An oxygen-independent and membrane-less glucose biobattery/supercapacitor hybrid device.

Enzymatic biofuel cells can generate electricity directly from the chemical energy of biofuels in physiological fluids, but their power density is significantly limited by the performance of the cathode which is based on oxygen reduction for in vivo applications. An oxygen-independent and membrane-less glucose biobattery was prepared that consists of a dealloyed nanoporous gold (NPG) supported glucose dehydrogenase (GDH) bioanode, immobilised with the assistance of conductive polymer/Os redox polymer composites, and a solid-state NPG/MnO2 cathode. In a solution containing 10mM glucose, a maximum power density of 2.3µWcm-2 at 0.21V and an open circuit voltage (OCV) of 0.49V were registered as a biobattery. The potential of the discharged MnO2 could be recovered, enabling a proof-of-concept biobattery/supercapacitor hybrid device. The resulting device exhibited a stable performance for 50 cycles of self-recovery and galvanostatic discharge as a supercapacitor at 0.1mAcm-2 over a period of 25h. The device could be discharged at current densities up to 2mAcm-2 supplying a maximum instantaneous power density of 676 μW cm-2, which is 294 times higher than that from the biobattery alone. A mechanism for the recovery of the potential of the cathode, analogous to that of RuO2 (Electrochim. Acta 42(23), 3541-3552) is described.

[1]  Sergey Shleev,et al.  Quo Vadis, Implanted Fuel Cell? , 2017, ChemPlusChem.

[2]  A. Hirata,et al.  High-energy-density nonaqueous MnO2@nanoporous gold based supercapacitors , 2013 .

[3]  S. Shleev,et al.  Laccase electrode for direct electrocatalytic reduction of O2 to H2O with high-operational stability and resistance to chloride inhibition. , 2008, Biosensors & bioelectronics.

[4]  S. Shleev,et al.  Direct electron transfer of Trametes hirsuta laccase adsorbed at unmodified nanoporous gold electrodes. , 2013, Bioelectrochemistry.

[5]  Feng Xu,et al.  Oxidation of phenols, anilines, and benzenethiols by fungal laccases: correlation between activity and redox potentials as well as halide inhibition. , 1996, Biochemistry.

[6]  S. Ardizzone,et al.  "Inner" and "outer" active surface of RuO2 electrodes , 1990 .

[7]  Z. Blum,et al.  Ex vivo electric power generation in human blood using an enzymatic fuel cell in a vein replica , 2016 .

[8]  Y. Gogotsi,et al.  Materials for electrochemical capacitors. , 2008, Nature materials.

[9]  Li Zhuang,et al.  Manganese dioxide as an alternative cathodic catalyst to platinum in microbial fuel cells. , 2009, Biosensors & bioelectronics.

[10]  C. Kieda,et al.  Why is the partial oxygen pressure of human tissues a crucial parameter? Small molecules and hypoxia , 2011, Journal of cellular and molecular medicine.

[11]  Yi Cui,et al.  Microbial battery for efficient energy recovery , 2013, Proceedings of the National Academy of Sciences.

[12]  Meilin Liu,et al.  Investigation into the origin of high stability of δ-MnO2 pseudo-capacitive electrode using operando Raman spectroscopy , 2016 .

[13]  Michael Holzinger,et al.  Supercapacitor/biofuel cell hybrids based on wired enzymes on carbon nanotube matrices: autonomous reloading after high power pulses in neutral buffered glucose solutions , 2014 .

[14]  L. Gorton,et al.  Heterologous overexpression of Glomerella cingulata FAD-dependent glucose dehydrogenase in Escherichia coli and Pichia pastoris , 2011, Microbial cell factories.

[15]  Sergey Shleev,et al.  Mediatorless sugar/oxygen enzymatic fuel cells based on gold nanoparticle-modified electrodes. , 2012, Biosensors & bioelectronics.

[16]  J. L. Costa-Krämer,et al.  Interface double-exchange ferromagnetism in the Mn-Zn-O system: new class of biphase magnetism. , 2005, Physical review letters.

[17]  D. Tench,et al.  Electrodeposition of Conducting Transition Metal Oxide/Hydroxide Films from Aqueous Solution , 1983 .

[18]  D. Leech,et al.  Evaluation of performance and stability of biocatalytic redox films constructed with different copper oxygenases and osmium-based redox polymers. , 2009, Bioelectrochemistry.

[19]  Wolfgang Schuhmann,et al.  Enzymatic fuel cells: Recent progress , 2012 .

[20]  Shaojun Dong,et al.  Recoverable hybrid enzymatic biofuel cell with molecular oxygen-independence. , 2016, Biosensors & bioelectronics.

[21]  Michelle A. Rasmussen,et al.  Enzymatic biofuel cells: 30 years of critical advancements. , 2016, Biosensors & bioelectronics.

[22]  Shelley D. Minteer,et al.  Hybrid Glucose/O2 Biobattery and Supercapacitor Utilizing a Pseudocapacitive Dimethylferrocene Redox Polymer at the Bioanode , 2016 .

[23]  Evgeny Katz,et al.  From “cyborg” lobsters to a pacemaker powered by implantable biofuel cells , 2013 .

[24]  R. Forster,et al.  Synthesis, characterization, and properties of a series of osmium- and ruthenium-containing metallopolymers , 1990 .

[25]  V. Neff Some Performance Characteristics of a Prussian Blue Battery , 1985 .

[26]  P. Si,et al.  An overview of dealloyed nanoporous gold in bioelectrochemistry. , 2016, Bioelectrochemistry.

[27]  M. Pita,et al.  Immobilization of Redox Enzymes on Nanoporous Gold Electrodes: Applications in Biofuel Cells. , 2017, ChemPlusChem.

[28]  Shelley D. Minteer,et al.  Towards a rechargeable alcohol biobattery , 2011 .

[29]  C. Santoro,et al.  Self-feeding paper based biofuel cell/self-powered hybrid μ-supercapacitor integrated system. , 2016, Biosensors & bioelectronics.

[30]  Matsuhiko Nishizawa,et al.  Enzymatic biofuel cells designed for direct power generation from biofluids in living organisms , 2011 .

[31]  W. Tamborlane,et al.  Interstitial fluid concentrations of glycerol, glucose, and amino acids in human quadricep muscle and adipose tissue. Evidence for significant lipolysis in skeletal muscle. , 1995, The Journal of clinical investigation.

[32]  S. Dong,et al.  A miniature origami biofuel cell based on a consumed cathode. , 2016, Chemical communications.

[33]  Kevin W Eliceiri,et al.  NIH Image to ImageJ: 25 years of image analysis , 2012, Nature Methods.

[34]  Scott Calabrese Barton,et al.  Enzymatic biofuel cells for implantable and microscale devices. , 2004, Chemical reviews.

[35]  Xing Xie,et al.  Use of low cost and easily regenerated Prussian Blue cathodes for efficient electrical energy recovery in a microbial battery , 2015 .

[36]  Sergey Shleev,et al.  Supercapacitive Photo‐Bioanodes and Biosolar Cells: A Novel Approach for Solar Energy Harnessing , 2017 .

[37]  Alexey Serov,et al.  Self-powered supercapacitive microbial fuel cell: The ultimate way of boosting and harvesting power. , 2016, Biosensors & bioelectronics.

[38]  Wendy G. Pell,et al.  Self-discharge and potential recovery phenomena at thermally and electrochemically prepared RuO2 supercapacitor electrodes , 1997 .

[39]  Adam Heller,et al.  On the stability of the "wired" bilirubin oxidase oxygen cathode in serum. , 2006, Bioelectrochemistry.

[40]  Roland Ludwig,et al.  A symmetric supercapacitor/biofuel cell hybrid device based on enzyme-modified nanoporous gold: An autonomous pulse generator. , 2017, Biosensors & bioelectronics.

[41]  A. Hirata,et al.  Enhanced supercapacitor performance of MnO2 by atomic doping. , 2013, Angewandte Chemie.

[42]  P. Si,et al.  Nanoporous gold assembly of glucose oxidase for electrochemical biosensing , 2014 .

[43]  E. Magner,et al.  A biofuel cell in non-aqueous solution. , 2015, Chemical communications.

[44]  Zhaohui Wang,et al.  Biosupercapacitors for powering oxygen sensing devices. , 2015, Bioelectrochemistry.

[45]  B. P. Sullivan,et al.  Synthetic routes to new polypyridyl complexes of osmium(II) , 1988 .

[46]  Z. Blum,et al.  Self-Charging Electrochemical Biocapacitor , 2014 .

[47]  D. Leech,et al.  A glucose/oxygen enzymatic fuel cell based on redox polymer and enzyme immobilisation at highly-ordered macroporous gold electrodes. , 2012, The Analyst.

[48]  Chi Zhang,et al.  Pre-expression of a sulfhydryl oxidase significantly increases the yields of eukaryotic disulfide bond containing proteins expressed in the cytoplasm of E.coli , 2011, Microbial cell factories.

[49]  M. Allendorf,et al.  Low-temperature magnetic circular dichroism studies of native laccase: confirmation of a trinuclear copper active site , 1986 .