南京农业大学工学院,南京 210031
College of Engineering, Nanjing Agricultural University, Nanjing 210031, China
吸附脱附等温线、FT-IR、XPS和阳极溶出伏安法对OMC-MAP的物化性质及其改性玻碳电极电化学性能进行了表征和分析。结果表明:OMC-MAP具有较高的孔容(0.835 mL·g
)和丰富的氨基、羧基、羰基等氮氧官能团,以及P—C、P—O—C等含磷官能团,介孔主要分布在5~10 nm区域,峰值在7.45 nm;OMC-MAP良好的介孔结构及其分散在微介孔表面的氮、磷、氧活性官能团为其改性玻碳电极传感器提供了良好的电子传递通道和高识别铅离子的活性位点。在醋酸-醋酸钠支持电解质底液下,OMC-MAP介孔碳改性玻碳电极传感器对溶液铅显示极优的电催化还原活性,当pH=3.8、富集电位为?1.2 V和富集时间为240 s时,循环伏安溶出电流的响应值达到最大。在该条件下,OMC-MAP改性玻碳电极在1~10 000 μg·L
>0.98,灵敏度高、检测范围广,说明OMC-MAP是一种潜在痕量铅的电极材料。
N/P co-doped OMC-MAP modified glassy carbon electrode with high sensitivity for lead ions was prepared when common ammonium dihydrogen phosphate, formaldehyde/resorcinol and F127 were taken as modifier, carbon source and template agent of OMC-MAP, respectively. N
adsorption-desorption isotherm, FT-IR, XPS and anodic stripping voltammetry were used to characterize the physicochemical properties of OMC-MAP and electrochemical performance of modified glassy carbon electrode. The results showed that OMC-MAP had high pore volume (0.835 mL·g
), which contained amino nitrogen, carboxyl, carbonyl and other nitroxide functional groups, as well as P—C, P—O—C and other phosphorus functional groups. The mesopores were mainly distributed in the region of 5~10 nm, with a peak at 7.45 nm. The great mesoporous structure of OMC-MAP and the active functional groups of nitrogen, phosphorus and oxygen dispersed on the surface of the micro-mesopores provided a good electron transfer channel and active sites for high lead ions identification. Under the condition of acetic acid-sodium acetate supporting electrolyte solution, modified glassy carbon electrode sensor of OMC-MAP showed excellent electrocatalytic reduction activity on lead solution. When pH was 3.8, enrichment potential was ?1.2 V and enrichment time was 240 s, the cyclic voltammetric stripping current response value reached the maximum. Under this condition, the OMC-MAP modified glassy carbon electrode showed excellent responsiveness and regularity to lead ions within a wide range of 1~10 000 μg·L
. The linear correlation of
was higher than 0.98, with high sensitivity and wide detection range. This indicated that OMC-MAP modified glassy carbon electrode was a potential electrode material for trace lead ions detection.
.
adsorption-desorption isotherm curve and TEM image of mesoporous carbon OMC-MAP
OMC-MAP的DFT全孔与BJH介孔分布
DFT total pore size and BJH mesoporous distribution of OMC-MAP
OMC-MAP的FT-IR图谱与XPS图谱
FT-IR spectra of OMC-MAP and XPS spectra
Effect of different electrolytes on the determination of lead by a modified glassy carbon electrode
Effect of solution pH on peak current measurement of modified glassy carbon electrode
Effect of enriched potential on peak current measurement of modified glassy carbon electrode
Effect of enrichment time on lead enrichment peak current of modified glassy carbon electrode
不同浓度铅离子在改性电极上的溶出伏安图及峰电流与铅离子浓度之间的线性关系
Stripping voltammogram of different concentrations of lead ions on modified electrodes and linear relationship between peak current and lead ions concentration
[1] | BLAIR S M, BRODBELT J S, MARCHAND A P, et al. Evaluation of binding selectivities of aged crown ligands toward heavy metals by electrospray ionization/quadrupole ion trap mass spectrometry[J]. Analytical Chemistry, 2000, 72(11): 2433-2445. doi: 10.1021/ac991125t |
[2] | BAZZI A, KREUZ B, WUOKILA J, et al. Separation and determination of Cr(III) and Cr(VI) with cation-exchange chromatography and atomic absorption spectroscopy. An experiment for quantitative methods of analysis[J]. Journal of Chemical Education, 2005, 82(3): 435-438. doi: 10.1021/ed082p435 |
[3] | WANG L, XIA T, LIU J, et al. Preparation and application of a novel core/shell organic nanoparticle as a fluorescence probe in the selective determination of Cr(VI)[J]. Spectrochimica Acta Part A: Molecular & Biomolecular Spectroscopy, 2005, 62(1): 1386-1425. |
[4] | WILLIAMS T, JONES P, EBDON L. Simultaneous determination of Cr(III) and Cr(VI) at ultratrace levels using ion chromatography with chemiluminescence detection[J]. Journal of Chromatography A, 1989, 482(2): 361-366. doi: 10.1016/S0021-9673(01)83924-8 |
[5] | 袁彩霞. 碳基材料电化学传感研究[D]. 兰州: 西北师范大学, 2014. |
[6] | FUJITA S I, WATANABE H, KATAGIRI A, et al. Nitrogen and oxygen-doped metal-free carbon catalysts for chemoselective transfer hydrogenation of nitrobenzene, styrene, and 3-nitrostyrene with hydrazine[J]. Journal of Molecular Catalysis A: Chemical, 2014, 393: 1381-1169. |
[7] | LIU N, DING L, LI H, et al. N-doped nanoporous carbon as efficient catalyst for nitrobenzene reduction in sulfide-containing aqueous solutions[J]. Journal of Colloid and Interface Science, 2017, 490: 677-684. |
[8] | QIAO X, PENG H, YOU C, et al. Nitrogen, phosphorus and iron doped carbon nanospheres with high surface area and hierarchical porous structure for oxygen reduction[J]. Journal of Power Sources, 2015, 288: 253-260. doi: 10.1016/j.jpowsour.2015.04.118 |
[9] | ZHANG Z A, LAI Y Q, LI J, et al. Electrochemical behavior of wound supercapacitors with propylene carbonate and acetonitrile based nonaqueous electrolytes[J]. Journal of Central South University of Technology, 2009, 16(2): 247-252. doi: 10.1007/s11771-009-0042-2 |
[10] | 高杨, 岳荣, 鲁青, 等. 基于聚吡咯纳米线修饰玻碳电极的硝酸根电流型传感器研究[J]. 分析科学学报, 2012, 28(5): 6-10. |
[11] | DUAN X, INDRAWIRAWAN S, SUN H, et al. Effects of nitrogen-, boron-, and phosphorus-doping or codoping on metal-free graphene catalysis[J]. Catalysis Today, 2015, 249: 84-191. |
[12] | YANG L, JIANG S, ZHAO Y, et al. Boron-doped carbon nanotubes as metal-free electrocatalysts for the oxygen reduction reaction[J]. Angewandte Chemie International Edition, 2011, 50(31): 7132-7135. doi: 10.1002/anie.201101287 |
[13] | PEREIRA L, PEREIRA R, PEREIRA M F, et al. Effect of different carbon materials as electron shuttles in the anaerobic biotransformation of nitroanilines[J]. Biotechnology and Bioengineering, 2016, 113(6): 1194-1202. doi: 10.1002/bit.25896 |
[14] | 李坤权, 李烨, 郑正, 等. 富含中孔与酸性基团的生物质炭的制备与吸附性能[J]. 环境科学, 2013, 34(6): 2479-2485. |
[15] | WU X, ZHAO W, WANG H, et al. Enhanced capacity of chemically bonded phosphorus/carbon composite as an anode material for potassium-ion batteries[J]. Journal of Power Sources, 2018, 378: 460-467. doi: 10.1016/j.jpowsour.2017.12.077 |
[16] | LIU Y, GONG X, DONG W, et al. Nitrogen and phosphorus dual-doped carbon dots as a label-free sensor for curcumin determination in real sample and cellular imaging[J]. Talanta, 2018, 401: 330-354. |
[17] | 翁诗甫. 傅里叶变换红外光谱分析[M]. 北京: 化学工业出版社, 2010. |
[18] | PARK J A, JUNG S M, YI I G, et al. Adsorption of microcystin-LR on mesoporous carbons and its potential use in drinking water source[J]. Chemosphere, 2017, 177(6): 15-23. |
[19] | YANG H, LI S, CHEN J, et al. Adsorption of Pb(II) on mesoporous activated carbons fabricated from water hyacinth using H3PO4, activation: Adsorption capacity, kinetic and isotherm studies[J]. Applied Surface Science, 2014, 293: 160-168. doi: 10.1016/j.apsusc.2013.12.123 |
[20] | TORRELLAS S A, LOVERA R G, ESCALONA N, et al. Chemical-activated carbons from peach stones for the adsorption of emerging contaminants in aqueous solutions[J]. Chemical Engineering Journal, 2015, 279: 788-798. doi: 10.1016/j.cej.2015.05.104 |
[21] | LI K, CAO J, LI H, et al. Nitrogen functionalized hierarchical microporous/mesoporous carbon with a high surface area and controllable nitrogen content for enhanced lead(II) adsorption[J]. RSC Advances, 2016, 6: 9218-92196. |
[22] | WAN Z, LI K. Effect of pre-pyrolysis mode on simultaneous introduction of nitrogen/oxygen-containing functional groups into the structure of bagasse-based mesoporous carbon and its influence on Cu(II) adsorption[J]. Chemosphere, 2017, 194: 370-389. |
[23] | YAN X, LIU Y, FAN X, et al. Nitrogen/phosphorus co-doped nonporous carbon nanofibers for high-performance supercapacitors[J]. Journal of Power Sources, 2014, 248: 745-751. doi: 10.1016/j.jpowsour.2013.09.129 |
[24] | XIAO L, XU H, ZHOU S, et al. Simultaneous detection of cd(II) and Pb(II) by differential pulse anodic stripping voltammetry at a nitrogen-doped microporous carbon/Nafion/bismuth-film electrode[J]. Electrochimica Acta, 2014, 143: 143-151. doi: 10.1016/j.electacta.2014.08.021 |
[25] | JOSE P, JUAN J, JUANA M, et al. Selective nitrogen functionalization of phosphorus-containing activated carbons[J]. Fuel Processing Technology, 2017, 156: 236-241. |
[26] | YAN X, YU Y, RYU S K, et al. Simple and scalable synthesis of phosphorus and nitrogen enriched porous carbons with high volumetric capacitance[J]. Electrochimica Acta, 2014, 136: 466-472. doi: 10.1016/j.electacta.2014.05.031 |
[27] | LIN Y, ZHANG J, PAN Y, et al. Nickel phosphide nanoparticles decorated nitrogen and phosphorus co-doped porous carbon as efficient hybrid catalyst for hydrogen evolution[J]. Applied Surface Science, 2017, 422(15): 828-837. |
[28] | 李静, 王文成, 范钦莉, 等. 铋膜修饰碳离子液体糊电极测定痕量铅离子的研究[J]. 海南师范大学学报(自然科学版), 2015, 28(4): 400-403. |
[29] | 戴兴欣. 氨基改性介孔硅修饰电极在检测重金属离子中的应用[D]. 苏州: 苏州大学, 2015. |
[30] | 童基均, 汪亚明, 黄文清, 等. 基于平面印刷碳电极的重金属离子检测[J]. 传感技术学报, 2004, 17(1): 22-25. doi: 10.3969/j.issn.1004-1699.2004.01.006 |
[31] | 王栋萍. 类石墨相氮化碳电极材料的制备及其在铅离子检测中的应用研究[D]. 广州: 华南理工大学, 2013. |
[32] | 于璐洋, 王会才, 赵修青, 等. 巯基功能化石墨烯修饰玻碳电极测定水中痕量重金属镉[J]. 天津工业大学学报, 2014, 33(3): 34-39. doi: 10.3969/j.issn.1671-024X.2014.03.007 |
[33] | SLAVEC M, HOEVAR S B, BALDRIANOVA L, et al. Antimony film microelectrode for anodic stripping measurement of cadmium(II), lead(II) and copper(II)[J]. Electroanalysis, 2010, 22(14): 1617-1622. doi: 10.1002/elan.200900583 |
[34] | DAI X, QIU F, ZHOU X, et al. Amino-functionalized MCM-41 for the simultaneous electrochemical determination of trace lead and cadmium[J]. Electrochimica Acta, 2014, 144: 161-167. doi: 10.1016/j.electacta.2014.08.093 |
[35] | KEFALA G, ECONOMOU A. Polymer-coated bismuth film electrodes for the determination of trace metals by sequential-injection analysis/anodic stripping voltammetry[J]. Analytica Chimica Acta, 2006, 576(2): 283-289. doi: 10.1016/j.aca.2006.06.006 |