Cuprous oxide microspheres on graphene nanosheets: an enhanced material for non-enzymatic electrochemical detection of H2O2 and glucose

We report here a facile one-step green synthesis of cuprous oxide microspheres (Cu2OMS) on reduced graphene oxide (RGO) by reducing Cu2+ ions and GO with sodium ascorbate synchronously in the presence of sodium hydroxide. Cu2OMS with different sizes on the surface of RGO were successfully synthesized by adjusting the mass ratio of GO to CuSO4·5H2O in this reaction system. It was found that uniform Cu2OMS were formed on RGO by increasing the mass ratio from 1 : 20 to 1 : 80. The synthesized Cu2OMS–RGO composites with different structures were immobilized onto glassy carbon electrodes and applied to construct electrochemical hydrogen peroxide (H2O2) and glucose sensors. The results indicate that the Cu2OMS–RGO composite created with the mass ratio of 1 : 80 presents the best sensor performances. The fabricated H2O2 sensor exhibits a fast amperometric response to H2O2 with a linear detection range from 0.005 to 2.775 mM and a detection limit of 0.0108 mM, and the glucose sensor has a linear detection range from 0.001 to 0.419 mM and a detection limit of 7.288 × 10−4 mM. The superior performance is ascribed to the unique structure of the synthesized Cu2OMS and the excellent conductivity of the RGO content. In addition, the synthesized Cu2OMS–RGO composites exhibited improved electrochemical stability. Such novel Cu2OMS–RGO hybrid materials represent promising non-enzymatic electrochemical glucose and H2O2 sensors with high sensitivity and selectivity, improved stability, and fast amperometric response.

[1]  Zhuang Li,et al.  Graphene–Pt nanocomposite for nonenzymatic detection of hydrogen peroxide with enhanced sensitivity , 2011 .

[2]  A. Gopalan,et al.  Glucose sensing, photocatalytic and antibacterial properties of graphene–ZnO nanoparticle hybrids , 2012 .

[3]  Wenzhong Wang,et al.  Template-free room temperature solution phase synthesis of Cu2O hollow spheres , 2010 .

[4]  Gang Wei,et al.  Hydrothermal synthesis of zinc oxide-reduced graphene oxide nanocomposites for an electrochemical hydrazine sensor , 2015 .

[5]  Michael H. Huang,et al.  Seed‐Mediated Synthesis of Monodispersed Cu2O Nanocubes with Five Different Size Ranges from 40 to 420 nm , 2007 .

[6]  Wei Zhang,et al.  Fixure-reduce method for the synthesis of Cu2O/MWCNTs nanocomposites and its application as enzyme-free glucose sensor. , 2009, Biosensors & bioelectronics.

[7]  Taeseup Song,et al.  Gold nanoparticle-composite nanofibers for enzymatic electrochemical sensing of hydrogen peroxide. , 2013, The Analyst.

[8]  Kyoung-Shin Choi,et al.  Elucidating the effect of additives on the growth and stability of Cu2O surfaces via shape transformation of pre-grown crystals. , 2006, Journal of the American Chemical Society.

[9]  Li Wang,et al.  Electrochemical behavior of cuprous oxide–reduced graphene oxide nanocomposites and their application in nonenzymatic hydrogen peroxide sensing , 2013 .

[10]  S. Lim,et al.  A glucose biosensor based on electrodeposition of palladium nanoparticles and glucose oxidase onto Nafion-solubilized carbon nanotube electrode. , 2005, Biosensors & bioelectronics.

[11]  Weiwei Zhou,et al.  Facile synthesis and shape evolution of highly symmetric 26-facet polyhedral microcrystals of Cu2O , 2009 .

[12]  Zhiqiang Su,et al.  Biomimetic graphene-FePt nanohybrids with high solubility, ferromagnetism, fluorescence, and enhanced electrocatalytic activity , 2012 .

[13]  K. Suslick,et al.  Sonochemical preparation of functionalized graphenes. , 2011, Journal of the American Chemical Society.

[14]  M. Otyepka,et al.  Functionalization of graphene: covalent and non-covalent approaches, derivatives and applications. , 2012, Chemical reviews.

[15]  C. M. Kim,et al.  Facile synthesis of cuprous oxide using ultrasound, microwave and electric heating: effect of heating methods on synthesis kinetics, morphology and yield , 2011 .

[16]  Juan Wang,et al.  Facile fabrication of gold nanoparticles-poly(vinyl alcohol) electrospun water-stable nanofibrous mats: efficient substrate materials for biosensors. , 2012, ACS applied materials & interfaces.

[17]  Cheol-Woong Yang,et al.  Evidence of graphitic AB stacking order of graphite oxides. , 2008, Journal of the American Chemical Society.

[18]  Maurizio Prato,et al.  Organic functionalization of graphene in dispersions. , 2013, Accounts of chemical research.

[19]  Zhiqiang Su,et al.  One-pot green synthesis, characterizations, and biosensor application of self-assembled reduced graphene oxide-gold nanoparticle hybrid membranes. , 2013, Journal of materials chemistry. B.

[20]  Zhiqiang Wang,et al.  Environment-Friendly Method To Produce Graphene That Employs Vitamin C and Amino Acid , 2010 .

[21]  Jannik C. Meyer,et al.  The structure of suspended graphene sheets , 2007, Nature.

[22]  N. Mohanty,et al.  Graphene-based single-bacterium resolution biodevice and DNA transistor: interfacing graphene derivatives with nanoscale and microscale biocomponents. , 2008, Nano letters.

[23]  Xiaoping Song,et al.  Template-Free Synthesis of Well-Defined Truncated Edge Polyhedral Cu2O Architectures , 2010 .

[24]  Xian‐Wen Wei,et al.  A non-enzymatic hydrogen peroxide sensor based on a glassy carbon electrode modified with cuprous oxide and nitrogen-doped graphene in a nafion matrix , 2014, Microchimica Acta.

[25]  H. Pang,et al.  Glycine-assisted double-solvothermal approach for various cuprous oxide structures with good catalytic activities , 2010 .

[26]  Xinhong Song,et al.  Recent advances in electrochemiluminescent enzyme biosensors , 2011 .

[27]  S. Stankovich,et al.  Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide , 2007 .

[28]  Lei Jiang,et al.  Hollow Micro/Nanomaterials with Multilevel Interior Structures , 2009 .

[29]  Gang Wei,et al.  Fabrication, characterization and sensor application of electrospun polyurethane nanofibers filled with carbon nanotubes and silver nanoparticles. , 2013, Journal of materials chemistry. B.

[30]  Yiying Wu,et al.  Coassembly of graphene oxide and nanowires for large-area nanowire alignment. , 2009, Journal of the American Chemical Society.

[31]  Chun Li,et al.  Flexible graphene films via the filtration of water-soluble noncovalent functionalized graphene sheets. , 2008, Journal of the American Chemical Society.

[32]  Selvakumar Palanisamy,et al.  A novel nonenzymatic hydrogen peroxide sensor based on reduced graphene oxide/ZnO composite modified electrode , 2012 .

[33]  C. Macosko,et al.  Graphene/Polymer Nanocomposites , 2010 .

[34]  Q. Gong,et al.  One-Pot Synthesis of Uniform Cu2O and CuS Hollow Spheres and Their Optical Limiting Properties , 2008 .

[35]  Zelin Li,et al.  Nonenzymatic amperometric response of glucose on a nanoporous gold film electrode fabricated by a rapid and simple electrochemical method. , 2011, Biosensors & bioelectronics.

[36]  Jinlong Yang,et al.  Shape-Dependent Reducibility of Cuprous Oxide Nanocrystals , 2010 .

[37]  H. Abruña,et al.  Dithiobissuccinimidyl propionate as an anchor for assembling peroxidases at electrodes surfaces and its application in a H2O2 biosensor. , 1999, Analytical chemistry.

[38]  Kang Wang,et al.  Highly Ordered Platinum‐Nanotubule Arrays for Amperometric Glucose Sensing , 2005 .

[39]  Kaiming Liao,et al.  Porous cuprous oxide microcubes for non-enzymatic amperometric hydrogen peroxide and glucose sensing , 2009 .

[40]  C. Fan,et al.  Graphene-based high-efficiency surface-enhanced Raman scattering-active platform for sensitive and multiplex DNA detection. , 2012, Analytical chemistry.

[41]  L. Bai,et al.  Morphology Evolution of Cu2O from Octahedra to Hollow Structures , 2010 .

[42]  Wei Chen,et al.  Graphene wrapped Cu2O nanocubes: non-enzymatic electrochemical sensors for the detection of glucose and hydrogen peroxide with enhanced stability. , 2013, Biosensors & bioelectronics.

[43]  X. Xia,et al.  A green approach to the synthesis of graphene nanosheets. , 2009, ACS nano.

[44]  Zhiqiang Su,et al.  Electrospun doping of carbon nanotubes and platinum nanoparticles into the β-phase polyvinylidene difluoride nanofibrous membrane for biosensor and catalysis applications. , 2014, ACS applied materials & interfaces.

[45]  A. Star,et al.  Carbon Nanotube Field‐Effect‐Transistor‐Based Biosensors , 2007 .