Tue, 2013-04-09 15:57 | 
Glucose is the most abundant carbohydrate in nature easily produced by photosynthesis in plants such as sugar cane or corn and by a large amount of waste biomass that is generated by agricultural
activities [1,2]. Glucose’s theoretical energy is 4430 Wh kg-1 and its complete oxidation to carbon dioxide can produce 24 electrons in accordance with the following chemical equations:
Theoretical anode reaction: C6H12O6+24OH---> 6CO2+18H2O+24e- (1)
Theoretical cathode reaction: 6O2+12H2O+24e- --> 24OH- (2)
Overall reaction: C6H12O6+ 6O2 --> 6CO2+ 6H2O (3)
A potential approach to obtain energy from glucose is to be fed into a fuel cell, which directly oxidize the fuel to generate electricity, such as direct methanol and direct ethanol fuel cells. The development of glucose fuel cells research today has mainly two purposes: i) the in vivo applications and ii) the development of highly stable and efficient electrocatalysts. The fuel (glucose) could be withdrawn virtually without limit from the flow of blood providing a long-term or even permanent power supply for such devices as pacemakers, glucose sensors for diabetics or small valves for bladder control. On this purpose many attempts have been focused on the development of enzymatic and microbial fuel cells [3-9]. In the past few decades most research in the field has been focused on immobilization methods for enzymatic catalysts in an effort to increase the lifetime of glucose fuel cells. Enzymatic catalysts for glucose/O2 fuel cells have excellent selectivity and can produce power densities of the order of several mW cm-2. However they have very short lifetime, typically less than thirty days, due to the fragile nature of the enzymes and poor immobilization techniques. This makes them generally unsuitable for long-term implantable applications despite having been successfully tested in-vivo. Thus, recently, it is observed an increase interest in non-enzymatic fuel cells that use mainly platinum [10-15] and gold alloys [10,15-17] as anodes electrocatalysts and usually activated carbon as cathode electrocatalyst [18-20] . The researches’ results prove that such fuel cells have shown good time stability and have been successfully tested in-vivo [21] . The biggest challenge however remains the poor anode selectivity towards glucose oxidation in presence of oxygen. Recently, Kerzenmacher et al. [22-24] proposed novel direct glucose fuel cell structures fabricating Raney platinum and Raney platinum doped with zinc electrodes as anodes and thin layer platinum as cathode, examining also their compatibility with a body tissue environment. Direct electrooxidation of glucose on non-enzymatic noble metal electrodes has been studied in the last few years as the alternative solution to the complexity and drawbacks of the microbial and enzymatic fuel cells. Many of them have been focused on Pt [11,25], Au [16,26] and on their bi-metallic catalysts, Pt-Bi [19] , Pt-Pd [27], Pt-Ru [18], Pt-Au [28,20], Ag-Au [29-31] and tri-metallic catalysts [32] .
The present PhD study aims to investigate for the first time in the literature the electrocatalytic activity of low metal loading 20%wt Pdx-(Sn, Rh & Ru) on carbon bi-metallic electrocatalysts for glucose electrooxidation. The preparation and physical characterization of different electrocatalysts scanning electron microscope (SEM) and X-ray diffraction (XRD) are reported. Glucose electro-oxidation on the examined electrocatalysts in alkaline electrolyte (KOH) are electrochemically characterized using cyclic voltammetry (CV) and chronoamperometry (CA) technique. Additionally, will be used the RDE technique for evaluating the electrochemical activity of the electrocatalysts towards glucose electrooxidation in presence of oxygen.
References
[1] Van Wyk J P H. Biotechnology and the utilization of biowaste as a resource for bioproduct development.Trends in Biotechnology(2001);19(5):172-177.
[2] Swades K C, Derek R L. Electricity generation by direct oxidation of glucose in mediatorless microbial fuel cells.Nature Biotechnology(2003);211229-1232.
[3] Barton S C, Kim H-H, Binyamin G, Zhang Y, Heller A. The "Wired" Laccase Cathode:High Current Density Electroreduction of O2 to Water at +0.7 V (NHE) at pH 5.Journal of the American Chemical Society(2001);123(24):5802-5803.
[4] Barton S C, Gallaway J, Atanassov P. Enzymatic biofuel cells for implantable and microscale devices.Chem Rev(2004);104(10):4867-4886.
[5] Kim H-H, Zhang Y, Heller A. Bilirubin Oxidase Label for an Enzyme-Linked Affinity Assay with O2 as Substrate in a Neutral pH NaCl Solution.Analytical Chemistry(2004);76(8):2411-2414.
[6] Shleev S, Tkac J, Christenson A, Ruzgas T, Yaropolov A I, Whittaker J W, Gorton L. Direct electron transfer between copper-containing proteins and electrodes.Biosensors and Bioelectronics(2005);20(12):2517-2554.
[7] Bullen R A, Arnot T C, Lakeman J B, Walsh F C. Biofuel cells and their development.Biosensors and Bioelectronics(2006);21(11):2015-2045.
[8] Kang C, Shin H, Heller A. On the stability of the "wired" bilirubin oxidase oxygen cathode in serum.Bioelectrochemistry(2006);68(1):22-26.
[9] Gao F, Yan Y, Su L, Wang L, Mao L. An enzymatic glucose/O2 biofuel cell: Preparation, characterization and performance in serum.Electrochem Commun(2007);9(5):989-996.
[10] Jia F, Yu C, Deng K, Zhang L. Nanoporous Metal (Cu, Ag, Au) Films with High Surface Area: General Fabrication and Preliminary Electrochemical Performance.J Phys Chem C(2007);111(24):8424-8431.
[11] Shen Q, Jiang L, Zhang H, Min Q, Hou W, Zhu J-J. Three-dimensional Dendritic Pt Nanostructures: Sonoelectrochemical Synthesis and Electrochemical Applications.J Phys Chem C(2008);112(42):16385-16392.
[12] Kloke A, Kloke C, Zengerle R, Kerzenmacher S. Porous Platinum Electrodes Fabricated by Cyclic Electrodeposition of PtCu Alloy: Application to Implantable Glucose Fuel Cells.J Phys Chem C(2012);116(37):19689-19698.
[13] Apblett C A, Ingersoll D, Sarangapani S, Kelly M, Atanassov P (2010) Direct Glucose Fuel Cell: Noble Metal Catalyst Anode Polymer Electrolyte Membrane Fuel Cell with Glucose Fuel. vol 157. First published. doi:10.1149/1.3248004.
[14] Yan X, Ge X, Cui S (2011) Pt-decorated nanoporous gold for glucose electrooxidation in neutral and alkaline solutions. vol 6. First published.
[15] Xie F, Huang Z, Chen C, Xie Q, Huang Y, Qin C, Liu Y, Su Z, Yao S. Preparation of Au-film electrodes in glucose-containing Au-electroplating aqueous bath for high-performance nonenzymatic glucose sensor and glucose/O2 fuel cell.Electrochem Commun(2012);18(0):108-111.
[16] Huang W, Wang M, Zheng J, Li Z. Facile Fabrication of Multifunctional Three-Dimensional Hierarchical Porous Gold Films via Surface Rebuilding.J Phys Chem C(2009);113(5):1800-1805.
[17] Pasta M, Ruffo R, Falletta E, Mari C M, Pina C D. Alkaline glucose oxidation on nanostructured gold electrodes.Gold Bulletin(2010);43(1):57-64.
[18] Basu D, Basu S. A study on direct glucose and fructose alkaline fuel cell.Electrochim Acta(2010);55(20):5775-5779.
[19] Basu D, Basu S. Synthesis, characterization and application of platinum based bi-metallic catalysts for direct glucose alkaline fuel cell.Electrochim Acta(2011);56(17):6106-6113.
[20] Basu D, Basu S. Synthesis and characterization of Pt-Au/C catalyst for glucose electro-oxidation for the application in direct glucose fuel cell.Int J Hydrogen Enrg(2011);36(22):14923-14929.
[21] Oncescu V, Erickson D (2013) High volumetric power density, non-enzymatic, glucose fuel cells. Scientific Reports, vol 3.
[22] Kerzenmacher S, Kräling U, Metz T, Zengerle R, von Stetten F. A potentially implantable glucose fuel cell with Raney-platinum film electrodes for improved hydrolytic and oxidative stability.J Power Sources(2011);196(3):1264-1272.
[23] Kerzenmacher S, Kräling U, Schroeder M, Brämer R, Zengerle R, Von Stetten F. Raney-platinum film electrodes for potentially implantable glucose fuel cells. Part 2: Glucose-tolerant oxygen reduction cathodes.J Power Sources(2010);195(19):6524-6531.
[24] Kerzenmacher S, Schroeder M, Brämer R, Zengerle R, Von Stetten F. Raney-platinum film electrodes for potentially implantable glucose fuel cells. Part 1: Nickel-free glucose oxidation anodes.J Power Sources(2010);195(19):6516-6523.
[25] Fujiwara N, Yamazaki S-i, Siroma Z, Ioroi T, Senoh H, Yasuda K. Nonenzymatic glucose fuel cells with an anion exchange membrane as an electrolyte.Electrochem Commun(2009);11(2):390-392.
[26] Yin H, Zhou C, Xu C, Liu P, Xu X, Ding Y. Aerobic Oxidation of d-Glucose on Support-Free Nanoporous Gold.J Phys Chem C(2008);112(26):9673-9678.
[27] Spets J P, Kiros Y, Kuosa M A, Rantanen J, Lampinen M J, Saari K. Bioorganic materials as a fuel source for low-temperature direct-mode fuel cells.Electrochim Acta(2010);55(26):7706-7709.
[28] Yan X, Ge X, Cui S. Pt-decorated nanoporous gold for glucose electrooxidation in neutral and alkaline solutions.Nanoscale Res Lett(2011);6(1):313.
[29] Liu Z, Huang L, Zhang L, Ma H, Ding Y. Electrocatalytic oxidation of d-glucose at nanoporous Au and Au-Ag alloy electrodes in alkaline aqueous solutions.Electrochim Acta(2009);54(28):7286-7293.
[30] Jin C, Taniguchi I. Electrocatalytic activity of silver modified gold film for glucose oxidation and its potential application to fuel cells.Mater Lett(2007);61(11-12):2365-2367.
[31] Cuevas-Muñiz F M, Guerra-Balcázar M, Castaneda F, Ledesma-García J, Arriaga L G. Performance of Au and AuAg nanoparticles supported on Vulcan in a glucose laminar membraneless microfuel cell.J Power Sources(2011);196(14):5853-5857.
[32] Basu D, Basu S. Performance studies of Pd-Pt and Pt-Pd-Au catalyst for electro-oxidation of glucose in direct glucose fuel cell.Int J Hydrogen Enrg(2012);37(5):4678-4684.
[33] Song S, Wang Y, Shen P K. Pulse-microwave assisted polyol synthesis of highly dispersed high loading Pt/C electrocatalyst for oxygen reduction reaction.J Power Sources(2007);170(1):46-49.
