- Nano Express
- Open Access
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.
- Hollow porous architecture
- Coordinating etching and precipitating
- Electrochemical sensor
- Glucose detection
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.
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.
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Open AccessThis article is distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made.
- Nai JW, Wang SQ, Bai Y, Guo L (2013) Amorphous Ni(OH)2 nanoboxes: fast fabrication and enhanced sensing for glucose. Small 9:3147-3152Google Scholar
- Noh HB, Lee KS, Chandra P, Won MS, Shim YB (2012) Application of a Cu-Co alloy dendrite on glucose and hydrogen peroxide sensors. Electrochim Acta 61:36–43View ArticleGoogle Scholar
- Wang MQ, Ye C, Bao SJ, Xu MW, Zhang Y, Wang L, Ma XQ, Guo J, Li CM (2017) Nanostructured cobalt phosphates as excellent biomimetic enzymes to sensitively detect superoxide anions released from living cells. Biosens Bioelectron 87:998–1004View ArticleGoogle Scholar
- Bao SJ, Li CM, Zang JF, Cui XQ, Qiao Y, Guo J (2008) New nanostructured TiO2 for direct electrochemistry and glucose sensor applications. Adv Funct Mater 18:591–599View ArticleGoogle Scholar
- Wang J (2008) Electrochemical glucose biosensors. Chem Rev 108:814–825View ArticleGoogle Scholar
- Gouveia-Carida C, Pauliukaite R, Brett CMA (2008) Development of electrochemical oxidase biosensors based on carbon nanotube-modified carbon film electrodes for glucose and ethanol. Electrochim Acta 53:6732–6739View ArticleGoogle Scholar
- Kang X, Mai Z, Zou X, Cai P, Mo J (2007) A sensitive nonenzymatic glucose sensor in alkaline media with a copper nanocluster/multiwall carbon nanotube-modified glassy carbon electrode. Anal Biochem 363:143–150View ArticleGoogle Scholar
- Feng D, Wang F, Chen ZL (2009) Electrochemical glucose sensor based on one-step construction of gold nanoparticle–chitosan composite film. Sensors Actuators B 138:539–544View ArticleGoogle Scholar
- Başkaya G, Yıldız Y, Savk A, Okyay TO, Eriş S, Sert H, Şen F (2017) Rapid, sensitive and reusable detection of glucose by highly monodisperse nickel nanoparticles decorated functionalized multi-walled carbon nanotubes. Biosens Bioelectron 91:728–733View ArticleGoogle Scholar
- Chen C, Xie QJ, Yang DW, Xiao HL, Fu YC, Tan YM, Yao SZ (2013) Recent advances in electrochemical glucose biosensors: a review. RSC Adv 3:4473–4491Google Scholar
- Heller A, Feldman B (2008) Electrochemical glucose sensors and their applications in diabetes management. Chem Rev 108:2482–2505View ArticleGoogle Scholar
- Scognamiglio V (2013) Nanotechnology in glucose monitoring: advances and challenges in the last 10 years. Biosens Bioelectron 47:12–25View ArticleGoogle Scholar
- Kaneti YV, Tang J, Salunkhe RR, Jiang XC, Yu A, Wu KCW, Yamauchi Y (2017) Nanoarchitectured design of porous materials and nanocomposites from metal-organic frameworks. Adv Mater 29:1604898–1604938View ArticleGoogle Scholar
- Xu Y, Tu WG, Zhang BW, Yin SM, Huang YZ, Kraft M, Xu R (2017) Nickel nanoparticles encapsulated in few-layer nitrogen-doped graphene derived from metal-organic frameworks as efficient bifunctional electrocatalysts for overall water splitting. Adv Mater 29:1605957–1605965View ArticleGoogle Scholar
- Bak SM, Kim KH, Lee CW, Kim KB (2011) Mesoporous nickel/carbon nanotube hybrid material prepared by electroless deposition. J Mater Chem 21:1984–1990View ArticleGoogle Scholar
- Liu H, Wang GX, Liu J, Qiao SZ, Ahnc H (2011) Highly ordered mesoporous NiO anode material for lithium ion batteries with an excellent electrochemical performance. J Mater Chem 21:3046–3052View ArticleGoogle Scholar
- Ci SQ, Huang TZ, Wen ZH, Cui SM, Mao S, Steeber DA, Chen JH (2014) Nickel oxide hollow microsphere for non-enzyme glucose detection. Biosens Bioelectron 54:251–257View ArticleGoogle Scholar
- Cao CY, Guo W, Cui ZM, Song WG, Cai W (2011) Microwave-assisted gas/liquid interfacial synthesis of flowerlike NiO hollow nanosphere precursors and their application as supercapacitor electrodes. J Mater Chem 21:3204–3209View ArticleGoogle Scholar
- Tian LL, Zhong XH, Hu WP, Liu BT, Li YF (2014) Fabrication of cubic PtCu nanocages and their enhanced electrocatalytic activity towards hydrogen peroxide. Nanoscale Res Lett 9:1–5View ArticleGoogle Scholar
- Kim SI, Lee JS, Ahn HJ, Song HK, Jang JH (2013) Facile route to an efficient NiO supercapacitor with a three-dimensional nanonetwork morphology. ACS Appl Mater Interfaces 5:1596–1603View ArticleGoogle Scholar
- Liang K, Tang XZ, Hu WC (2012) High-performance three-dimensional nanoporous NiO film as a supercapacitor electrode. J Mater Chem 22:11062–11067View ArticleGoogle Scholar
- Chigane M, Ishikawa M (1998) XRD and XPS characterization of electrochromic nickel oxide thin films prepared by electrolysis-chemical deposition. J Chem Soc Faraday Trans 94:3665–3670View ArticleGoogle Scholar
- Biesinger MC, Payne BP, Lau LWM, Gerson A, Smart RSC (2009) X-ray photoelectron spectroscopic chemical state quantification of mixed nickel metal, oxide and hydroxide systems. Surf Interface Anal 41:324–332View ArticleGoogle Scholar
- Varghese B, Reddy MV, Wu ZY, Lit CS, Hoong TC, Rao GVS, Chowdari BVR, Wee ATS, Lim CT, Sow CH (2008) Fabrication of NiO nanowall electrodes for high performance lithium ion battery. Chem Mater 20:3360–3367View ArticleGoogle Scholar
- Zhu H, Gu L, Yu D, Sun YJ, Wan M, Zhang M, Wang L, Wu WW, Yao JM, ML D, Guo SJ (2017) The marriage and integration of nanostructures with different dimensions for synergistic electrocatalysis. Energy Environ Sci 10:321–330View ArticleGoogle Scholar
- Bao HZ, Zhang ZH, Hua Q, Huang WX (2014) Compositions, structures and catalytic activities of CeO2@Cu2O nanocomposites prepared by the template-assisted method. Langmuir 30:6427–6436View ArticleGoogle Scholar
- Sun SD, Yang ZM (2014) Cu2O-templated strategy for synthesis of definable hollow architectures. Chem Commun 50:7403–7415View ArticleGoogle Scholar
- Sohn JH, Cha HG, Kim CW, Kim DK, Kang YS (2013) Fabrication of hollow metal oxide nanocrystals by etching cuprous oxide with metal(II) ions: approach to the essential driving force. Nano 5:11227–11233Google Scholar
- Yang P, Tong XL, Wang GZ, Gao Z, Guo XY, Qin Y (2015) NiO/SiC nanocomposite prepared by atomic layer deposition used as a novel electrocatalyst for non-enzymatic glucose sensing. ACS Appl Mater Interfaces 7:4772–4778View ArticleGoogle Scholar
- Li M, Bo XJ, Mu ZC, Zhang YF, Guo LP (2014) Electrodeposition of nickel oxide and platinum nanoparticles on electrochemically reduced graphene oxide film as a nonenzymatic glucose sensor. Sensors Actuators B 192:261–268View ArticleGoogle Scholar
- Safavi A, Maleki N, Farjami E (2009) Fabrication of a glucose sensor based on a novel nanocomposite electrode. Biosens Bioelectron 24:1655–1660View ArticleGoogle Scholar
- Wu CH, Deng SX, Wang H, Sun YX, Liu JB, Yan H (2014) Preparation of novel three-dimensional NiO/Ultrathin derived graphene hybrid for supercapacitor applications. ACS Appl Mater Interfaces 6:1106–1112View ArticleGoogle Scholar
- Kong CC, Tang LL, Zhang XZ, Sun SD, Yang SC, Song XP, Yang ZM (2014) Templating synthesis of hollow CuO polyhedron and its application for nonenzymatic glucose detection. J Mater Chem A 2:7306–7312View ArticleGoogle Scholar
- Tyagi M, Tomar M, Gupta V (2014) Glad assisted synthesis of NiO nanorods for realization of enzymatic reagentless urea biosensor. Biosens Bioelectron 52:196–201View ArticleGoogle Scholar
- Xia KD, Yang C, Chen YL, Tian LL, Su YY, Wang JB, Li L (2017) In situ fabrication of Ni(OH)2 flakes on Ni foam through electrochemical corrosion as high sensitive and stable binder-free electrode for glucose sensing. Sensors Actuators B 240:979–987View ArticleGoogle Scholar
- Niu XH, Li X, Pan JM, He YF, Qiu FX, Yan YS (2016) Recent advances in non-enzymatic electrochemical glucose sensors based on non-precious transition metal materials: opportunities and challenges. RSC Adv 6:84893–84905View ArticleGoogle Scholar
- Liu MM, Liu R, Chen W (2013) Graphene wrapped Cu2O nanocubes: non-enzymatic electrochemical sensors for the detection of glucose and hydrogen peroxide with enhanced stability. Biosens Bioelectron 45:206–212View ArticleGoogle Scholar
- Wang L, Lu XP, Wen CJ, Xie YZ, Miao LF, Chen SH, Li HB, Li P, Song YH (2015) One-step synthesis of Pt-NiO nanoplate array/reduced graphene oxide nanocomposites for nonenzymatic glucose sensing. J Mater Chem A 3:608–616View ArticleGoogle Scholar
- Li M, Bo XJ, Mu ZC, Zhang YF, Guo LP (2014) Electrodeposition of nickel oxide and platinum nanoparticles on electrochemically reduced graphene oxide film as a nonenzymatic glucose sensor. Sensors Actuators B Chem 192:261–268View ArticleGoogle Scholar
- Soomro RA, Ibupoto ZH, Sirajuddin, Willander M (2015) Electrochemical sensing of glucose based on novel hedgehog-like NiO nanostructures. Sens Actuators B 209:966–974View ArticleGoogle Scholar
- Ding Y, Liu YX, Zhang LC, Wang Y, Bellagamba M, Parisi J, Li CM, Lei Y (2011) Sensitive and selective nonenzymatic glucose detection using functional NiO-Pt hybrid nanofibers. Electrochim Acta 58:209–214View ArticleGoogle Scholar
- Ding Y, Wang Y, Su LA, Zhang H, Lei Y (2010) Preparation and characterization of NiO-Ag nanofibers, NiO nanofibers, and porous Ag: towards the development of a highly sensitive and selective non-enzymatic glucose sensor. J Mater Chem 20:9918–9926View ArticleGoogle Scholar
- Reddy YAK, Ajitha B, Reddy PS, Reddy MSP, Lee JH (2014) Effect of substrate temperature on structural, optical and electrical properties of sputtered NiO-Ag nanocrystalline thin films. Electron Mater Lett 5:907–913View ArticleGoogle Scholar
- Li CC, Liu YL, Li LM, Du ZF, Xu SJ, Zhang M, Yin XM, Wang TH (2008) A novel amperometric biosensor based on NiO hollow nanospheres for biosensing glucose. Talanta 77:455–459View ArticleGoogle Scholar
- Ding Y, Wang Y, Zhang LC, Zhang H, Lei Y (2012) Preparation, characterization and application of novel conductive NiO-CdO nanofibers with dislocation feature. J Mater Chem 22:980–986View ArticleGoogle Scholar
- Zhang XJ, Gu AX, Wang GF, Huang Y, Ji HQ, Fang B (2011) Porous Cu-NiO modified glass carbon electrode enhanced nonenzymatic glucose electrochemical sensors. Analyst 136:5175–5180View ArticleGoogle Scholar