Conjugated schiff base polymer foam/macroporous carbon integrated electrode for electrochemical sensing

doi:10.1016/j.snb.2018.03.041

Sensors and Actuators B: Chemical

Volume 265, 15 July 2018, Pages 227-233

https://doi.org/10.1016/j.snb.2018.03.041 Get rights and content

Highlights

•
The novel 3D-KSCs/CSBP foam integrated electrode was proposed for the first time.
•
The crystalline CSBP presented in lamella structure with single atomic thickness and formed foam.
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Lots of small CuNPs with several nanometers were uniformly electrodeposited on CSBP.
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The glucose sensor based on 3D-KSC/CSBP/CuNPs electrode showed good performances.

Abstract

Conjugated Schiff base polymer (CSBP) foam was grown on three-dimensional macroporous kenaf stem-derived carbon (3D-KSCs/CSBP) integrated electrode via aldimine condensation between hydrazine anhydrous and terephthalaldehyde for the first time. The CSBP nanosheets with thickness of 0.5 nm forming CSBP foam on the 3D-KSC was used as supporting matrix to develop new electrode which owned low electrical resistance, wide potential window, rapid electron/mass transfer and good stability toward pH and temperature. Through the electrodeposition of Cu nanoparticles (CuNPs) on the surface of 3D-KSCs/CSBP integrated electrode, an original nonenzymatic glucose sensor was designed as an example to explore the practicability of 3D-KSCs/CSBP for electrochemical sensing. Owing to its high stability, hierarchically porous nanostructures, large specific surface as well as the good catalytic activity of CuNPs, glucose can be quantitatively detected ranging from 3.39 μM to 3.57 mM based on 3D-KSCs/CSBP/CuNPs- integrated electrode and the detection limit was 1.12 μM with a high sensitivity of 2.95 mA cm⁻² mM⁻¹. The 3D-KSCs/CSBP integrated electrode can be not only used to load metal or bimetallic NPs for glucose detection, but also employed as potential material for various filed including supercapacitors, biosensor and fuel cells.

Graphical abstract

Introduction

Electrochemical sensors are attracting increased interests owing to their convenient operating, low cost, high sensitivity along with facile miniaturization [[1], [2], [3]]. The performance of electrochemical sensors strongly depends on the electron/mass transfer between electrode surface and electroactive substances, background current of the modified electrode and effective surface concentration of electroactive substances [[4], [5], [6]]. Among these crucial factors, the effective surface concentration of electroactive substances plays a decisive role in the performance of electrochemical sensors [6]. Therefore, how to design and construct modified electrodes to increase the effective surface concentration of electroactive substances is very important for electrochemical sensors.

Some materials owning high active surface area, including graphene [7], carbon nanotube [8], hierarchical nanostructures [9,10], metal-organic frameworks (MOFs) [11,12], conjugated polymer nanostructures [13], etc, were proposed to modify electrodes. These materials were directly used as electroactive substances or as supporting matrix to load electroactive substances. Among these materials, conjugated polymer such as ployaniline (PANI) has attracted special attention due to the high specific surface area, strong absorption properties and superior electrical conductivity. The PANI modified electrode exhibited some enhanced electrochemical properties, such as increased amount of electroactive substances loaded on electrode surface, accelerated electron transfer, enhanced uniform distribution of electroactive substances, improved electrocatalytic activity and stability [14,15]. For example, a novel flexible electrochemical glucose sensor was developed on gold nanoparticles (NPs)/PANI arrays/carbon cloth and showed good performance [15]. However, PANI arrays were only composited of PANI nanowires with height about 200 nm and diameter about 100 nm. Similar to PANI, conjugated Schiff base polymer (CSBP) has also caught the eyes of researchers owing to the high thermal stability, good mechanical strength, electrical conductivity and remarkable photo- and electroluminescence [[16], [17], [18], [19]]. CSBP refers to a kind of polymer obtained by aldimine condensation. There are single bond CH double bond N groups in the main chain and so polyazomethines is another name of Schiff base polymers. In the past decade, Schiff base polymer has gradually become the candidate for photorefractive holographic materials [20], organic field effect transistors [21] and solar cells [22] due to their excellent nonlinear optical properties. Although these materials could increase the active surface area of the electrode greatly, unfortunately they were inevitably aggregated or fallen off from the electrode.

To avoid these defects, some materials such as carbon nanotube [8], PANI [23], MOFs [5,24], etc, were arrayed on three-dimensional macroporous kenaf stem-derived carbon (3D-KSCs) to make integrated electrode maintaining the porous structure [5,25]. The 3D-KSCs integrated electrode could provide an ultrahigh specific surface area which was beneficial to immobilize enough electroactive materials effectively. The loading of electroactive materials was also greatly promoted by those microporosities or defects inside the 3D-KSCs. Both the abundant porous nanostructures and the high conductivity enhanced the mass and electron transfer together [6,23]. Accordingly, the 3D-KSCs integrated electrode derived sensors provided good performances.

In this work, novel CSBP foam was grown on 3D-KSCs to form the 3D-KSCs/CSBP foam integrated electrode for the first time and CuNPs were subsequently electrodeposited on the surface of 3D-KSCs/CSBP to test its electrochemical sensing application. Owing to its ultra-high stability, hierarchically porous nanostructures, large specific surface as well as the excellent catalytic activity of CuNPs, the glucose sensor based on 3D-KSCs/CSBP/CuNPs integrated electrode showed good performances.

Section snippets

Materials

Kenaf stem (KS) was obtained from Futian farm (Ji’an, China). Terephthalaldehyde (90%), hydrazine anhydrous, 1,4-dioxane, glucose, glacial acetic acid, mannose, galactose, fructose, cysteine, uric acid (UA), KCl, NaCl, ascorbic acid (AA), dopamine (DA), CuCl2, K2SO4, KNO3, Na2SO3, etc, were obtained from Sinopharm Chemical Reagent Co., Ltd (Shanghai, China). Ultrapure water was purified by a Millipore-Q System (18.2 MΩ cm).

Preparation of the CSBP

The novel CSBP was synthesized via aldimine condensation between

Characteristics of the 3D-KSCs/CSBP/CuNPs integrated electrode

The formation of the CSBP and 3D-KSCs/CSBP was firstly confirmed by FTIR (Fig. S1, Supporting Information). For the CSBP, peaks at 3447 cm⁻¹, 1690 cm⁻¹, 1623 cm⁻¹, 1420 cm⁻¹, 1300 cm⁻¹ and 1215 cm⁻¹ were ascribed to single bond OH stretching vibration of water, C double bond N stretching vibration, CC stretching vibration of benzene ring, NN stretching vibration and the CH bending vibration of benzene ring and CN bond, respectively [26,27]. The disappearance of CO and the appearance of CN bond clearly confirmed the

Conclusions

In conclusion, 3D-KSCs/CSBP integrated electrode was proposed for the first time by the growth of CSBP foam on 3D-KSCs and CuNPs were electrodeposited subsequently on the surface of 3D-KSC/CSBP to develop a nonenzymatic glucose sensor. The crystalline CSBP presented in a lamella with single atomic thickness and these lamella formed foam structure on the 3D-KSC surface. Lots of small CuNPs with several nanometers was subsequently uniformly electrodeposited on the surface of CSBP based on the

Acknowledgements

This work was financially supported by National Natural Science Foundation of China (21765009, 21465014, 21465015 and 21665012), Natural Science Foundation of Jiangxi Province (20143ACB21016), the Ground Plan of Science and Technology Projects of Jiangxi Educational Committee (KJLD14023) and the Open Project Program of Key Laboratory of Functional Small Organic Molecule, Ministry of Education, Jiangxi Normal University (No. KLFS-KF-201708; KLFS-KF-201713).

Linyu Wang received her science bachelor in chemistry in 2016 from Jiangxi Normal University, China. She is working for her master’s degree in Jiangxi Normal University, China. Her research interests are biosensor.

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Coucong Gong received her science bachelor in chemistry in 2014 from Jiangxi Normal University, China. She is working for her master’s degree in Jiangxi Normal University, China. Her research interests are electrochemical biosensor.

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Mengli Xu received her science bachelor in chemistry in 2016 from Jiangxi Normal University, China. She is working for her master’s degree in Jiangxi Normal University, China. Her research interests are electrochemical sensor.

Guanghua He received his science bachelor in chemistry in 2013 from Jiangxi Normal University, China. He is working for his PhD’s degree in Jiangxi Normal University, China. His research interests are nanomaterials-based sensor.

Li Wang received her Ph.D. in analytical chemistry from the Changchun Institute of Applied Chemistry, Chinese Academy of Science, China. She is currently working as a professor at Jiangxi Normal University. Her current research interest is focused on biosensors.

Yonghai Song received his Ph.D. in analytical chemistry from the Changchun Institute of Applied Chemistry, Chinese Academy of Science, China. He is currently working as a professor at Jiangxi Normal University. His current research interests focus on biosensors.

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Conjugated schiff base polymer foam/macroporous carbon integrated electrode for electrochemical sensing

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Materials

Preparation of the CSBP

Characteristics of the 3D-KSCs/CSBP/CuNPs integrated electrode

Conclusions

Acknowledgements

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