碳基全固态离子选择性电极材料研究进展

doi:10.16085/j.issn.1000-6613.2021-2618

摘要/Abstract

摘要：

离子选择性电极作为一种常见的电位型化学传感器，具有结构简单、制作成本低、易微型化、可穿戴化等特点，被广泛应用到工业分析、环境监测、生物医疗等领域。固态转导层作为全固态离子选择性电极的组成部件之一，对电极的性能起着至关重要影响。碳基材料具有良好的离子-电子信号转换效率和化学稳定性，被认为是理想的固态转导层材料。本文阐述了碳基材料在全固态离子选择性电极中的响应机理，综述了石墨烯、碳纳米管、多孔碳材料及其他碳基材料作为固态转导层材料的研究进展，分析对比了上述材料的导电性、电容性、比表面积、疏水性等性能，并展望了其未来的发展趋势。

关键词: 固态转导层, 碳基材料, 全固态离子选择性电极

Abstract:

As a common potentiometric sensor, solid-state ion-selective electrodes (SS-ISEs) have attracted much more attention due to simple structure, low cost, easy miniaturization and wearability, therefore have been widely used in industrial analysis, environmental monitoring, biomedical and related fields. As one of the components of an all-solid-state ion-selective electrode, the solid-state transduction layer plays a crucial role in the performance of the electrode. Carbon-based materials have good ion-electron signal conversion efficiency and chemical stability, are considered as an ideal materials for solid-state transduction layers. This article briefly describes the response mechanism of carbon-based materials in all-solid-state ion-selective electrodes, reviews the research progress of graphene, carbon nanotubes, porous carbon materials and other kinds of carbon-based nano materials as solid-state transconductance layer materials. Finally, we analyze and compare the properties of the above materials such as electrical conductivity, capacitance, specific surface area and hydrophobicity as well as their prospective and future development trends.

Key words: solid-contact layer, carbon derived materials, all solid-state ion selective electrode

中图分类号:

TP212.2

王锡民, 魏潇然, 冯瑛, 黄国勇, 王春霞. 碳基全固态离子选择性电极材料研究进展[J]. 化工进展, 2022, 41(10): 5456-5464.

WANG Ximin, WEI Xiaoran, FENG Ying, HUANG Guoyong, WANG Chunxia. Studies on all solid-state ion-selective electrodes based on carbon derived materials[J]. Chemical Industry and Engineering Progress, 2022, 41(10): 5456-5464.

图/表 6

参考文献 74

1	TURNER Anthony P F. Biosensors: sense and sensibility[J]. Chemical Society Reviews, 2013, 42(8): 3184-3196.
2	FRANT M S, ROSS J W. Electrode for sensing fluoride ion activity in solution[J]. Science, 1966, 154(3756): 1553-1555.
3	CUNNINGHAM L, FREISER H. Coated-wire ion-selective electrodes[J]. Analytica Chimica Acta, 1986, 180: 271-279.
4	ABRAMOVA Natalia, Javier MORAL-VICO, SOLEY Jordi, et al. Solid contact ion sensor with conducting polymer layer copolymerized with the ion-selective membrane for determination of calcium in blood serum[J]. Analyst, 2016, 943: 50-57.
5	HERNáNDEZ R, RIU J, RIUS F X. Determination of calcium ion in sap using carbon nanotube-based ion-selective electrodes[J]. Analytical Chemistry, 2010, 135(8): 1979-1985.
6	YIN Tanji, PAN Dawei, QIN Wei. All-solid-state polymeric membrane ion-selective miniaturized electrodes based on a nanoporous gold film as solid contact[J]. Analytical Chemistry, 2014, 86(22): 11038-11044.
7	IVANOVA N M, LEVIN M B, MIKHELSON K N. Problems and prospects of solid contact ion-selective electrodes with ionophore-based membranes[J]. Russian Chemical Bulletin, 2012, 61(5): 926-936.
8	Xavier RIUS-RUIZ F, Diego BEJARANO-NOSAS, BLONDEAU Pascal, et al. Disposable planar reference electrode based on carbon nanotubes and polyacrylate membrane[J]. Analytical Chemistry, 2011, 83(14): 5783-5788.
9	PING Jianfeng, WANG Yixian, WU Jian, et al. Development of an all-solid-state potassium ion-selective electrode using graphene as the solid-contact transducer[J]. Electrochemistry Communications, 2011, 13(12): 1529-1532.
10	LAI Chunze, FIERKE Melissa A, STEIN Andreas, et al. Ion-selective electrodes with three-dimensionally ordered macroporous carbon as the solid contact[J]. Analytical Chemistry, 2007, 79(12): 4621-4626.
11	FIERKE Melissa A, LAI Chunze, Philippe BÜHLMANN, et al. Effects of architecture and surface chemistry of three-dimensionally ordered macroporous carbon solid contacts on performance of ion-selective electrodes[J]. Analytical Chemistry, 2010, 82(2): 680-688.
12	NOVOSELOV K S, GEIM A K, MOROZOV S V, et al. Electric field effect in atomically thin carbon films[J]. Science, 2004, 306(5696): 666-669.
13	Rafael HERNÁNDEZ, Jordi RIU, BOBACKA Johan, et al. Reduced graphene oxide films as solid transducers in potentiometric all-solid-state ion-selective electrodes[J]. The Journal of Physical Chemistry C, 2012, 116(42): 22570-22578.
14	STANKOVICH Sasha, DIKIN Dmitriy A, PINER Richard D, et al. Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide[J]. Carbon, 2007, 45(7): 1558-1565.
15	PING Jianfeng, WANG Yixian, YING Yibin, et al. Application of electrochemically reduced graphene oxide on screen-printed ion-selective electrode[J]. Analytical Chemistry, 2012, 84(7): 3473-3479.
16	GARLAND Nate T, MCLAMORE Eric S, CAVALLARO Nicholas D, et al. Flexible laser-induced graphene for nitrogen sensing in soil[J]. ACS Applied Materials & Interfaces, 2018, 10(45): 39124-39133.
17	HJORT Robert G, SOARES Raquel R A, LI Jingzhe, et al. Hydrophobic laser-induced graphene potentiometric ion-selective electrodes for nitrate sensing[J]. Mikrochimica Acta, 2022, 189(3): 122.
18	HE Qing, Suprem R DAS, GARLAND Nathaniel T, et al. Enabling inkjet printed graphene for ion selective electrodes with postprint thermal annealing[J]. ACS Applied Materials & Interfaces, 2017, 9(14): 12719-12727.
19	AN Qingbo, GAN Shiyu, XU Jianan, et al. A multichannel electrochemical all-solid-state wearable potentiometric sensor for real-time sweat ion monitoring[J]. Electrochemistry Communications, 2019, 107: 106553.
20	LI Jinghui, QIN Wei. A freestanding all-solid-state polymeric membrane Cu²⁺-selective electrode based on three-dimensional graphene sponge[J]. Analytica Chimica Acta, 2019, 1068: 11-17.
21	YOON Jo Hee, PARK Hong Jun, PARK Seung Hwa, et al. Electrochemical characterization of reduced graphene oxide as an ion-to-electron transducer and application of screen-printed all-solid-state potassium ion sensors[J]. Carbon Letters, 2020, 30(1): 73-80.
22	SUN Qinqin, LI Wanzhen, SU Bin. Highly hydrophobic solid contact based on graphene-hybrid nanocomposites for all solid state potentiometric sensors with well-formulated phase boundary potentials[J]. Journal of Electroanalytical Chemistry, 2015, 740: 21-27.
23	Magdalena PIĘK, FENDRYCH Katarzyna, SMAJDOR Joanna, et al. High selective potentiometric sensor for determination of nanomolar con-centration of Cu(Ⅱ) using a polymeric electrode modified by a graphene/7,7,8,8-tetracyanoquinodimethane nanoparticles[J]. Talanta, 2017, 170: 41-48.
24	Magdalena PIĘK, PIECH Robert, Beata PACZOSA-BATOR. All-solid-state nitrate selective electrode with graphene/tetrathiafulvalene nanocomposite as high redox and double layer capacitance solid contact[J]. Electrochimica Acta, 2016, 210: 407-414.
25	TAKAMATSU Hiroki, OHBA Tomonori. Water adsorption control by surface nanostructures on graphene-related materials by grand canonical Monte Carlo simulations[J]. Langmuir, 2021, 37(50): 14646-14656.
26	MAO Shun, LU Ganhua, CHEN Junhong. Three-dimensional graphene-based composites for energy applications[J]. Nanoscale, 2015, 7(16): 6924-6943.
27	BOEVA Zhanna A, LINDFORS Tom. Few-layer graphene and polyaniline composite as ion-to-electron transducer in silicone rubber solid-contact ion-selective electrodes[J]. Sensors and Actuators B: Chemical, 2016, 224: 624-631.
28	LI Jinghui, YIN Tanji, QIN Wei. An effective solid contact for an all-solid-state polymeric membrane Cd²⁺-selective electrode: three-dimensional porous graphene-mesoporous platinum nanoparticle composite[J]. Sensors and Actuators B: Chemical, 2017, 239: 438-446.
29	LIU Yuandong, ZHANG Limin, MO Jingwen, et al. Ion selective electrode mediated by transfer layer of graphene oxide for detection of Ca²⁺ with highly sensitivity and selectivity[J]. Journal of the Electrochemical Society, 2022, 169(1): 016514.
30	SCHROEDER Vera, SAVAGATRUP Suchol, HE Maggie, et al. Carbon nanotube chemical sensors[J]. Chemical Reviews, 2019, 119(1): 599-663.
31	ZHAO Fengnian, WU Jian, YING Yibin, et al. Carbon nanomaterial-enabled pesticide biosensors: design strategy, biosensing mechanism, and practical application[J]. TrAC Trends in Analytical Chemistry, 2018, 106: 62-83.
32	JIANG Chengmei, LAN Lingyi, YAO Yao, et al. Recent progress in application of nanomaterial-enabled biosensors for ochratoxin A detection[J]. Trends in Analytical Chemistry, 2018, 102: 236-249.
33	Daniel QUESADA-GONZÁLEZ, Arben MERKOÇI. Nanomaterial-based devices for point-of-care diagnostic applications[J]. Chemical Society Reviews, 2018, 47(13): 4697-4709.
34	WEN Lei, LI Feng, CHENG Huiming. Carbon nanotubes and graphene for flexible electrochemical energy storage: from materials to devices[J]. Advanced Materials, 2016, 28(22): 4306-4337.
35	CRESPO Gastón A, GUGSA Derese, MACHO Santiago, et al. Solid-contact pH-selective electrode using multi-walled carbon nanotubes[J]. Analytical and Bioanalytical Chemistry, 2009, 395(7): 2371-2376.
36	PARRA Enrique J, CRESPO Gastón A, Jordi RIU, et al. Ion-selective electrodes using multi-walled carbon nanotubes as ion-to-electron transducers for the detection of perchlorate[J]. Analyst, 2009, 134(9): 1905-1910.
37	MOUSAVI Zekra, TETER Agnieszka, LEWENSTAM Andrzej, et al. Comparison of multi-walled carbon nanotubes and poly(3-octylthiophene) as ion-to-electron transducers in all-solid-state potassium ion-selective electrodes[J]. Electroanalysis, 2011, 23(6): 1352-1358.
38	YUAN Dajing, ANTHIS Alexandre H C, AFSHAR Majid Ghahraman, et al. All-solid-state potentiometric sensors with a multiwalled carbon nanotube inner transducing layer for anion detection in environmental samples[J]. Analytical Chemistry, 2015, 87(17): 8640-8645.
39	CUARTERO María, DEL RÍO Jonathan Sabaté, BLONDEAU Pascal, et al. Rubber-based substrates modified with carbon nanotubes inks to build flexible electrochemical sensors[J]. Analytica Chimica Acta, 2014, 827: 95-102.
40	NOVELL Marta, GUINOVART Tomàs, BLONDEAU Pascal, et al. A paper-based potentiometric cell for decentralized monitoring of Li levels in whole blood[J]. Lab on a Chip, 2014, 14(7): 1308-1314.
41	VAISMAN Linda, Daniel WAGNER H, MAROM Gad. The role of surfactants in dispersion of carbon nanotubes[J]. Advances in Colloid and Interface Science, 2006, 128: 37-46.
42	JAWORSKA Ewa, LEWANDOWSKI Wiktor, Józef MIECZKOWSKI, et al. Simple and disposable potentiometric sensors based on graphene or multi-walled carbon nanotubes—Carbon-plastic potentiometric sensors[J]. Analyst, 2013, 138(8): 2363-2371.
43	Cristina OCAÑA, ABRAMOVA Natalia, BRATOV Andrey, et al. Calcium-selective electrodes based on photo-cured polyurethane-acrylate membranes covalently attached to methacrylate functionalized poly(3,4-ethylenedioxythiophene) as solid-contact[J]. Talanta, 2018, 186: 279-285.
44	MOUSAVI Zekra, BOBACKA Johan, LEWENSTAM Andrzej, et al. Poly(3,4-ethylenedioxythiophene) (PEDOT) doped with carbon nanotubes as ion-to-electron transducer in polymer membrane-based potassium ion-selective electrodes[J]. Journal of Electroanalytical Chemistry, 2009, 633(1): 246-252.
45	RAJABI Hamid Reza, ROUSHANI Mahmoud, SHAMSIPUR Mojtaba. Development of a highly selective voltammetric sensor for nanomolar detection of mercury ions using glassy carbon electrode modified with a novel ion imprinted polymeric nanobeads and multi-wall carbon nanotubes[J]. Journal of Electroanalytical Chemistry, 2013, 693: 16-22.
46	MALIK Lateef Ahmad, PANDITH Altaf Hussain, BASHIR Arshid, et al. Zinc oxide-decorated multiwalled carbon nanotubes: a selective electrochemical sensor for the detection of Pb(Ⅱ) ion in aqueous media[J]. Journal of Materials Science: Materials in Electronics, 2022, 33(9): 6178-6189.
47	MU Jiahui, WONG Shao Ing, LI Qiang, et al. Fishbone-derived N-doped hierarchical porous carbon as an electrode material for supercapacitor[J]. Journal of Alloys and Compounds, 2020, 832: 154950.
48	NEAL Justin N, WESOLOWSKI David J, HENDERSON Douglas, et al. Ion distribution and selectivity of ionic liquids in microporous electrodes[J]. The Journal of Chemical Physics, 2017, 146(17): 174701.
49	PARK Suji, MAIER Claudia S, KOLEY Dipankar. Anodic stripping voltammetry on a carbon-based ion-selective electrode[J]. Electrochimica Acta, 2021, 390: 138855.
50	HU Jinbo, ZOU Xu U, STEIN Andreas, et al. Ion-selective electrodes with colloid-imprinted mesoporous carbon as solid contact[J]. Analytical Chemistry, 2014, 86(14): 7111-7118.
51	HU Jinbo, ZHAO Wenyang, Philippe BÜHLMANN, et al. Paper-based all-solid-state ion-sensing platform with a solid contact comprising colloid-imprinted mesoporous carbon and a redox buffer[J]. ACS Applied Nano Materials, 2018, 1(1): 293-301.
52	ANDREDAKIS George E, MOSCHOU Elizabeth A, MATTHAIOU Katherine, et al. Theoretical and experimental studies of metallated phenanthroline derivatives as carriers for the optimization of the nitrate sensor[J]. Analytica Chimica Acta, 2001, 439(2): 273-280.
53	VAMVAKAKI Maria, CHANIOTAKIS Nikolas A. Solid-contact ion-selective electrode with stable internal electrode[J]. Analytica Chimica Acta, 1996, 320(1): 53-61.
54	WEBER Andrew W, O'NEIL Glen D, KOUNAVES Samuel P. Solid contact ion-selective electrodes for in situ measurements at high pressure[J]. Analytical Chemistry, 2017, 89(9): 4803-4807.
55	DAI Runying, MA Xue, XU Quan, et al. Controllable synthesis of three-dimensional nitrogen-doped hierarchical porous carbon and its application in the detection of lead[J]. RSC Advances, 2019, 9(33): 18902-18908.
56	GULDI Dirk M. Fullerenes: three dimensional electron acceptor materials[J]. Chemical Communications, 2000(5): 321-327.
57	JANDA Pavel, KRIEG Torsten, DUNSCH Lothar. Nanostructuring of highly ordered C₆₀ films by charge transfer[J]. Advanced Materials, 1998, 10(17): 1434-1438.
58	XIE Qingshan, Eduardo PEREZ-CORDERO, ECHEGOYEN Luis. Electrochemical detection of C₆₀ ^6- and C₇₀ ^6-: enhanced stability of fullerides in solution[J]. Journal of the American Chemical Society, 1992, 114(10): 3978-3980.
59	KROTO H W, HEATH J R, OBRIEN S C, et al. Long carbon chain molecules in circumstellar shells[J]. The Astrophysical Journal Letters, 1987, 314: 352.
60	FOUSKAKI Maria, NIKOS Chaniotakis. Fullerene-based electrochemical buffer layer for ion-selective electrodes[J]. Analyst, 2008, 133(8): 1072-1075.
61	LI Jinghui, YIN Tanji, QIN Wei. An all-solid-state polymeric membrane Pb²⁺-selective electrode with bimodal pore C₆₀ as solid contact[J]. Analytica Chimica Acta, 2015, 876: 49-54.
62	YE Junjin, LI Fenghua, GAN Shiyu, et al. Using sp2-C dominant porous carbon sub-micrometer spheres as solid transducers in ion-selective electrodes[J]. Electrochemistry Communications, 2015, 50: 60-63.
63	ZHAO Lijun, JIANG Ying, WEI Huan, et al. In vivo measurement of calcium ion with solid-state ion-selective electrode by using shelled hollow carbon nanospheres as a transducing layer[J]. Analytical Chemistry, 2019, 91(7): 4421-4428.
64	JIANG Zidengya, XI Xin, QIU Shi, et al. Ordered mesoporous carbon sphere-based solid-contact ion-selective electrodes[J]. Journal of Materials Science, 2019, 54(21): 13674-13684.
65	JIANG Chengmei, YAO Yao, CAI Yalu, et al. All-solid-state potentiometric sensor using single-walled carbon nanohorns as transducer[J]. Sensors and Actuators B: Chemical, 2019, 283: 284-289.
66	Beata PACZOSA-BATOR. All-solid-state selective electrodes using carbon black[J]. Talanta, 2012, 93: 424-427.
67	MOUSAVI Maral P S, AINLA Alar, TAN Edward K W, et al. Ion sensing with thread-based potentiometric electrodes[J]. Lab on a Chip, 2018, 18(15): 2279-2290.
68	TIMOFEEV V V, LEVIN M B, STARIKOVA A A, et al. Solid-contact ion-selective electrodes with copper hexacyanoferrate in the transducer layer[J]. Russian Journal of Electrochemistry, 2018, 54(4): 400-408.
69	SAMSONOVA Elisaveta N, LUTOV Viktor M, MIKHELSON Konstantin N. Solid-contact ionophore-based electrode for determination of pH in acidic media[J]. Journal of Solid State Electrochemistry, 2009, 13(1): 69-75.
70	IVANOVA Nataliya M, PODESHVO Irina V, GOIKHMAN Mikhail Ya, et al. Potassium-selective solid contact electrodes with poly(amidoacid) Cu(I) complex, electron-ion exchanging resin and different sorts of carbon black in the transducer layer[J]. Sensors and Actuators B: Chemical, 2013, 186: 589-596.
71	Beata PACZOSA-BATOR. Ion-selective electrodes with superhydrophobic polymer/carbon nanocomposites as solid contact[J]. Carbon, 2015, 95: 879-887.
72	VEDIYAPPAN Veeramania, RAJESH Madhua, CHEN Shenming, et al. Heteroatom-enriched porous carbon/nickel oxide nanocomposites as enzyme-free highly sensitive sensors for detection of glucose. Sensors and Actuators B: Chemical, 2015, 221: 1384-1390.
73	KIM Dongwon, KIM Jong Min, JEON Youngmoo, et al. Novel two-step activation of biomass-derived carbon for highly sensitive electrochemical determination of acetaminophen[J]. Sensors and Actuators B: Chemical, 2018, 259: 50-58.
74	WANG Shuqi, WU Yongjin, GU Yang, et al. Wearable sweatband sensor platform based on gold nanodendrite array as efficient solid contact of ion-selective electrode[J]. Analytical Chemistry, 2017, 89(19): 10224-10231.

碳基材料	检测离子	检测限	稳定性	灵敏度
化学还原氧化石墨烯（CRGNO）	K⁺	10^-6.2mol/L	(12.6±1.1)μV/h	58.4mV/decade
还原型氧化石墨烯（RGO）	Ca²⁺	10^-6.2mol/L	10μV/h	29.5mV/decade
三维石墨烯海绵（3D GS）	Cu²⁺	2.5×10^-9mol/L	2μV/h	(28.6±0.7)mV/decade
石墨烯/金纳米颗粒	K⁺	10^-5.9mol/L	36μV/h	(59.6±0.2)mV/decade
单壁碳纳米管（SWCNTs）	K⁺	10^-6mol/L	27.4μV/h	58.1mV/decade
多壁碳纳米管（MWCNTs）	Na⁺	7.08×10^-7mol/L	—	58mV/decade
二茂铁功能化多壁碳纳米管（Fc-MWCNT）	K⁺	4×10^-7mol/L	15μV/h	—
三维有序大孔碳（3DOMC）	K⁺	10^-6.2mol/L	11.7μV/h	56.4mV/decade
空心碳纳米球（HCN）	Ca²⁺	10^-5mol/L	20μV/h	28mV/decade
有序介孔碳（OMC）	K⁺	10^-5.27mol/L	(28±1.9)μV/h	(63.5±0.6)mV/decade
碳黑（CB）	K⁺/Na⁺/Ca²⁺	10^-4mol/L	—	(59.2/59.2/29.6)mV/decade

碳基材料	检测离子	检测限	稳定性	灵敏度
化学还原氧化石墨烯（CRGNO）	K⁺	10^-6.2mol/L	(12.6±1.1)μV/h	58.4mV/decade
还原型氧化石墨烯（RGO）	Ca²⁺	10^-6.2mol/L	10μV/h	29.5mV/decade
三维石墨烯海绵（3D GS）	Cu²⁺	2.5×10^-9mol/L	2μV/h	(28.6±0.7)mV/decade
石墨烯/金纳米颗粒	K⁺	10^-5.9mol/L	36μV/h	(59.6±0.2)mV/decade
单壁碳纳米管（SWCNTs）	K⁺	10^-6mol/L	27.4μV/h	58.1mV/decade
多壁碳纳米管（MWCNTs）	Na⁺	7.08×10^-7mol/L	—	58mV/decade
二茂铁功能化多壁碳纳米管（Fc-MWCNT）	K⁺	4×10^-7mol/L	15μV/h	—
三维有序大孔碳（3DOMC）	K⁺	10^-6.2mol/L	11.7μV/h	56.4mV/decade
空心碳纳米球（HCN）	Ca²⁺	10^-5mol/L	20μV/h	28mV/decade
有序介孔碳（OMC）	K⁺	10^-5.27mol/L	(28±1.9)μV/h	(63.5±0.6)mV/decade
碳黑（CB）	K⁺/Na⁺/Ca²⁺	10^-4mol/L	—	(59.2/59.2/29.6)mV/decade

[1]	朱子翼, 张英杰, 董鹏, 孟奇, 曾晓苑, 章艳佳, 吉金梅, 和秋谷, 黎永泰, 李雪. 高性能钠离子电池负极材料的研究进展[J]. 化工进展, 2019, 38(05): 2222-2232.
[2]	李烁, 姚楠. 掺氮碳基材料在费托合成反应中的应用[J]. 化工进展, 2015, 34(11): 3933-3937.
[3]	刘贵, 宁平, 李凯, 汤立红, 宋辛, 王驰. 介质阻挡放电等离子体改性碳基材料研究进展[J]. 化工进展, 2015, 34(07): 1905-1912.