CN106928153B - 一种对甲醛具有电催化活性的钴配合物及其制备方法 - Google Patents

一种对甲醛具有电催化活性的钴配合物及其制备方法 Download PDF

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CN106928153B
CN106928153B CN201710181530.4A CN201710181530A CN106928153B CN 106928153 B CN106928153 B CN 106928153B CN 201710181530 A CN201710181530 A CN 201710181530A CN 106928153 B CN106928153 B CN 106928153B
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徐欢
李星
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Abstract

本发明公开了一种对甲醛具有电催化活性的钴配合物及其制备方法，该钴配合物是一种具有准确空间结构的电催化材料，其化学式为CoC8H12N6O12，结构单元为[Co(C4H2N3O4)2(H2O)4]，晶系为三斜晶系，空间群为P‑1，晶胞参数为 α＝97.141°，β＝108.592°，γ＝115.555°，钴离子为六配位的八面体几何构型。所述对甲醛具有电催化活性的钴配合物的制备方法为：将5‑硝基乳清酸钾单水合物与具有电催化活性的钴离子进行化学反应，制得一种钴配合物。该制备方法操作简单，成本低廉，适合规模化生产。本发明所得的钴配合物对甲醛具有良好的电催化活性，作为电催化材料具有潜在的应用前景。

Description

一种对甲醛具有电催化活性的钴配合物及其制备方法
技术领域
本发明属于材料化学领域，具体涉及一种对甲醛具有电催化活性的钴配合物及其制备方法。
背景技术
电催化是能够加速电极和电解质界面上的电荷转移反应的一种催化作用。电催化作用包括电极反应和催化作用两个方面，因此电催化剂必需同时具有这两种功能：一能导电和比较自由地传递电子；二能对底物进行有效的催化活化作用。目前电催化主要应用于污水的电催化处理；含铬废水的电催化降解；烟道气及原料煤的电解脱硫；电催化同时脱除NOx和SO2；二氧化碳的电解还原等方面。选用合适的电极材料，可以加速电极反应的速率。实验研究结果表明一些过渡金属化合物或配合物对甲醛或过氧化氢具有良好的电催化活性，例如，冉繁敏等公开了一种对甲醛具有电化学响应的化合物及其制备方法，授权号CN103396458B；赵亚云等公开了一种对过氧化氢具有电催化活性的钴配合物，授权号：CN103467367B；李星等公开了一种对过氧化氢具有电催化活性的铜配合物及其制备方法，授权号：CN 103467498B。基于一些过渡金属化合物具有良好的电催化性能，可作为电极修饰材料或制作成传感器用于检测一些有毒有害气体。
甲醛作为一种重要的有机原料在物料中大量分布，是一种破坏细胞蛋白质的原生质毒物，对皮肤、呼吸道及内脏都会造成损害，麻醉中枢神经，引起肺水肿、肾衰竭等。目前甲醛检测方法主要有分光光度法、电化学检测法、液相色谱法、传感器法等。例如使用拉曼光谱检测甲醛(张倩暄，关旭春，崔厚欣，一种甲醛检测的装置和方法，申请公布号CN102749318)，该方法操作、分析过于复杂。还有使用热传感性质检测甲醛的方法(刘东方，姜风，马晓聪，甲醛气体传感器，申请公布号CN 101825604A)，该方法使用时，加热电极组必须将气体感测层加热到很高温度(300℃)才能正常检测，耗能大，安全性差。
本发明公开一种对甲醛具有电催化活性的化合物，可作为电极修饰材料，制备性能稳定，可用于制备快速检测甲醛的电化学传感器等。本发明所制备的化合物为钴配合物，其对甲醛具有良好的电催化活性，在电催化传感检测中具有潜在的应用前景。
发明内容
本发明所要解决的技术问题是针对现有技术，提供一种反应条件温和，制备过程简单，成本低廉，对甲醛具有电催化活性的钴配合物及其制备方法。
本发明为解决上述技术问题所采取的技术方案为：一种对甲醛具有电催化活性的钴配位化合物(简称配合物)，该配合物具有一定空间结构，其结构单元为[Co(C4H2N3O4)2(H2O)4]，其化学式为CoC8H12N6O12，晶系为三斜晶系，空间群为P-1，晶胞参数为α＝97.141°，β＝108.592°，γ＝115.555°，钴离子为六配位的八面体几何构型。
一种上述对甲醛具有电催化活性的钴配合物的制备方法，包括以下步骤：
(1)称取一定量的水合二氯化钴和5-硝基乳清酸钾单水合物，置于烧杯中，按照Co(II)离子与5-硝基乳清酸钾的物质量的比为1:1～2的比例加入，加水10～15mL，并加热、搅拌使其溶解，得反应混合物水溶液；
(2)将上述反应混合物水溶液转移到25mL具有聚四氟乙烯内衬的不锈钢反应釜中，密封反应釜后置于鼓风干燥箱中，100～120℃加热反应24～72小时，反应结束冷却到室温，打开反应釜得棕红色块状晶体；
(3)将棕红色块状晶体取出，自然风干，即得所述的钴配合物。
优选的，所述参加反应的物质均为化学纯，所述水合二氯化钴为六水合二氯化钴。
与现有技术相比，本发明的优点在于：
将具有刚性平面共轭的硝基乳清酸与具有电化学催化活性的钴离子进行水热化学反应，在反应中5-硝基乳清酸的羧基脱去，并使用其氮与钴离子配位，形成新的钴配位化合物，其结构单元具有刚性共轭特性，有利于电子跃迁与能量传递，从而使化合物具有良好的光电活性，从而呈现对甲醛具有良好的电催化活性。所制备的钴配合物具有准确的空间结构和准确的分子式，作为电催化活性材料具有潜在的应用前景。
附图说明
图1为本发明的钴配合物结构单元图(为图示清晰，碳原子和对称操作出来的原子没有标记)；
图2为本发明的钴配合物对甲醛的电化学催化响应图。
具体实施方式
以下结合附图实施例对本发明作进一步详细描述。
实施例1：
称取CoCl2·6H2O(0.3mmol，0.0714g)，5-硝基乳清钾单水合物(0.3mmol，0.0772g)置于烧杯中，加水10mL，加热、搅拌使其溶解，得反应混合物水溶液；将反应混合物水溶液转移到25mL具有聚四氟乙烯内衬的不锈钢反应釜中，密封反应釜后置于鼓风干燥箱中，100℃加热反应72小时，反应结束冷却到室温，打开反应釜得棕红色块状晶体；将棕红色块状晶体取出，自然风干，即获得钴配合物。
实施例2：
称取CoCl2·6H2O(0.3mmol，0.0714g)，5-硝基乳清钾单水合物(0.6mmol，0.154g)置于烧杯中，加水15mL，加热、搅拌使其溶解，得反应混合物水溶液；将反应混合物水溶液转移到25mL具有聚四氟乙烯内衬的不锈钢反应釜中，密封反应釜后置于鼓风干燥箱中，120℃加热反应24小时，反应结束冷却到室温，打开反应釜得棕红色块状晶体；将棕红色块状晶体取出，自然风干，即获得钴配合物。
实施例3：
称取CoCl2·6H2O(0.2mmol，0.0475g)，5-硝基乳清钾单水合物(0.3mmol，0.0772g)置于烧杯中，加水13mL，加热、搅拌使其溶解，得反应混合物水溶液；将反应混合物水溶液转移到25mL具有聚四氟乙烯内衬的不锈钢反应釜中，密封反应釜后置于鼓风干燥箱中，110℃加热反应48小时，反应结束冷却到室温，打开反应釜得棕红色块状晶体；将棕红色块状晶体取出，自然风干，即获得钴配合物。
将实施例1-3制得的钴配合物进行结构测试，结果表明在反应过程中5-硝基乳清酸的羧基脱去，并使用其氮与钴离子配位，形成新的钴配位化合物。本发明所制得的钴配合物其化学式为CoC8H12N6O12，其结构单元为[Co(C4H2N3O4)2(H2O)4]，晶系为三斜晶系，空间群为P-1，晶胞参数为 α＝97.141°，β＝108.592°，γ＝115.555°，钴离子为六配位的八面体几何构型。所制备的钴配合物的结构单元如图1所示(为了图示清晰，碳原子和对称操作出来的原子没有标记)。
将所制得的钴配合物对甲醛进行电催化性能测试，结果显示该配合物对甲醛具有良好的电催化性能(如图2)。

Claims (2)

1.一种对甲醛具有电催化活性的钴配合物，其特征在于，该配合物具有一定空间结构，其化学式为CoC8H12N6O12，结构单元为[Co(C4H2N3O4)2(H2O)4]，晶系为三斜晶系，空间群为P-1，晶胞参数为α＝97.141°，β＝108.592°，γ＝115.555°，C4H2N3O4为5-硝基乳清酸的羧基脱去后形成配体的分子式，钴离子为六配位的八面体几何构型，其中两个氮配位原子来自于配体C4H2N3O4，四个氧配位原子来自配位水分子；所述配体结构如下：
2.一种如权利要求1所述的对甲醛具有电催化活性的钴配合物的制备方法，其特征在于，包括以下步骤：
(1)称取一定量的水合二氯化钴和5-硝基乳清酸钾单水合物，置于烧杯中，按照Co(II)离子与5-硝基乳清酸钾的物质量的比为1:1～2的比例加入，加水10～15mL，并加热、搅拌使其溶解，得反应混合物水溶液；
(2)将上述反应混合物水溶液转移到25mL具有聚四氟乙烯内衬的不锈钢反应釜中，密封反应釜后置于鼓风干燥箱中，100～120℃加热反应24～72小时，反应结束冷却到室温，打开反应釜得棕红色块状晶体；
(3)将棕红色块状晶体取出，自然风干，即得所述的钴配合物；
所述参加反应的物质均为化学纯，所述水合二氯化钴为六水合二氯化钴。
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CN103435659A (zh) * 2013-08-12 2013-12-11 宁波大学 一种具有电化学催化活性的钴配合物
CN103467367A (zh) * 2013-09-13 2013-12-25 宁波大学 一种对过氧化氢具有电催化活性的钴配合物
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CN104926888A (zh) * 2015-05-29 2015-09-23 南京信息工程大学 一种钴配合物及其制备方法与应用
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US20140371446A1 (en) * 2010-07-16 2014-12-18 Abbvie Inc. Phosphine ligands for catalytic reactions
CN103396458A (zh) * 2013-08-12 2013-11-20 宁波大学 一种对甲醛具有电化学响应的化合物及其制备方法
CN103435659A (zh) * 2013-08-12 2013-12-11 宁波大学 一种具有电化学催化活性的钴配合物
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CN103709204A (zh) * 2013-12-09 2014-04-09 南京信息工程大学 一种钴配合物、制备方法及其用途
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