CN106861643B - 用于检测和吸附铜离子的双功能材料及其合成方法和应用 - Google Patents
用于检测和吸附铜离子的双功能材料及其合成方法和应用 Download PDFInfo
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Abstract
本发明公开了一种用于检测和吸附铜离子的双功能材料的合成方法,以生物相容的海藻酸盐和壳聚糖为原料,通过羧基和氨基的缩合反应使其相结合,后在碱土金属离子溶液中凝胶化,经干燥制备得到该双功能材料,本发明还公开了该双功能材料及其应用,该双功能材料能够快速检测出水体中的铜离子,对铜离子灵敏度高、吸附率高、且可循环使用,适用于江河湖泊水质调查、企业工厂排水水质监测和生活用水、食品、人畜血液与体液以及通过处理各类固态样品后获得的各种水样的检测和处理,具有广泛的应用价值。
Description
技术领域
本发明属于铜离子检测领域,具体涉及一种用于检测和吸附铜离子的双功能材料及其合成方法和应用。
背景技术
铜是人体必需的微量元素之一,但过量的铜会造成肝脏损伤和引发肺癌,所以国家生活饮用水卫生标准规定生活饮用水中含铜量须低于1.0mg/L。水体中铜离子主要来源于铜矿的开采和冶炼、电镀和电器工业等。开发能够快速检测和吸附去除水体中铜离子的功能材料具有重要意义。
目前,关于水体中铜离子的检测,主要是通过金或银纳米粒子溶液比色检测和仪器检测来实现,其中金或银纳米粒子溶液比色检测操作简单,且适用于野外检测,但其灵敏度易受水样中其他成份干扰。仪器检测主要是使用紫外-可见分光光度计、原子吸收分光光度计或等离子发射光谱仪等大型仪器对水样进行检测,需对样品进行预处理,且测试费用较高。去除水体中铜离子的方法目前主要有化学沉淀法、离子交换法、膜过滤法、吸附法、反渗透、电化学等方法,其中吸附法由于操作简便、处理效率高、可实现铜离子回收利用等特点越来越受到重视。已报道的铜离子吸附剂主要有农业废弃物、无机纳米材料、有机高分子聚合物等,这些铜离子吸附剂具有如下的缺点:(1)农业废弃物吸附容量有限,且在使用过程中向释放有机质,造成水体化学耗氧量(COD)升高;(2)纳米材料吸附剂由于颗粒较小,回收困难不利于循环使用。(3)有机高分子聚合物,水溶性较差,只能应用于有机溶剂或有机溶剂和水的混合溶液;(4)只能吸附去除铜离子,不能同时实现铜离子的快速检测。目前,有关用于检测和吸附水体中铜离子的双功能材料的报道较少。
发明内容
本发明的目的在于:提供了一种用于检测和吸附铜离子的双功能材料的合成方法及应用,所合成的双功能材料适用于检测和吸附水体中Cu2+,并且易于回收,可循环使用。
为了实现上述发明目的,本发明提供如下技术方案:
一种用于检测和吸附铜离子的双功能材料含有羧基和氨基功能基团及碱土金属离子,能够与Cu2+发生配位反应和离子交换反应;该双功能材料结合Cu2+后,显示出特有的蓝色,其中,氨基和羧基的摩尔比大于1:1。
优选地,氨基和羧基的摩尔比为1.5:1。
优选地,一种用于检测和吸附铜离子的双功能材料的合成方法,包括如下步骤:
(1)将功能试剂溶于缓冲溶液中,搅拌条件下,加入修饰剂和缩合剂进行反应,得到混合液;
(2)在搅拌条件下,将步骤(1)制得的混合液滴入含碱土金属离子的溶液,反应完全之后,经固液分离、洗涤、干燥,制得所述的双功能材料。
优选地,步骤(1)中所述的功能试剂为海藻酸钠、海藻酸钾或海藻酸中的至少一种;所述的修饰试剂为粘度≤200mPs·s的低粘度壳聚糖、甲基乙二醇壳聚糖或羧化壳聚糖中的至少一种;所述的缩合剂为1-乙基-(3-二甲基氨基丙基)碳二亚胺盐酸盐、2-(7-氧化苯并三氮唑)-N,N,N',N'-四甲基脲六氟磷酸酯、N-羟基琥珀酰亚胺和1-羟基苯并三唑中的至少一种。
优选地,步骤(1)中所述的功能试剂为海藻酸钠;所述的修饰试剂为羧化壳聚糖;所述的缩合剂为1-乙基-(3-二甲基氨基丙基)碳二亚胺盐酸盐和N-羟基琥珀酰亚胺。
优选地,步骤(1)中,反应温度为1~90℃;反应时间大于2小时;所述的缓冲溶液pH为4.5~6.5。
优选地,步骤(1)中,反应温度为10~30℃;反应时间为6小时;所述的缓冲溶为pH5.5的2-(N-吗啡啉)乙磺酸缓冲液。
优选地,步骤(2)中所述的含碱土金属离子的溶液为含钙离子、锶离子、钡离子中的一种或多种离子的溶液;所述的干燥方法为真空干燥或真空冷冻干燥法。
优选地,步骤(2)中所述的含碱土金属离子的溶液为含钙离子的水溶液。所述的干燥方法为真空冷冻干燥法。
优选地,一种用于检测和吸附铜离子的双功能材料的应用,能用用于检测环境中的水样,也能够检测漂浮在大气中的灰尘、食品样品、人体或动物的血液及其他体液经过处理后获得的水溶液。
本发明的有益效果在于:
(1)该发明基于双功能材料与Cu2+的选择性络合,引起固体颜色变化,因此,可以利用比色法或紫外-可见分光光度计进行判定,即能快速地检测出溶液中是否含有Cu2+,实现对水溶液中Cu2+的快速检测与定量分析;
(2)该双功能材料属宏观多孔材料,易于固液分离;
(3)该双功能材料对铜离子具有灵敏的选择性响应,能吸附铜离子;
(4)该双功能材料经过无机酸处理,可循环使用,具有广阔的工业应用前景。
附图说明
图1为实施例1中双功能材料的合成路线图;
图2为实施例1中双功能材料的红外光谱图;
图3为实施例13绘制得到的标准曲线图。
具体实施方式
实施例1:合成双功能材料
图1为本实施例中合成双功能材料的化学反应路线图,如图1所示,具体过程如下:
(1)称取2.0g海藻酸钠(粘度:200±20mPa·s)溶于98.0gpH5.5的MES(2-(N-吗啡啉)乙磺酸)缓冲溶液中,搅拌条件下,加入0.15g 1-乙基-(3-二甲基氨基丙基)碳二亚胺盐酸盐、0.12g N-羟基琥珀酰亚胺和3.0g羧化壳聚糖,25℃条件下反应6h,制得混合液;
(2)搅拌条件下,采用10mL医用注射器将步骤(1)制得的混合液逐滴滴入500mL0.25mol/L硝酸钙溶液中,滴完后继续搅拌30分钟,经过滤,蒸馏水洗涤,制得海藻酸钙-壳聚糖水凝胶;
(3)将步骤(2)制得的海藻酸钙-壳聚糖水凝胶浸泡于蒸馏水中,置于真空冷冻干燥机中冷冻、真空干燥,制得双功能材料,该双功能材料的红外光谱图如图2所示。
实施例2:合成双功能材料
(1)称取2.0g海藻酸钾溶于98.0gpH 5.5的MES(2-(N-吗啡啉)乙磺酸)缓冲溶液中,搅拌条件下,加入0.15g 1-乙基-(3-二甲基氨基丙基)碳二亚胺盐酸盐、0.12gN-羟基琥珀酰亚胺和3.0g羧化壳聚糖,25℃条件下反应6h,制得混合液;
(2)搅拌条件下,采用10mL医用注射器将步骤(1)制得的混合液逐滴滴入500mL0.25mol/L硝酸钙溶液中,滴完后继续搅拌30分钟,经过滤,蒸馏水洗涤,制得海藻酸钙-壳聚糖水凝胶;
(3)将步骤(2)制得的海藻酸钙-壳聚糖水凝胶浸泡于蒸馏水中,置于真空冷冻干燥机中冷冻、真空干燥,制得双功能材料。
实施例2相对于实施例1的区别在于:将海藻酸钠替换为海藻酸钾。
实施例3:合成双功能材料
(1)称取2.0g海藻酸溶于98.0gpH 5.5的MES(2-(N-吗啡啉)乙磺酸)缓冲溶液中,搅拌条件下,加入0.15g 1-乙基-(3-二甲基氨基丙基)碳二亚胺盐酸盐、0.12gN-羟基琥珀酰亚胺和3.0g羧化壳聚糖,25℃条件下反应6h,制得混合液;
(2)搅拌条件下,采用10mL医用注射器将步骤(1)制得的混合液逐滴滴入500mL0.25mol/L硝酸钙溶液中,滴完后继续搅拌30分钟,经过滤,蒸馏水洗涤,制得海藻酸钙-壳聚糖水凝胶;
(3)将步骤(2)制得的海藻酸钙-壳聚糖水凝胶浸泡于蒸馏水中,置于真空冷冻干燥机中冷冻、真空干燥,制得双功能材料。
实施例3相对于实施例1的区别在于:将海藻酸钠替换为海藻酸。
实施例4:合成双功能材料
(1)称取2.0g海藻酸钠溶于98.0gpH 5.5的MES(2-(N-吗啡啉)乙磺酸)缓冲溶液中,搅拌条件下,加入0.15g 1-乙基-(3-二甲基氨基丙基)碳二亚胺盐酸盐、0.12gN-羟基琥珀酰亚胺和3.0g低粘度壳聚糖(≤200mPs·s),25℃条件下反应6h,制得混合液;
(2)搅拌条件下,采用10mL医用注射器将步骤(1)制得的混合液逐滴滴入500mL0.25mol/L硝酸钙溶液中,滴完后继续搅拌30分钟,经过滤,蒸馏水洗涤,制得海藻酸钙-壳聚糖水凝胶;
(3)将步骤(2)制得的海藻酸钙-壳聚糖水凝胶浸泡于蒸馏水中,置于真空冷冻干燥机中冷冻、真空干燥,制得双功能材料。
实施例4相对于实施例1的区别在于:将羧化壳聚糖替换为低粘度壳聚糖(≤200mPs·s)。
实施例5:合成双功能材料
(1)称取2.0g海藻酸钠溶于98.0gpH 5.5的MES(2-(N-吗啡啉)乙磺酸)缓冲溶液中,搅拌条件下,加入0.15g 2-(7-氧化苯并三氮唑)-N,N,N',N'-四甲基脲六氟磷酸酯和3.0g羧化壳聚糖,25℃条件下反应6h,制得混合液;
(2)搅拌条件下,采用10mL医用注射器将步骤(1)制得的混合液逐滴滴入500mL0.25mol/L硝酸钙溶液中,滴完后继续搅拌30分钟,经过滤,蒸馏水洗涤,制得海藻酸钙-壳聚糖水凝胶;
(3)将步骤(2)制得的海藻酸钙-壳聚糖水凝胶浸泡于蒸馏水中,置于真空冷冻干燥机中冷冻、真空干燥,制得双功能材料。
实施例5相对于实施例1的区别在于:将缩合剂1-乙基-(3-二甲基氨基丙基)碳二亚胺盐酸盐和N-羟基琥珀酰亚胺替换为2-(7-氧化苯并三氮唑)-N,N,N',N'-四甲基脲六氟磷酸酯。
实施例6:合成双功能材料
(1)称取2.0g海藻酸钠溶于98.0gpH 5.5的MES(2-(N-吗啡啉)乙磺酸)缓冲溶液中,搅拌条件下,加入0.15g 1-乙基-(3-二甲基氨基丙基)碳二亚胺盐酸盐、0.12gN-羟基琥珀酰亚胺和3.0g羧化壳聚糖,10℃条件下反应6h,制得混合液;
(2)搅拌条件下,采用10mL医用注射器将步骤(1)制得的混合液逐滴滴入500mL0.25mol/L硝酸钙溶液中,滴完后继续搅拌30分钟,经过滤,蒸馏水洗涤,制得海藻酸钙-壳聚糖水凝胶;
(3)将步骤(2)制得的海藻酸钙-壳聚糖水凝胶浸泡于蒸馏水中,置于真空冷冻干燥机中冷冻、真空干燥,制得双功能材料。
实施例6相对于实施例1的区别在于:将步骤(1)反应温度由25℃替换为10℃。
实施例7:合成双功能材料
(1)称取2.0g海藻酸钠溶于98.0gpH 5.5的MES(2-(N-吗啡啉)乙磺酸)缓冲溶液中,搅拌条件下,加入0.15g 1-乙基-(3-二甲基氨基丙基)碳二亚胺盐酸盐、0.12gN-羟基琥珀酰亚胺和3.0g羧化壳聚糖,70℃条件下反应6h,制得混合液;
(2)搅拌条件下,采用10mL医用注射器将步骤(1)制得的混合液逐滴滴入500mL0.25mol/L硝酸钙溶液中,滴完后继续搅拌30分钟,经过滤,蒸馏水洗涤,制得海藻酸钙-壳聚糖水凝胶;
(3)将步骤(2)制得的海藻酸钙-壳聚糖水凝胶浸泡于蒸馏水中,置于真空冷冻干燥机中冷冻、真空干燥,制得双功能材料。
实施例7相对于实施例1的区别在于:将步骤(1)反应温度由25℃替换为70℃。
实施例8:合成双功能材料
(1)称取2.0g海藻酸钠(粘度:200±20mPa·s)溶于98.0gpH5.5的MES(2-(N-吗啡啉)乙磺酸)缓冲溶液中,搅拌条件下,加入0.15g 1-乙基-(3-二甲基氨基丙基)碳二亚胺盐酸盐、0.12g N-羟基琥珀酰亚胺和3.0g羧化壳聚糖,25℃条件下反应10h,制得混合液;
(2)搅拌条件下,采用10mL医用注射器将步骤(1)制得的混合液逐滴滴入500mL0.25mol/L硝酸钙溶液中,滴完后继续搅拌30分钟,经过滤,蒸馏水洗涤,制得海藻酸钙-壳聚糖水凝胶;
(3)将步骤(2)制得的海藻酸钙-壳聚糖水凝胶浸泡于蒸馏水中,置于真空冷冻干燥机中冷冻、真空干燥,制得双功能材料。
实施例8相对于实施例1的区别在于:将步骤(1)反应时间由6h替换为10h。
实施例9:合成双功能材料
(1)称取2.0g海藻酸钠(粘度:200±20mPa·s)溶于98.0gpH5.5的MES(2-(N-吗啡啉)乙磺酸)缓冲溶液中,搅拌条件下,加入0.15g 1-乙基-(3-二甲基氨基丙基)碳二亚胺盐酸盐、0.12g N-羟基琥珀酰亚胺和6.0g羧化壳聚糖,25℃条件下反应6h,制得混合液;
(2)搅拌条件下,采用10mL医用注射器将步骤(1)制得的混合液逐滴滴入500mL0.25mol/L硝酸钙溶液中,滴完后继续搅拌30分钟,经过滤,蒸馏水洗涤,制得海藻酸钙-壳聚糖水凝胶;
(3)将步骤(2)制得的海藻酸钙-壳聚糖水凝胶浸泡于蒸馏水中,置于真空冷冻干燥机中冷冻、真空干燥,制得双功能材料。
实施例9相对于实施例1的区别在于:将步骤(1)中羧化壳聚糖的质量由3.0g替换为6.0g。
实施例10:双功能材料对Cu2+的选择性
(1)配制浓度为10-4mol/L的各金属离子标准储备液(Ag+,Ba2+,Ca2+,Cd2+,Co2+,Hg2 +,K+,Mg2+,Mn2+,Ni2+,Pb2+,Zn2+,Fe2+,Fe3+,Cr3+,Cr6+),配制浓度为10-5mol/L的Cu2+标准储备液;
(2)称取100mg实施例1制得的双功能材料分别加入10mL步骤(1)配制的金属离子标准储备液,5分钟后,观察双功能材料颜色变化,后经过滤、40℃烘箱干燥得吸附有金属离子的双功能材料,用紫外-可见分光光度计测定其吸光强度,并记录波长700nm处吸光强度值(A:吸光强度);
(3)由实验现象和所得数据(AAg+=0.013,ABa2+=0.014,ACa2+=0.012,ACd2+=0.016,ACo2+=0.020,AHg2+=0.018,AK+=0,AMg2+=0.022,AMn2+=0.027,ANi2+=0.027,APb2+=0.016,AZn2+=0.024,AFe2+=0.023,AFe3+=0.028,ACr3+=0.026,ACr6+=0.028,ACu2+=0.110)可知,当加入其他金属离子溶液时,双功能材料不变色或不变为蓝色,在波长700nm处吸光强度值很小或为零。当加入Cu2+溶液时,双功能材料颜色由无色变为蓝色,且在波长700nm处有较大的吸光强度值,双功能材料对Cu2+具有高选择性。
实施例11:河水、湖水水样中Cu2+的检测
(1)待检测水样采集:用水样采集瓶在河、湖三个不同地点的一定深度(10~50cm)处采集水样,然后用盐酸或氢氧化钠调节其pH至3.0~7.0,得到待检测水样;
(2)称取100mg双功能材料加入10mL步骤(1)待检测水样中,5分钟后,观察双功能材料颜色变化,如变蓝,则判定后待检测水样中含有Cu2+,且溶液中所含Cu2+浓度大于或等于10-5mol/L;如颜色无变化或不变蓝,则判定待检测水样中不含有Cu2+或Cu2+浓度小于10- 5mol/L。
实施例12:工矿、电器、电镀厂水样中Cu2+的检测
(1)待检测水样采集:在废水排放口的取样位置处每隔一段时间(如1h,2h…)采集水样,然后等量混合成混合样品,之后用盐酸或氢氧化钠调节其pH至3.0~7.0,得到待检测水样;
(2)称取100mg双功能材料加入10mL步骤(1)待检测水样中,5分钟后,观察双功能材料颜色变化,如变蓝,则判定后待检测水样中含有Cu2+,且溶液中所含Cu2+浓度大于或等于10-5mol/L;如颜色无变化或不变蓝,则判定待检测水样中不含有Cu2+或Cu2+浓度小于10- 5mol/L。
实施例13:绘制标准曲线
(1)分别吸取10-3mol/L的铜标准储备液0.00、1.00、3.00、5.00、7.00、10.00mL至100mL容量瓶,加蒸馏水稀释至刻度,摇匀,静置;
(2)称取100mg实施例1制得的双功能材料分别加入10mL步骤(1)配制的铜离子标准液,5分钟后,过滤、40℃烘箱干燥得吸附有Cu2+的双功能材料,用紫外-可见分光光度计测定其吸光强度,并记录波长700nm处吸光强度值;
(3)以吸光强度值为纵坐标,铜离子浓度为横坐标绘制出标准曲线,参见图3。
实施例14:水样中Cu2+浓度的测定
(1)待检测水样采集:用水样采集瓶在河、湖三个不同地点的一定深度(20~50cm)处采集水样,然后用盐酸或氢氧化钠调节其pH至3.0~7.0,得到待检测水样;
(2)称取100mg实施例1制得的双功能材料分别加入10mL步骤(1)配制的铜离子标准液,5分钟后,过滤、40℃烘箱干燥得吸附有Cu2+的双功能材料,用紫外-可见分光光度计测定其吸光强度,并记录波长700nm处吸光强度值;
(3)将步骤(2)所测得吸光强度值代入标准曲线方程,从而计算得出待测水样中Cu2+浓度(河水中Cu2+浓度为1.32×10-5mol/L,河水中不含Cu2+或Cu2+浓度低于1×10-5mol/L)。
实施例15:吸附铜矿水样中Cu2+
(1)待吸附水样采集:在安庆铜矿废水排放口的取样位置处每隔2h采集水样,然后等量混合成混合样品(pH值为5.3),得到待吸附水样;
(2)采用电感耦合等离子光谱仪测定待吸附水样中Cu2+浓度(1.57×10-3mol/L);
(3)称取100mg实施例1制得的双功能材料加入10mL步骤(1)待吸附水样,5分钟后,过滤,通过电感耦合等离子光谱仪测定滤液中剩余Cu2+浓度(1.26×10-5mol/L),从而计算出双功能材料对Cu2+的吸附率,吸附率为99.2%。
实施例16:双功能材料的循环使用
(1)称取100mg实施例1制得的双功能材料加入10mL含Cu2+待检测水样,5分钟后,过滤,得已吸附Cu2+的双功能材料;
(2)将步骤(1)得到的已吸附Cu2+的双功能材料加入20mL 0.1mol/L盐酸溶液中,搅拌10分钟后,过滤,蒸馏水洗涤3次,40℃烘箱中干燥,即可重新得到双功能材料,循环使用10次,其检测和吸附Cu2+性能基本稳定。
以上所述的实施例对本发明的技术方案进行了详细说明,应理解的是以上所述仅为本发明的具体实施例,并不用于限制本发明,凡在本发明的原则范围内所做的任何修改和改进等,均应包含在本发明的保护范围之内。
Claims (7)
1.一种用于检测和吸附铜离子的双功能材料,其特征在于:含有羧基和氨基功能基团及碱土金属离子,能够与Cu2+发生配位反应和离子交换反应;该双功能材料结合Cu2+后,显示出特有的蓝色,其中,氨基和羧基的摩尔比大于1:1;
所述的双功能材料采用如下方法合成,具体包括如下步骤:
(1)将功能试剂溶于缓冲溶液中,搅拌条件下,加入修饰剂和缩合剂进行反应,得到混合液;
(2)在搅拌条件下,将步骤(1)制得的混合液滴入含碱土金属离子的溶液,反应完全之后,经固液分离、洗涤、干燥,制得所述的双功能材料;
其中,步骤(1)中,反应温度为1~90℃;反应时间大于2小时;
所述的功能试剂为海藻酸钠、海藻酸钾或海藻酸中的至少一种;所述的修饰试剂为粘度≤200mPs·s的低粘度壳聚糖、甲基乙二醇壳聚糖或羧化壳聚糖中的至少一种;所述的缩合剂为1-乙基-(3-二甲基氨基丙基)碳二亚胺盐酸盐、2-(7-氧化苯并三氮唑)-N,N,N',N'-四甲基脲六氟磷酸酯、N-羟基琥珀酰亚胺和1-羟基苯并三唑中的至少一种;
所述的缓冲溶液 为pH5.5的2-(N-吗啡啉)乙磺酸缓冲液;
所述的含碱土金属离子的溶液为含钙离子、锶离子、钡离子中的一种或多种离子的溶液。
2.根据权利要求1所述的用于检测和吸附铜离子的双功能材料,其特征在于:氨基和羧基的摩尔比为1.5:1。
3.根据权利要求1所述的用于检测和吸附铜离子的双功能材料,其特征在于:
步骤(1)中所述的功能试剂为海藻酸钠;所述的修饰试剂为羧化壳聚糖;所述的缩合剂为1-乙基-(3-二甲基氨基丙基)碳二亚胺盐酸盐和N-羟基琥珀酰亚胺。
4.根据权利要求1所述的用于检测和吸附铜离子的双功能材料,其特征在于:
步骤(1)中,反应温度为10~30℃;反应时间为6小时。
5.根据权利要求1所述的用于检测和吸附铜离子的双功能材料,其特征在于:
步骤(2)中所述的干燥方法为真空干燥或真空冷冻干燥法。
6.根据权利要求5所述的用于检测和吸附铜离子的双功能材料,其特征在于:
步骤(2)中所述的含碱土金属离子的溶液为含钙离子的水溶液; 所述的干燥方法为真空冷冻干燥法。
7.一种如权利要求1-6任意一项所述的用于检测和吸附铜离子的双功能材料的应用,其特征在于:能用于检测环境中的水样,也能够检测漂浮在大气中的灰尘、食品样品、人体或动物的血液及其他体液经过处理后获得的水溶液。
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