CN111848650A - 具有催化光降解染料性质的铜配合物及其制备方法 - Google Patents
具有催化光降解染料性质的铜配合物及其制备方法 Download PDFInfo
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- 150000004699 copper complex Chemical class 0.000 title claims abstract description 36
- 238000001782 photodegradation Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 230000003197 catalytic effect Effects 0.000 title description 7
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 24
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 12
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 12
- 239000003446 ligand Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- JWPDUQLIPMJLOF-UHFFFAOYSA-N 1-(4-imidazol-1-ylphenyl)imidazole Chemical group C1=NC=CN1C1=CC=C(N2C=NC=C2)C=C1 JWPDUQLIPMJLOF-UHFFFAOYSA-N 0.000 claims abstract description 9
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- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 6
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- 239000013110 organic ligand Substances 0.000 claims description 2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- RAYLUPYCGGKXQO-UHFFFAOYSA-N n,n-dimethylacetamide;hydrate Chemical compound O.CN(C)C(C)=O RAYLUPYCGGKXQO-UHFFFAOYSA-N 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 238000004729 solvothermal method Methods 0.000 claims 1
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 abstract description 12
- 239000000975 dye Substances 0.000 abstract description 12
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 12
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
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- -1 copper metal complex Chemical class 0.000 abstract description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 2
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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Abstract
本发明提供一种铜金属配合物，制备方法及其在催化光降解染料的应用。所述配合物的化学式为[Cu(L)(1，4‑BIB)·DMA]n，其中，H2L＝3，3’‑(1H，1’H‑2，2’‑联咪唑‑1，1’‑二亚甲基)苯甲酸，1，4‑BIB＝1，4‑二(1‑咪唑基)苯，DMA＝N，N‑二甲基乙酰胺。所述铜金属配合物为铜离子通过与L2‑和1，4‑BIB配体自组装而成三维结构。实验结果表明：该铜配合物具有良好的催化光降解去除水中亚甲基蓝有机染料性质，在环境污染治理领域具有潜在的应用价值。该配合物合成工艺简单，反应条件温和，使用方便，为环境中有害物质的治理提供了一种新的手段。
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3，3’-(1H，1’H-2，2’-联咪唑 -1，1’-二亚甲基)苯甲酸和1，4-二(1-咪唑基)苯为配体的铜配合物的制备及其在催化光降解水中有机染料方面的应用。
背景技术
我国纺织等一些轻工业排放的印染废水中具有携带浓度高，颜色深，处理难等问题，对于印染废水怎么解决达到排放指标成了一个重要技术难题。目前的大多数光催化剂存在能隙太宽，只能响应不足太阳能辐射5％的紫外光区，光利用率低；价带和导带的电位很难同时满足完全分解污染物的电位；光生电子-空穴易复合，量子效率很低的问题。因此，设计合成环境友好的、合成方法简单的、具有优异光催化性能的环境净化材料是一个重要的挑战。
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)可配位的活性位点促进了配合物高效利用太阳能；(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穴，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。
3，3’-(1H，1’H-2，2’-联咪唑-1，1’-二亚甲基)苯甲酸是配位能力较强的桥连配体：在这个配体的两端具有两个羧酸基，两个苯环之间通过联咪唑连接，有利于配合物的合成；它可以部分或完全去质子化，允许与金属离子有不同的配位模型，易合成具有不同维数的配合物，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，涉及具有三维结构铜配合物的合成，更具体的说是以3，3’-(1H，1’H-2，2’-联咪唑-1，1’-二亚甲基)苯甲酸为配体的铜配合物的合成及其作为光降解催化剂应用。本发明分别采用二价铜离子作为主体，以3，3’-(1H，1’H-2，2’- 联咪唑-1，1’-二亚甲基)苯甲酸为配体合成的铜配合物对亚甲基蓝染料具有良好光降解性质：在110分钟内亚甲基蓝染料基本降解完全，且易于分离并多次循环使用，催化效率基本保持不变。
发明内容
本发明提供一种具有催化光降解染料性质的铜配合物及其制备方法。本发明选用有机配体3，3’-(1H，1’H-2，2’-联咪唑-1，1’-二亚甲基)苯甲酸、1，4-二(1-咪唑基)苯和三水合硝酸铜构筑具有三维结构的配合物。该化合物具有很高的催化活性，可高效降解水中的亚甲基蓝，尤其重要的是该催化剂不溶于水，可分离并多次循环使用。
本发明的铜配合物在常温下具有稳定和高效的催化光降解染料性质，以亚甲基蓝为例， 110分钟内亚甲基蓝基本降解完全，而且易于分离并多次循环使用，催化效率基本保持不变。此外，在本发明中，该铜配合物具有制备方法简单、成本低、效率高、重现性好，收率高等优点。
本发明所涉及的具有催化光降解染料性质的铜配合物的化学式为：[Cu(L)(1， 4-BIB)·DMA]n，其中，H2L＝3，3’-(1H，1’H-2，2’-联咪唑-1，1’-二亚甲基)苯甲酸，1，4-BIB＝1，4-二(1-咪唑基)苯，DMA＝N，N-二甲基乙酰胺。H2L、1，4-BIB的结构式如下：
本发明所涉及的一种具有催化光降解染料性质的三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＝71-057(19)°，β＝78-587(14)°，γ＝75.438(17)°；所述配合物中每个Cu1和Cu2的配位中心都于两个来自不同的1，4-BIB配体中的两个氮原子和两个来自不同L2-配体中的两个氧原子配位，形成了一个三维结构，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：3，3’-(1H，1’H-2，2’-联咪唑-1，1’-二亚甲基)苯甲酸：1，4-二(1-咪唑基) 苯：三水合硝酸铜＝1∶1∶1，加入N，N-二甲基乙酰胺(0.5mL)和去离子水(2.5mL)，超声振荡5分钟混合均匀，混合后放入水热反应釜的聚四氟乙烯内胆中，得到混合液；
(2)将上述混合液在100℃下烘制72小时，取出产物后将固体分离；
(3)用H2O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方面的应用，用于治理印染废水中的亚甲基蓝等染料。
本发明的优点是：该制备方法工艺简单，产率高、重现性好，可以得到单一晶型、高纯度的晶体材料，易工业化生产；该产品光催化能够快速有效的降解水体中的亚甲基蓝并且多次循环使用的催化效率基本保持不变，该方法具有高效、操作简便和去除效果好等优点。
附图说明
图1(a)本发明铜配合物的晶体结构图；图1(b)本发明铜配合物的三维结构图。
图2本发明铜配合物的热重图。
图3本发明铜配合物的固体荧光图。
图4本发明铜配合物的光催化10mg/L亚甲基蓝的吸光度变化图。
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：
12.08mg的三水合硝酸铜(Cu(NO3)2·3H2O)、20.1mg的3，3-(1H，1’H-2，2’-联咪唑-1，1’- 二亚甲基)苯甲酸(H2L)、10.5mg的1，4-二(1-咪唑基)苯(1，4-BIB)溶于0.5mLN，N-二甲基乙酰胺和2.5mL水溶液中，超声振荡5分钟混合均匀，混合后放入水热反应釜的聚四氟乙烯内胆中，得到混合液，将上述混合液在100℃下烘制72小时，取出产物后将固体分离，可得到蓝色块状晶体。
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]/Σ[w(Fo 2)2]1/2
实施例3：配合物的热重测试：
为了探究本发明的铜配合物的热稳定性，对其样品进行了热重测试。测试条件为：保护气为20mL/min流速的氮气，吹扫气为30mL/min流速的空气，以10℃/min的速率从室温升温至900℃，在温度40-180℃范围内，本发明的铜配合物质量损失约为1.09％，这可能是失去游离水分子和有机溶剂而导致的；本发明的铜配合物在300-350℃范围内迅速失重，这可能是因为晶体结构发生了坍塌导致；当温度升高到830℃时，本发明的铜配合物的剩余质量分数约为35.06％，这是由于最后生成了相对稳定的氧化铜。本发明的铜配合物的质量在260℃之前内没有出现剧烈的变化，说明本发明的铜配合物的热稳定性较好(图2)。
实施例4：配合物的固体荧光性质测试：
在室温下测试本发明的铜配合物的固体荧光，使用电子天平准确称量5.0mg的样品，置于固体荧光模具中间，测试得到本发明的铜配合物荧光最大发射峰297nm(激发波长为246 nm)(图3)。
实施例5：配合物的光降解性质测试：
对本发明的铜配合物进行光催化性质研究，在光催化反应器中加入30mg的本发明的铜配合物，50mL浓度为10mg/L的亚甲基蓝。黑暗条件下搅拌30min，达到吸附-脱附平衡，30min后打开光源，10min取样一次，用紫外分光光度计测试其吸光度。测试结果为在110min内，本发明的铜配合物可以使亚甲基蓝降解93.0％(图4)。
Claims (3)
1.一种用作催化光降解和具有固体荧光性质的铜配合物，其特征在于，其化学式为[Cu(L)(1，4-BIB)·DMA]n，其中，H2L＝3，3’-(1H，1’H-2，2’-联咪唑-1，1’-二亚甲基)苯甲酸，1，4-BIB＝1，4-二(1-咪唑基)苯，DMA＝N，N-二甲基乙酰胺；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＝71.057(19)°，β＝78.587(14)°，γ＝75.438(17)°；所述配合物中每个Cu1和Cu2的配位中心都于两个来自不同的1，4-BIB配体中的两个氮原子和两个来自不同L2-配体中的两个氧原子配位，形成了一个三维结构。
2.根据权利要求1所述的铜配合物的制备方法，其特征在于，步骤如下：有机配体3，3’-(1H，1'H-2，2’-联咪唑-1，1'-二亚甲基)苯甲酸、1，4-二(1-咪唑基)苯与三水合硝酸铜在水和N，N-二甲基乙酰胺混合溶液中，经由溶剂热法得到铜配合物。
3.根据权利要求2所述的制备方法，其特征在于，其中：3，3’-(1H，1'H-2，2’-联咪唑-1，1’-二亚甲基)苯甲酸，1，4-二(1-咪唑基)苯和三水合硝酸铜的摩尔比为1∶1∶1，每0.05mmol的三水合硝酸铜对应2.5mL去离子水和0.5mL N，N-二甲基乙酰胺的混合溶液，温度为100℃，反应时间为三天。
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