Abstract
Uniform, ordered mesoporous ZnCo2O4 (meso-ZnCo2O4) nanospheres were successfully synthesized using a sacrificing template method. The meso-ZnCo2O4 nanospheres were used for the first time for H2O2 biosensing and in glucose biofuel cells (GBFCs) as an enzyme mimic. The meso-ZnCo2O4 nanospheres not only exhibited excellent catalytic performance in the H2O2 sensor, achieving a high sensitivity (658.92 μA·mM–1·cm–2) and low detection limit (0.3 nM at signal-to-noise ratio (S/N) = 3), but also performed as an excellent cathode material in GBFCs, resulting in an open circuit voltage of 0.83 V, maximum power density of 0.32 mW·cm–2, and limiting current density of 1.32 mA·cm–2. The preeminent catalytic abilities to H2O2 and glucose may be associated with the large specific surface area of the mesoporous structure in addition to the intrinsic catalytic activity of ZnCo2O4. These significant findings provide a successful basis for developing methods for the supersensitive detection of H2O2 and enriching catalytic materials for biofuel cells.
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Yao, S. J.; Guvench, S.; Guvench, M. G.; Kuller, A. E.; Chan, L. T.; Wolfson, S. K., Jr. Glucose sensing in the low and negative region: Utilization of a thin-film electrode. J. Electroanal. Chem. Interfacial Electrochem. 1991, 321, 211–222.
Stahl, S. S. Palladium-catalyzed oxidation of organic chemicals with O2. Science 2005, 309, 1824–1826.
Yuhashi, N.; Tomiyama, M.; Okuda, J.; Igarashi, S.; Ikebukuro, K.; Sode, K. Development of a novel glucose enzyme fuel cell system employing protein engineered PQQ glucose dehydrogenase. Biosens. Bioelectron. 2005, 20, 2145–2150.
Gu, J.; Zhang, Y. W.; Tao, F. Shape control of bimetallic nanocatalysts through well-designed colloidal chemistry approaches. Chem. Soc. Rev. 2012, 41, 8050–8065.
Zhang, E. H.; Yu, X.; Ci, S. Q.; Jia, J. C.; Wen, Z. H. Porous Co3O4 hollow nanododecahedra for nonenzymatic glucose biosensor and biofuel cell. Biosens. Bioelectron. 2016, 81, 46–53.
Ci, S. Q.; Wen, Z. H.; Mao, S.; Hou, Y.; Cui, S. M.; He, Z.; Chen, J. H. One-pot synthesis of high-performance Co/ graphene electrocatalysts for glucose fuel cells free of enzymes and precious metals. Chem. Commun. 2015, 51, 9354–9357.
Liu, M. M.; Liu, R.; Chen, W. Graphene wrapped Cu2O nanocubes: Non-enzymatic electrochemical sensors for the detection of glucose and hydrogen peroxide with enhanced stability. Biosens. Bioelectron. 2013, 45, 206–212.
Hua, M. Y.; Chen, H. C.; Tsai, R. Y.; Leu, Y. L.; Liu, Y. C.; Lai, J. T. Synthesis and characterization of carboxylated polybenzimidazole and its use as a highly sensitive and selective enzyme-free H2O2 sensor. J. Mater. Chem. 2011, 21, 7254–7262.
Kuwahara, T.; Ohta, H.; Kondo, M.; Shimomura, M. Immobilization of glucose oxidase on carbon paper electrodes modified with conducting polymer and its application to a glucose fuel cell. Bioelectrochemistry 2008, 74, 66–72.
Hu, L. H.; Peng, Q.; Li, Y. D. Selective synthesis of Co3O4 nanocrystal with different shape and crystal plane effect on catalytic property for methane combustion. J. Am. Chem. Soc. 2008, 130, 16136–16137.
Xiao, X. L.; Liu, X. F.; Zhao, H.; Chen, D. F.; Liu, F. Z.; Xiang, J. H.; Hu, Z. B.; Li, Y. D. Facile shape control of Co3O4 and the effect of the crystal plane on electrochemical performance. Adv. Mater. 2012, 24, 5762–5766.
Kuo, C. C.; Lan, W. J.; Chen, C. H. Redox preparation of mixed-valence cobalt manganese oxide nanostructured materials: Highly efficient noble metal-free electrocatalysts for sensing hydrogen peroxide. Nanoscale 2014, 6, 334–341.
Wu, M. Y.; Meng, S. J.; Wu, Q.; Si, W. L.; Huang, W.; Dong, X. C. Nickel–cobalt oxide decorated three-dimensional graphene as an enzyme mimic for glucose and calcium detection. ACS Appl. Mater. Interfaces 2015, 7, 21089–21094.
Sun, C. C.; Yang, J.; Dai, Z. Y.; Wang, X. W.; Zhang, Y. F.; Li, L. Q.; Chen, P.; Huang, W.; Dong, X. C. Nanowires assembled from MnCo2O4@C nanoparticles for water splitting and all-solid-state supercapacitor. Nano Res. 2016, 9, 1300–1309.
Guan, B. K.; Guo, D.; Hu, L. L.; Zhang, G. H.; Fu, T.; Ren, W. J.; Li, J. D.; Li, Q. H. Facile synthesis of ZnCo2O4 nanowire cluster arrays on Ni foam for high-performance asymmetric supercapacitors. J. Mater. Chem. A 2014, 2, 16116–16123.
Zhao, R. Z.; Li, Q.; Wang, C. X.; Yin, L. W. Highly ordered mesoporous spinel ZnCo2O4 as a high-performance anode material for lithium-ion batteries. Electrochim. Acta 2016, 197, 58–67.
Sharma, Y.; Sharma, N.; Subba Rao, G. V.; Chowdari, B. V. R. Nanophase ZnCo2O4 as a high performance anode material for Li-ion batteries. Adv. Funct. Mater. 2007, 17, 2855–2861.
Luo, W.; Hu, X. L.; Sun, Y. M.; Huang, Y. H. Electrospun porous ZnCo2O4 nanotubes as a high-performance anode material for lithium-ion batteries. J. Mater. Chem. 2012, 22, 8916–8921.
Hu, L. L.; Qu, B. H.; Li, C. C.; Chen, Y. J.; Mei, L.; Lei, D. N.; Chen, L. B.; Li, Q. H.; Wang, T. H. Facile synthesis of uniform mesoporous ZnCo2O4 microspheres as a highperformance anode material for Li-ion batteries. J. Mater. Chem. A 2013, 1, 5596–5602.
Liu, B.; Liu, B. Y.; Wang, Q. F.; Wang, X. F.; Xiang, Q. Y.; Chen, D.; Shen, G. Z. New energy storage option: Toward ZnCo2O4 nanorods/nickel foam architectures for highperformance supercapacitors. ACS Appl. Mater. Interfaces 2013, 5, 10011–10017.
Zhou, G.; Zhu, J.; Chen, Y. J.; Mei, L.; Duan, X. C.; Zhang, G. H.; Chen, L. B.; Wang, T. H.; Lu, B. G. Simple method for the preparation of highly porous ZnCo2O4 nanotubes with enhanced electrochemical property for supercapacitor. Electrochim. Acta 2014, 123, 450–455.
Cheng, J. B.; Lu, Y.; Qiu, K. W.; Yan, H. L.; Hou, X. Y.; Xu, J. Y.; Han, L.; Liu, X. M.; Kim, J.-K.; Luo, Y. S. Mesoporous ZnCo2O4 nanoflakes grown on nickel foam as electrodes for high performance supercapacitors. Phys. Chem. Chem. Phys. 2015, 17, 17016–17022.
Park, H. J.; Kim, J.; Choi, N.-J.; Song, H.; Lee, D.-S. Nonstoichiometric Co-rich ZnCo2O4 hollow nanospheres for high performance formaldehyde detection at ppb levels. ACS Appl. Mater. Interfaces 2016, 8, 3233–3240.
Anu Prathap, M. U.; Wei, C.; Sun, S. G.; Xu, Z. J. A new insight into electrochemical detection of eugenol by hierarchical sheaf-like mesoporous NiCo2O4. Nano Res. 2015, 8, 2636–2645.
Zhu, M. Y.; Meng, D. H.; Wang, C. J.; Diao, G. W. Facile fabrication of hierarchically porous CuFe2O4 nanospheres with enhanced capacitance property. ACS Appl. Mater. Interfaces 2013, 5, 6030–6037.
Li, J. F.; Xiong, S. L.; Liu, Y. R.; Ju, Z. C.; Qian, Y. T. High electrochemical performance of monodisperse NiCo2O4 mesoporous microspheres as an anode material for Li-ion batteries. ACS Appl. Mater. Interfaces 2013, 5, 981–988.
Zhang, Z.; Liu, X. Q.; Wu, Y.; Zhao, H. Y. Graphene modified Li2FeSiO4/C composite as a high performance cathode material for lithium-ion batteries. J. Solid State Electrochem. 2015, 19, 469–475.
Shen, M. J.; Zhang, Z.; Ding, Y. P. Synthesizing NiAl-layered double hydroxide microspheres with hierarchical structure and electrochemical detection of hydroquinone and catechol. Microchem. J. 2016, 124, 209–214.
He, C.; Liu, X. H.; Shi, J. W.; Ma, C. Y.; Pan, H.; Li, G. L. Anionic starch-induced Cu-based composite with flake-like mesostructure for gas-phase propanal efficient removal. J. Colloid Interface Sci. 2015, 454, 216–225.
Deng, W. F.; Yuan, X. Y.; Tan, Y. M.; Ma, M.; Xie, Q. J. Three-dimensional graphene-like carbon frameworks as a new electrode material for electrochemical determination of small biomolecules. Biosens. Bioelectron. 2016, 85, 618–624.
Wang, D. S.; Zhao, P.; Li, Y. D. General preparation for Pt-based alloy nanoporous nanoparticles as potential nanocatalysts. Sci. Rep. 2011, 1, 37.
Kleitz, F.; Choi, S. H.; Ryoo, R. Cubic Ia3d large mesoporous silica: Synthesis and replication to platinum nanowires, carbon nanorods and carbon nanotubes. Chem. Commun. 2003, 2136–2137.
Wang, Y. Q.; Yang, C. M.; Schmidt, W.; Spliethoff, B.; Bill, E.; Schüth, F. Weakly ferromagnetic ordered mesoporous Co3O4 synthesized by nanocasting from vinyl-functionalized cubic Ia3d mesoporous silica. Adv. Mater. 2005, 17, 53–56.
Xu, D.; Luo, L. Q.; Ding, Y. P.; Jiang, L.; Zhang, Y. T.; Ouyang, X. Q.; Liu, B. D. A novel nonenzymatic fructose sensor based on electrospun LaMnO3 fibers. J. Electroanal. Chem. 2014, 727, 21–26.
Wu, C.; Cai, J. J.; Zhang, Q. B.; Zhou, X.; Zhu, Y.; Li, L. J.; Shen, P. K.; Zhang, K. L. Direct growth of urchin-like ZnCo2O4 microspheres assembled from nanowires on nickel foam as high-performance electrodes for supercapacitors. Electrochim. Acta 2015, 169, 202–209.
Vijayanand, S.; Joy, P. A.; Potdar, H. S.; Patil, D.; Patil, P. Nanostructured spinel ZnCo2O4 for the detection of LPG. Sens. Actuators B: Chem. 2011, 152, 121–129.
Varghese, B.; Teo, C. H.; Zhu, Y. W.; Reddy, M. V.; Chowdari, B. V. R.; Wee, A. T. S.; Tan, V. B. C.; Lim, C. T.; Sow, C. H. Co3O4 nanostructures with different morphologies and their field-emission properties. Adv. Funct. Mater. 2007, 17, 1932–1939.
Xu, J. B.; Gao, P.; Zhao, T. S. Non-precious Co3O4 nano-rod electrocatalyst for oxygen reduction reaction in anionexchange membrane fuel cells. Energy Environ. Sci. 2012, 5, 5333–5339.
Bai, J.; Li, X. G.; Liu, G. Z.; Qian, Y. T.; Xiong, S. L. Unusual formation of ZnCo2O4 3D hierarchical twin microspheres as a high-rate and ultralong-life lithium-ion battery anode material. Adv. Funct. Mater. 2014, 24, 3012–3020.
Tan, Y.; Wu, C. C.; Lin, H.; Li, J. B.; Chi, B.; Pu, J.; Jian, L. Insight the effect of surface Co cations on the electrocatalytic oxygen evolution properties of cobaltite spinels. Electrochim. Acta 2014, 121, 183–187.
Koza, J. A.; He, Z.; Miller, A. S.; Switzer, J. A. Electrodeposition of crystalline Co3O4—A catalyst for the oxygen evolution reaction. Chem. Mater. 2012, 24, 3567–3573.
Chou, N. H.; Ross, P. N.; Bell, A. T.; Tilley, T. D. Comparison of cobalt-based nanoparticles as electrocatalysts for water oxidation. ChemSusChem 2011, 4, 1566–1569.
Qian, L.; Gu, L.; Yang, L.; Yuan, H. Y.; Xiao, D. Direct growth of NiCo2O4 nanostructures on conductive substrates with enhanced electrocatalytic activity and stability for methanol oxidation. Nanoscale 2013, 5, 7388–7396.
Heli, H.; Pishahang, J. Cobalt oxide nanoparticles anchored to multiwalled carbon nanotubes: Synthesis and application for enhanced electrocatalytic reaction and highly sensitive nonenzymatic detection of hydrogen peroxide. Electrochim. Acta 2014, 123, 518–526.
Kong, L. J.; Ren, Z. Y.; Zheng, N. N.; Du, S. C.; Wu, J.; Tang, J. L.; Fu, H. G. Interconnected 1D Co3O4 nanowires on reduced graphene oxide for enzymeless H2O2 detection. Nano Res. 2015, 8, 469–480.
Lei, X. M.; Li, T. T.; Zuo, Y. P.; Yin, W. M.; Wu, L.; Shao, K.; Xiao, X. Y.; Lu, Z. C.; Han, H. Y. Platinum-based nitrogen-doped porous CxN1–x compounds used as a transducer for sensitive detection of hydrogen peroxide. Electrochim. Acta 2016, 209, 661–670.
Yan, Y. B.; Li, K. X.; Dai, Y. H.; Chen, X. P.; Zhao, J.; Yang, Y. H.; Lee, J.-M. Synthesis of 3D mesoporous samarium oxide hydrangea microspheres for enzyme-free sensor of hydrogen peroxide. Electrochim. Acta 2016, 208, 231–237.
Ensafi, A. A.; Rezaloo, F.; Rezaei, B. Electrochemical sensor based on porous silicon/silver nanocomposite for the determination of hydrogen peroxide. Sens. Actuators B: Chem. 2016, 231, 239–244.
Tang, K. K.; Wu, X. F.; Wang, G. D.; Li, L. X.; Wu, S. Y.; Dong, X. T.; Liu, Z. L.; Zhao, B. One-step preparation of silver nanoparticle embedded amorphous carbon for nonenzymatic hydrogen peroxide sensing. Electrochem. Commun. 2016, 68, 90–94.
Huang, S.; Si, Z. C.; Li, X. K.; Zou, J. S.; Yao, Y. W.; Weng, D. A novel Au/r-GO/TNTs electrode for H2O2, O2 and nitrite detection. Sens. Actuators B: Chem. 2016, 234, 264–272.
Du, S. C.; Ren, Z. Y.; Wu, J.; Xi, W.; Fu, H. G. Vertical α-FeOOH nanowires grown on the carbon fiber paper as a free-standing electrode for sensitive H2O2 detection. Nano Res. 2016, 9, 2260–2269.
Ding, Y.; Wang, Y.; Su, L.; Bellagamba, M.; Zhang, H.; Lei, Y. Electrospun Co3O4 nanofibers for sensitive and selective glucose detection. Biosens. Bioelectron. 2010, 26, 542–548.
Chen, Y.; Prasad, K. P.; Wang, X. W.; Pang, H. C.; Yan, R. Y.; Than, A.; Chan-Park, M. B.; Chen, P. Enzymeless multi-sugar fuel cells with high power output based on 3D graphene-Co3O4 hybrid electrodes. Phys. Chem. Chem. Phys. 2013, 15, 9170–9176.
Acknowledgements
Thank the National Natural Science Foundation of China (Nos. 21671132 and 81301345) for the supports. Thank Analysis and Determination Center, Shanghai University for the support.
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Uniform ordered mesoporous ZnCo2O4 nanospheres for super-sensitive enzyme-free H2O2 biosensing and glucose biofuel cell applications
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Cui, S., Li, L., Ding, Y. et al. Uniform ordered mesoporous ZnCo2O4 nanospheres for super-sensitive enzyme-free H2O2 biosensing and glucose biofuel cell applications. Nano Res. 10, 2482–2494 (2017). https://doi.org/10.1007/s12274-017-1452-3
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DOI: https://doi.org/10.1007/s12274-017-1452-3