CN105859799B - 一种用于检测六价铬的AgNPs@含氮二维π‑共轭金属有机框架复合材料 - Google Patents
一种用于检测六价铬的AgNPs@含氮二维π‑共轭金属有机框架复合材料 Download PDFInfo
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Abstract
本发明公开了一种用于检测六价铬的AgNPs@含氮二维π‑共轭金属有机框架复合材料，在六氨基三亚苯与钴盐的混合溶液中加入碱性溶液，反应后，将得到的沉淀物进行清洗、干燥，即得含氮二维π‑共轭金属有机框架材料Co3HITP2，该有机框架材料与纳米银颗粒反应即可制得复合材料。本发明的电化学传感器进行六价铬的检测，具有方法简单，条件温和，易操控、成本低廉，并且可以现场即时快速检测的优点。
Description
技术领域
本发明涉及电化学检测技术领域，具体涉及一种用于检测六价铬的AgNPs@含氮二维π-共轭金属有机框架复合材料。
背景技术
金属有机框架材料(MOFs)是一类由金属离子(簇)与有机桥联配体连接而成的具有纳米孔穴的超分子晶体材料。它们具有极大的比表面积、良好热稳定性和化学稳定性等优点，尤其是可调控的孔径和拓扑结构，可有效识别不同半径或体积的目标分子，使其在化学传感方面有良好的应用前景。
含氮平面二维π-共轭MOFs材料是通过选择合适的配体和金属来设计制备的一类高导电率MOFs材料，由N供体原子邻位双取代的苯或三亚苯衍生配体与多种后过渡金属节点组成，特殊的配体形成了一个平面正方形配位环境，配体经氧化后与金属节点达到电荷平衡。理论计算表明这类材料有着广泛分布的价带和导带，具有优异的带传输能力和较高的电荷迁移率，是目前已知的电传导性最好的MOFs材料。此类MOFs材料有着类石墨的片层堆垛结构，堆垛方式有平行和错列两类，具有一维的六边形孔结构，以苯衍生物为配体的MOFs孔尺寸大约为1.4nm，以三亚苯衍生物为配体的MOFs孔尺寸大约为2nm。
铬在自然界分布较广，并以多种形式存在，常见的是三价铬与六价铬。铬(Ⅵ)是一种重要的环境污染物，其毒性是铬(III)的毒性的将近100倍，对生存环境和人体健康都有着明显的危害，1990年铬(Ⅵ)被国际癌症研究机构划分在第一组致癌物质当中。在生产和应用铬及其化合物的生产工业中都会产生一些含有铬的废水废物，这些废水如若处理不好就会造成严重的环境污染，因此准确快捷地测定铬(Ⅵ)对生产和环境保护都有着重要意义。原子吸收光谱法、原子发射光谱、紫外可见分光光度法、质谱法、色谱法对六价铬检测操作复杂，成本高，并且样品需要前处理，不能做到现场即时检测。
发明内容
针对上述现有技术，本发明的目的是提供一种含氮二维π-共轭金属有机框架及其制备方法，该金属有机框架具有极大的比表面积，良好的热稳定性和化学稳定性，与纳米银配合制备的复合材料可以对六价铬的检测显示出优异的选择性。
本发明的另一个目的是提供一种用于检测六价铬的复合材料及其制备方法，该复合材料是由上述的含氮二维π-共轭金属有机框架和纳米银制备而成，利用该复合材料对六价铬进行检测，具有选择性好和灵敏度高的优点。
本发明还可以提供一种用于检测六价铬的电化学传感器及其制备方法，该电化学传感器是将上述用于检测六价铬的复合材料涂在电极表面，晾干制得。
本发明还有一个目的是提供上述用于检测六价铬的电化学传感器的应用。
为实现上述目的，本发明采用如下技术方案：
一种含氮二维π-共轭金属有机框架的制备方法，包括如下步骤：
在六氨基三亚苯(HATP·6HCl)与钴盐的混合溶液中加入碱性溶液，反应后，将得到的沉淀物进行清洗、干燥，即得含氮二维π-共轭金属有机框架材料Co3HITP2。
优选的，所述钴盐为硫酸钴、氯化钴或硝酸钴。
钴盐还可以为其他钴盐，只要能实现反应的目的即可，优选为完全电离的强酸盐。
优选的，所述六氨基三亚苯、钴盐和氨水的摩尔比为1.5-2.5:2-5:100-150。
优选的，上述制备方法的反应温度为20-30℃。
优选的，所述沉淀物的清洗方法，包括如下步骤：
将沉淀物在水中搅拌清洗，在水中搅拌清洗的时间不少于48h，并定期更换水，然后在丙酮中搅拌清洗，在丙酮中清洗的时间不少于12h。
上述制备方法制备得到含氮二维π-共轭金属有机框架。
一种用于检测六价铬的复合材料，由所述含氮二维π-共轭金属有机框架与纳米银制备而成。
上述复合材料的制备方法，包括如下步骤：
将纳米银颗粒溶液与Co3HITP2溶液混合，搅拌反应设定时间后，即得。
优选的，所述纳米银颗粒的制备方法，包括如下步骤：
1)冰水浴中，将硝酸银溶液缓慢加入到硼氢化钠溶液中，得到混合溶液；
2)将混合溶液移入热水浴中，加热设定时间后，在混合溶液中加入硼氢化钠溶液，剧烈搅拌；
3)将步骤2)中得到的溶液移出热水浴，继续剧烈搅拌至室温，即得。
优选的，步骤2)中，热水浴的温度为80-100℃。
优选的，搅拌反应的时间至少为1h。
优选的，所述含氮二维π-共轭金属有机框架与纳米银的质量比4-6:1。
上述复合材料的悬浮液，将上述复合材料分散于二甲基甲酰胺中制得。
一种用于检测六价铬的电化学传感器，将所述复合材料的悬浮液涂到电极表面，干燥后制得。
上述电化学传感器在检测废水中重金属污染中的应用，尤其在检测六价铬中的应用。
一种检测六价铬的三电极体系，工作电极为上述电化学传感器，参比电极为饱和甘汞电极，对电极为铂丝电极。
利用上述三电极体系检测六价铬的方法，包括如下步骤：
1)设定电位下，在酸性空白溶液中连续注入设定浓度、设定体积的六价铬溶液，绘制标准曲线；
2)取样，提取，测定，根据标准曲线测定样品中六价铬的浓度。
优选的，步骤1)中，所述六价铬溶液为K2Cr2O7。
优选的，绘制标准曲线的空白溶液和样品测定时的空白溶液均为0.1M HNO3溶液。
本发明的有益效果为：
(1)与原子吸收光谱法、原子发射光谱、紫外可见分光光度法、质谱法、色谱法相比，使用本发明的电化学传感器进行六价铬的检测，具有方法简单，条件温和，易操控、成本低廉，并且可以现场即时快速检测的优点。
(2)本发明在含氮二维π-共轭金属有机框架中嵌入AgNPs(纳米银颗粒)，形成AgNPs@含氮二维π-共轭金属有机框架复合材料，使得该复合材料具有非常大的比表面积，使得该传感器具有好的灵敏度和检测限。
(3)本发明利用AgNPs@含氮二维π-共轭金属有机框架复合材料具有良好的电子传导能力使得该传感器具有好的灵敏度和检测限。
附图说明
图1是本发明中电化学传感器构建循环伏安表征图；
图2是本发明的电化学传感器检测铬(Ⅵ)的线性关系图(1-19μM)。
图3是本发明的电化学传感器检测铬(Ⅵ)的线性关系图(0.1-0.9μM)。
具体实施方式
下面结合实施例对本发明作进一步的说明。
实验中所使用的仪器及试剂为：(1)仪器：CHI660电化学工作站(上海辰华仪器有限公司)；采用饱和甘汞电极(SCE)为参比电极，铂丝电极为对电极；(2)试剂均为分析纯，实验用水为二次蒸馏水。
实施例1
银纳米颗粒的制备。配置0.002M硝酸银溶液，0.003M硼氢化钠溶液。将0.003M硼氢化钠加入三口圆底烧瓶中，冰水浴中并剧烈搅拌；0.002M硝酸银缓慢加入到两倍体积的0.003M硼氢化钠中，硝酸银完全加入后再剧烈搅拌5分钟。将溶液移入100摄氏度热水浴中，加热1～2分钟，立即快速加入预留的20ml硼氢化钠溶液，剧烈搅拌2分钟；将烧瓶移出热水浴，继续剧烈搅拌冷却至室温，转入用王水浸泡过的棕色瓶中，4℃储存。
含氮二维π-共轭金属有机框架的制备。用王水浸泡两个50mL烧杯，过夜后二次水洗净。将烧杯中加入5mL去离子水，室温下加入15mg六氨基三亚苯(HATP·6HCl)搅拌使之完全溶解，形成有机配体溶液；在另一个烧杯中加入3mL去离子水中，将10mg的七水硫酸钴(CoSO4·7H2O)完全溶解，形成金属离子前驱体溶液；将有机配体溶液与金属离子前驱体溶液混合后加入浓度14M的氨水溶液200μL；混合溶液在离心机中离心去除上清液后，将沉淀物加入25mL去离子水中搅拌3天，并每天换两次去离子水；然后将沉淀物加入25mL丙酮中搅拌1天，真空干燥得到含氮二维π-共轭金属有机框架材料Co3HITP2。
AgNPs@含氮二维π-共轭金属有机框架复合材料的制备。将3mL银纳米颗粒溶液与2mL浓度为1mg/mL的Co3HITP2溶液混合，搅拌2小时，离心后将沉淀物用5mL去离子水洗涤3次，之后分散于5mL浓度为DMF溶液(pH＝7.0)中形成复合材料悬浮液。
AgNPs@含氮二维π-共轭金属有机框架复合材料修饰电极的制备。玻碳电极在麂皮上用0.3和0.05μm的氧化铝粉末依次打磨；后在乙醇和二次水中依次超声清洗的时间为20-25s，氮气吹干。移取5.0μL复合材料悬浮液滴涂至玻碳电极表面，室温下晾干，即得到银纳米颗粒@含氮二维π-共轭金属有机框架复合材料修饰电极AgNPs@Co3HITP2/GCE。
图1为该修饰电极的循环伏安表征图，循环伏安峰电流越大表明该电极导电性越好，图1中a的峰电流大于b大于c，表明AgNPs@Co3HITP2/GCE导电性好于Co3HITP2/GCE好于GCE，证明得到的材料有好的导电性，使得修饰电极具有好的灵敏度和检测限。
实施例2
其他步骤均与实施例相同，仅将七水硫酸钴(CoSO4·7H2O)替换为氯化钴。可以对反应温度、反应时间和反应物配比进行适当调整。
实施例3
其他步骤均与实施例相同，仅将七水硫酸钴(CoSO4·7H2O)替换为硝酸钴。
实施例4
实施例1制备的AgNPs@Co3HITP2/GCE修饰电极的循环伏安表征。将修饰好的电极在l00mmol/L K3Fe(CN)6溶液中扫描测定，扫速为100mV/s，循环伏安表征图如图1所示。
实施例5
标准曲线的绘制。在0.45V的电位下在0.1M HNO3溶液中连续注入1μM和0.1μMK2Cr2O7并进行I-T曲线测定，使用实施例1制备的AgNPs@Co3HITP2/GCE修饰电极。
实际样品检测。取200mL自来水，加入2.0M HCl酸化，旋转蒸发蒸干，将残留物再溶于2mL 0.2M HCl溶液中，过滤除去不溶物，以0.1M HNO3溶液为空白溶液，以滤液作为待测溶液，采用I-T法测定Cr(VI)的含量。
该修饰电极对于Cr(VI)目标物检测的线性范围分为两段，第一段的浓度范围为1-19μM，线性方程为I＝-0.08988C-0.82649，R2＝0.9938；另一段的浓度范围为0.1-0.9μM，线性方程为I＝-0.89427C+0.05598，R2＝0.9913，检测限为0.036μm(S/N＝3)，可见本发明的电极对六价铬的检测限较低。
本发明的修饰电极还可以对废水中的其他重金属离子进行检测，检测方法可以适当调整。
上述虽然结合附图对本发明的具体实施方式进行了描述，但并非对发明保护范围的限制，所属领域技术人员应该明白，在本发明的技术方案的基础上，本领域技术人员不需要付出创造性劳动即可做出的各种修改或变形仍在本发明的保护范围内。
Claims (8)
1.一种用于检测六价铬的复合材料，其特征在于：由含氮二维π-共轭金属有机框架与纳米银制备而成，含氮二维π-共轭金属有机框架的制备方法是在六氨基三亚苯与钴盐的混合溶液中加入碱性溶液，反应后，将得到的沉淀物进行清洗、干燥，即得。
2.根据权利要求1所述的复合材料，其特征在于：所述沉淀物的清洗方法，包括如下步骤：
将沉淀物在水中搅拌清洗，在水中搅拌清洗的时间不少于48h，并定期更换水，然后在丙酮中搅拌清洗，在丙酮中清洗的时间不少于12h。
3.权利要求1所述的复合材料的制备方法，其特征在于：包括如下步骤：
将纳米银颗粒溶液与含氮二维π-共轭金属有机框架溶液混合，搅拌反应设定时间后，即得。
4.权利要求3所述纳米银颗粒的制备方法，其特征在于：包括如下步骤：
1)冰水浴中，将硝酸银溶液缓慢加入到硼氢化钠溶液中，得到混合溶液；
2)将混合溶液移入热水浴中，加热设定时间后，在混合溶液中加入硼氢化钠溶液，剧烈搅拌；
3)将步骤2)中得到的溶液移出热水浴，继续剧烈搅拌至室温，即得。
5.一种用于检测六价铬的电化学传感器，其特征在于：将权利要求1或2所述复合材料的悬浮液涂到电极表面，干燥后制得。
6.权利要求5所述的电化学传感器在检测六价铬中的应用。
7.一种检测六价铬的三电极体系，其特征在于：工作电极为权利要求5所述电化学传感器，参比电极为饱和甘汞电极，对电极为铂丝电极。
8.利用权利要求7所述三电极体系检测六价铬的方法，其特征在于：包括如下步骤：
1)设定电位下，在酸性空白溶液中连续注入设定浓度、设定体积的六价铬溶液，绘制标准曲线；
2)取样，提取，测定，根据标准曲线测定样品中六价铬的浓度。
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