Sensitive Nonenzymatic Electrochemical Glucose Detection Based on Hollow Porous NiO
© The Author(s). 2018
Received: 6 November 2017
Accepted: 6 December 2017
Published: 9 January 2018
Transition metal oxides (TMOs) have attracted extensive research attentions as promising electrocatalytic materials. Despite low cost and high stability, the electrocatalytic activity of TMOs still cannot satisfy the requirements of applications. Inspired by kinetics, the design of hollow porous structure is considered as a promising strategy to achieve superior electrocatalytic performance. In this work, cubic NiO hollow porous architecture (NiO HPA) was constructed through coordinating etching and precipitating (CEP) principle followed by post calcination. Being employed to detect glucose, NiO HPA electrode exhibits outstanding electrocatalytic activity in terms of high sensitivity (1323 μA mM−1 cm−2) and low detection limit (0.32 μM). The excellent electrocatalytic activity can be ascribed to large specific surface area (SSA), ordered diffusion channels, and accelerated electron transfer rate derived from the unique hollow porous features. The results demonstrate that the NiO HPA could have practical applications in the design of nonenzymatic glucose sensors. The construction of hollow porous architecture provides an effective nanoengineering strategy for high-performance electrocatalysts.
Detection of glucose with fast, accurate, and low-cost process is importance for clinical biochemistry, pharmaceutical analysis, food industry, and environmental monitoring [1–3]. Among the multitudinous techniques, electrochemical detection has been considered as one of the most convenient approach owing to its high sensitivity, low cost, and attractive lower detection limit [4–6]. However, the common glucose oxidase-based electrochemical sensors are restricted by the drawback of insufficient stability originating from the nature of enzymes [7–9]. To address these issues, earth-abundant electrocatalysts based on TMOs were recommended due to their lower cost, physicochemical stability, and redox electroactivity [10–12]. However, the overall electrocatalytic activity of conventional TMOs is still far away from the requirements of applications. It is still a challenge to rationally design high-active TMO electrocatalysts for glucose.
Generally, the process of kinetics plays a decisive role in electrocatalytic activity for established electrocatalytic materials. Inspired by the intimate connection between kinetics and microstructures, improved electrocatalytic activity can be achieved by the engineering of microstructures, including surface area, pore structure, and architecture features [13, 14]. The porous structure offers large specific surface area (SSA) and provides amounts of active sites. Furthermore, the porous structure also affords enough diffusion channels for analyte and intermediate products, which are beneficial for mass transport process [15, 16]. On the other hand, hollow structures combining functional shells and inner voids can offer larger electrolyte-electrode contact area and reduce the length for both mass and electron transport . Furthermore, the available inner cavities effectively prevent electroactive nanoparticles from aggregation and accommodate the volume change and structural strain accompanied with repeated measurements . In conclusion, high-active TMO electrocatalysts can be acquired through the design of hollow porous architecture.
As a typical transition metal oxide, NiO was reported as an efficient catalyst for electrooxidation of glucose due to the redox couple of Ni3+/Ni2+ in alkaline medium, implying potential applications in electrochemical glucose sensor. In this work, cubic NiO HPA was constructed through a Cu2O-templated coordinating etching and precipitating (CEP) method and post calcination. The hollow porous structure provides large SSA, well-defined interior voids, abundant ordered transfer channels, and high electron transfer efficiency. Being employed to detect glucose, NiO HPA electrode presents higher sensitivity and lower detection limit compared to broken NiO HPA (NiO BHPA), demonstrating advantages of the hollow porous architecture. This facile strategy to construct hollow porous architecture provides a valid method in the development of highly efficient nanomaterials for electrochemical sensors.
CuCl2·2H2O, NiCl2·6H2O, Na2S2O3·5H2O, polyvinylpyrrolidone (PVP, Mw = 40,000), and NaOH were purchased from Chengdu Kelong. Glucose (Glu.), lactose (Lact.), sucrose (Sucr.), fructose (Fruc.), L-ascorbic acid (AA), uric acid (UA), and Nafion solution (5 wt% in mixture of lower aliphatic alcohols and water) were purchased from Sigma-Aldrich without further purification.
Synthesis of Cu2O Template
The cubic Cu2O templates were synthesized according to our previous work . In this typical procedure, 20 ml NaOH (2 M) was added dropwise into 200 mL CuCl2·2H2O (10 mM) under stirring at 55 °C. After 0.5 h, 4 mL AA (0.6 M) was introduced dropwise into the above solution. The suspension was further aged for 3 h and washed with water several times by centrifugation. The XRD pattern and SEM and TEM images are shown in Additional file 1: Figure S1.
Synthesis of NiO HPA
NiO HPA was synthesized by a CEP method. First, Cu2O (10 mg) and NiCl2·6H2O (3 mg) were dispersed into 10 mL ethanol-water mixed solvent (volume ratio = 1:1) for 7 min by ultrasonication. Then, PVP (0.33 g) was added into the solution with vigorous agitation for 30 min. Four milliliters Na2S2O3 (1 M) was dropped into the system; the reaction was proceeded at room temperature for 3 h until the color of the suspension changed from red to light green. The Ni(OH)2 precursor was washed several times by warm ethanol-water and dried at room temperature. Finally, NiO HPA was successively obtained under an air atmosphere at 400 °C for 2 h with a slow ramp rate of 1 °C/min. NiO BHPA was obtained through strong ultrasonic treatment of NiO HPA for 2 h.
The composition and structure of the products were characterized by X-ray diffraction (XRD, Rigaku D/Max-2400). The composition was further analyzed by the X-ray photoelectron spectroscopy (XPS, ESCALAB250Xi) with the C 1s peaks at 284.8 eV as an internal standard. The morphologies and microstructures of the products were observed using field emission scanning electron microscope (FESEM, FEI Quanta 250, Zeiss Gemini 500) and high-resolution transmission electron microscope (HRTEM, FEI F20). Brunauer-Emmett-Teller (BET, Belsort-max) was applied to analyze the specific surface area and pore structure.
All electrochemical measurements were operated in 0.1 M NaOH on μIII Autolab electrochemical workstation. A three-electrode configuration with NiO HPA (or NiO BHPA) modified glassy carbon electrode (GCE, Ф = 3 mm) as the working electrodes and Ag/AgCl (in saturated KCl) and platinum disk electrode (Ф = 2 mm) as the reference electrode and counter electrode, respectively. Typically, GCE was polished with alumina slurry (3, 0.5, and 0.05 μm). Then, the NiO HPA (10 mg) was dissolved into a mixture of 0.1 mL Nafion and 0.9 mL distilled water. Finally, 5 μL of the mixture was dropped onto the pretreated GCE (70.77 μg/cm2) and dried at room temperature. NiO BHPA-modified GCE was also prepared under the same condition to verify the advantages of NiO HPA. The modified electrodes were measured by cyclic voltammetry (CV), chronoamperometry (CA), and electrochemical impedance spectroscopy (EIS) to evaluate its electrocatalytic activity. EIS measurements were carried out over the frequency range between 0.01–100 kHz with a perturbation amplitude of 5 mV versus the open-circle potential.
Results and Discussion
As shown above, OH− plays an important role in the electrocatalytic reaction. Obviously, alkaline medium accelerates the redox of Ni2+/Ni3+ compared to neutral medium (Additional file 1: Figure S4), leading to higher electrocatalytic activity.
Nyquist plots of NiO HPA and NiO BHPA electrodes were displayed in Fig. 5b. Each plot is characterized by a semicircle in the high-frequency region and a straight line in the low-frequency region. Generally, the intercept on the real axis represents the solution resistance (Rs), which is composed of intrinsic resistance, ionic resistance, and contact resistance. The semicircle diameter related to electron transfer resistance is represented by Rct. As shown in Additional file 1: Table S3, NiO HPA electrode exhibits smaller Rs and Rct than NiO BHPA. The facts can be attributed to the beneficial electron transfer kinetics derived from the hollow feature. The slope of the impedance plot in the low frequency range corresponds to the Warburg impedance (Zw), which represents the diffusive resistance . It is clear that NiO HPA favors the diffusion kinetics; however, the NiO BHPA hinders the diffusion of electrolyte. This can be ascribed to the destruction of the ordered diffusion channels after ultrasonic. On the basis of above EIS discussions, NiO HPA electrode is more beneficial for both electron and mass transfer kinetics compared to the broken sample, implying the advantages of NiO HPA as an electrocatalyst for glucose.
The kinetics of NiO HPA electrode was determined from the CVs with different scan rates in 1 mM glucose solution (Fig. 5c). As depicted in Fig. 5d, the anodic and cathodic peak currents are proportional to the square root of scan rates, demonstrating a typical diffusion-controlled dynamic process. Furthermore, no significant positive/negative shift is observed for anodic/cathodic peak, implying unimpeded diffusion kinetics originated from the hollow porous structure.
The Selectivity, Reproducibility, and Stability of NiO HPA Electrode
Comparison of researched electrode with reported nonenzymatic glucose sensors based on NiO
Sensitivity (μA mM−1 cm−2)
Linear range (mM)
Up to 3.67
Up to 0.59
Up to 2.63
NiO hollow nanospheres
Up to 6.37
Detection of Glucose in Human Serum
Detection of glucose in human serum
Measured by medical equipment (mM)
Measured by NiO (mM)
After adding (mM)
In summary, we have successfully fabricated a NiO HPA electrocatalyst for glucose through a CEP method. The NiO HPA offers large SSA, ordered pore structure, and short electronic transfer route, which are beneficial for electrocatalytic kinetics. As a nonenzymatic glucose detection electrode, NiO HPA exhibits higher sensitivity of 1323 μA mM−1 cm−2 and lower LOD of 0.32 μM compared to NiO BHPA. In the term of selectivity, less than 8.7% interference is investigated for the common interfering species. Simultaneously, NiO HPA electrode retains 89.02% of its original response after 30 days. In addition, the designed NiO HPA was successfully applied to detect glucose in human serum. NiO HPA presents accredited stability and practicability compared to medical equipment. The design of hollow porous architecture paves a high efficient way to obtain low cost and high-performance electrocatalysts for glucose.
This work was financially supported by the National Natural Science Foundation of China (21403020, 51503022), Basic and Frontier Research Program of Chongqing Municipality (cstc2016jcyjAX0014, cstc2016jcyjA0367, cstc2015jcyjA50036, CSTC2015JCYJBX0126, CSTC2016SHMSZX20001), Scientific and Technological Research Program of Chongqing Municipal Education Commission (KJ1601133, KJ1601104), Open Foundation of State Key Laboratory of Electronic Thin Films and Integrated Devices (KFJJ201507), and Chongqing University of Arts and Sciences (M2017ME20).
GGH and LLT designed the experiment and wrote the paper. JKZ and WRP completed the synthesis of samples. SPW and HQY carried out the series characterization of the nanocomposites. YYS and YHC did the analysis of the data. LL gives some revision for the grammar of the manuscript. All authors read and approved the final manuscript.
The authors declare that they have no competing interests.
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