征在于，步骤如下：在密封条件下，有机配体3，5-二(1H-苯并咪唑-1-基)吡啶、5-氨基间苯二甲酸与六水合硝酸铜在水溶液中，经由水热反应得到晶体结构的铜配合物。
3.根据权利要求2所述的制备方法，其特征在于，其中：六水合硝酸铜∶3，5-二(1H-苯并咪唑-1-基)吡啶∶5-氨基间苯二甲酸为1∶1∶1，每0.05mmol的六水合硝酸铜对应8mL的去离子水，热反应的条件为150℃，反应时间为三天。
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