CN113418975A - 一种免电沉积技术的金属离子溶出伏安检测新方法 - Google Patents
一种免电沉积技术的金属离子溶出伏安检测新方法 Download PDFInfo
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- 238000001514 detection method Methods 0.000 title claims abstract description 15
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 13
- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 11
- 238000003950 stripping voltammetry Methods 0.000 title claims abstract description 11
- 238000005516 engineering process Methods 0.000 title claims abstract description 10
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims description 13
- 239000000725 suspension Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 3
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 3
- 238000000083 pulse voltammetry Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000000265 homogenisation Methods 0.000 claims description 2
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical group O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000000691 measurement method Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 4
- 238000004458 analytical method Methods 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 230000035945 sensitivity Effects 0.000 abstract 1
- 229910009819 Ti3C2 Inorganic materials 0.000 description 6
- 239000010936 titanium Substances 0.000 description 5
- 239000002041 carbon nanotube Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- -1 mercury ions Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 238000000835 electrochemical detection Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000002127 nanobelt Substances 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001903 differential pulse voltammetry Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000007922 dissolution test Methods 0.000 description 1
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- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
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- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明属于农业、环境及化学分析领域，公开了一种免电沉积技术的金属离子溶出伏安检测新方法，通过将MXene基纳米材料修饰电极应用于重金属的电化学传感研究。通过优化实验条件，利用MXene基纳米材对重金属的自还原吸附性能，实现对重金属的快速高灵敏检测。本发明具有简单、经济、灵敏度高、操作方便、易于现场检测的特点。
Description
技术领域
本发明属于农业、环境及化学分析领域，特别是一种快速测定金属离子的溶出伏安检测法。
背景技术
重金属通常是指相对原子质量在63.5和200.6之间，且相对密度大于或等于4.5g/cm3的金属元素，目前约发现45种。重金属是最危险的污染物之一，具有持久性、高毒性。因此，发展重金属含量的有效分析方法具有非常重大的意义。目前，常用的重金属电化学检测技术通常采用溶出伏安法，其一般包含两个步骤：(a)电沉积和(b)溶出测试。这两个步骤均需要在相应电化学仪器协助下完成，其电沉积步骤是为了将金属离子经电化学还原或氧化程序形成零价金属富集到电极表面。两个步骤均需在电化学仪器协助下完成无疑使得检测程序较为复杂耗时，不利于现场实时检测。
MXene材料是一类具有二维层状结构的金属碳/氮化物，许多MXene基(如碳化钛)纳米材料对多种重金属具有自还原性能，能在无需外加因素下使得重金属自还原到MXene材料表面，即在无需电沉积步骤下可实现对重金属的自还原富集，基于此，在电化学仪器协助下只需溶出步骤一个程序即可实现对重金属的检测。
发明内容
本发明的目的是在于提供一种免电沉积技术的金属离子溶出伏安检测新方法。该方法依次通过将MXene基材料修饰到电极表面、重金属自还原富集和溶出伏安测定，最终实现对重金属的高灵敏检测。
本发明是这样来实现的，其步骤为：
(1)将MXene基材料分散于溶剂中，超声均匀得悬浮液；
(2)移取步骤(1)所得的悬浮液滴加至电极表面，烘干，得到MXene基材料修饰电极；
(3)将重金属待测液的pH调节至5～7；
(4)将步骤(2)所得的MXene基材料修饰电极插入步骤(3)调节pH后的重金属待测液中，自还原富集1-30min后，采用脉冲伏安法进行浓度测定。
步骤(1)中，所述MXene基材料与溶剂的质量比为1:500-1:3000。
步骤(1)中，所述溶剂为水、乙醇或N,N-二甲基甲酰胺。
步骤(2)中，所述电极表面MXene基材料的修饰量为10-60μg/cm2。
步骤(2)中，所述电极为玻碳电极或丝网印刷电极。
本发明的有益效果为：
本发明中MXene基纳米材料对重金属的自还原和吸附富集作用，实现了对重金属离子无需电沉积步骤的溶出伏安检测。
附图说明
图1为本发明所得Ti3C2Tx MXene纳米片的扫描电镜图。
图2为本发明所得Ti3C2Tx MXene纳米带的扫描电镜图。
图3为本发明实施例1检测汞离子的浓度校正曲线图。
具体实施方式
下面结合实施例以及说明书附图对本发明做进一步详细说明，但本发明的保护范围并不限于此。
实施例1：
(1)将1.0mg Ti3C2Tx MXene纳米带/碳纳米管(Ti3C2Tx NR/CNTs)分散于2.0mL水中并超声搅拌20分钟。
(2)用移液枪移取(1)步悬浮液，滴加至玻碳电极表面，红外灯烘干，得到Ti3C2TxNR/CNTs电极，电极表面复合物修饰量为50μg/cm2.。
(3)将含有待测物汞离子的溶液调pH值为6.0。
(4)将第(2)步所得的修饰电极插入步骤(3)调节pH后的待测液中，自还原富集10min后，采用差分脉冲伏安法进行浓度测定。
图1和图2分别为通过该实施例制备得到的Ti3C2Tx MXene纳米片(Ti3C2Tx NS)和Ti3C2Tx NR扫描电镜图。
图3为通过该实施例制备的Ti3C2Tx NR/CNTs对汞离子的电化学检测的浓度校正曲线图，线性范围是0.01-7.0μM检测限为2.0nM。
实施例2：
(1)将1.0mg Ti3C2Tx NS分散于2mL乙醇中，超声使其分散均匀。
(2)用移液枪移取(1)步悬浮液，滴加至玻碳电极表面，红外灯烘干，得到Ti3C2TxNS修饰电极，电极表面复合物修饰量为40μg/cm2。
(3)将含有待测物镉离子的溶液调pH值为7.0。
(4)将第(2)步所得的修饰电极插入步骤(3)调节pH后的待测液中，自还原富集10min后，采用脉冲伏安法进行浓度测定。
所述实施例为本发明的优选的实施方式，但本发明并不限于上述实施方式，在不背离本发明的实质内容的情况下，本领域技术人员能够做出的任何显而易见的改进、替换或变型均属于本发明的保护范围。
Claims (5)
1.一种免电沉积技术的金属离子溶出伏安检测新方法，其特征在于，包括如下步骤：
(1)将MXene基材料分散于溶剂中，超声均匀得悬浮液；
(2)移取步骤(1)所得的悬浮液滴加至电极表面，烘干，得到MXene基材料修饰电极；
(3)将重金属待测液的pH调节至5～7；
(4)将步骤(2)所得的MXene基材料修饰电极插入步骤(3)调节pH后的重金属待测液中，自还原富集1-30min后，采用脉冲伏安法进行浓度测定。
2.如权利要求1所述的免电沉积技术的金属离子溶出伏安检测新方法，其特征在于，步骤(1)中，所述MXene基材料与溶剂的质量比为1:500-1:3000。
3.如权利要求1所述的免电沉积技术的金属离子溶出伏安检测新方法，其特征在于，步骤(1)中，所述溶剂为水、乙醇或N,N-二甲基甲酰胺。
4.如权利要求1所述的免电沉积技术的金属离子溶出伏安检测新方法，其特征在于，步骤(2)中，所述电极表面MXene基材料的修饰量为10-60μg/cm2。
5.如权利要求1所述的免电沉积技术的金属离子溶出伏安检测新方法，其特征在于，步骤(2)中，所述电极为玻碳电极或丝网印刷电极。
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110018148A (zh) * | 2019-01-08 | 2019-07-16 | 中国科学院金属研究所 | 一种表面增强拉曼试纸的制备方法 |
| CN110045121A (zh) * | 2019-04-30 | 2019-07-23 | 山东理工大学 | 一种基于空心立方体状的三金属纳米复合材料免疫传感器的制备方法及应用 |
| CN111933351A (zh) * | 2020-07-27 | 2020-11-13 | 邵峥业 | 一种碳纳米管复合透明导电薄膜及其制备方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110018148A (zh) * | 2019-01-08 | 2019-07-16 | 中国科学院金属研究所 | 一种表面增强拉曼试纸的制备方法 |
| CN110045121A (zh) * | 2019-04-30 | 2019-07-23 | 山东理工大学 | 一种基于空心立方体状的三金属纳米复合材料免疫传感器的制备方法及应用 |
| CN111933351A (zh) * | 2020-07-27 | 2020-11-13 | 邵峥业 | 一种碳纳米管复合透明导电薄膜及其制备方法 |
Non-Patent Citations (1)
| Title |
|---|
| YING HE 等: "Preparation and Application of Bismuth/MXene Nano-Composite as Electrochemical Sensor for Heavy Metal Ions Detection", 《NANOMATERIALS》 * |
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