氮掺杂石墨烯方法提升无膜酶生物燃料电池性能

Nitrogen-doped graphene approach to enhance the performance of a membraneless enzymatic biofuel cell

Abstract

Heteroatom-doping of pristine graphene is an effective route for tailoring new characteristics in terms of catalytic performance which opens up potentials for new applications in energy conversion and storage devices. Nitrogen-doped graphene (N-graphene), for instance, has shown excellent performance in many electrochemical systems involving oxygen reduction reaction (ORR), and more recently glucose oxidation. Owing to the excellent {\mathrm{H}}_2{\mathrm{O}}_2 sensitivity of N-graphene, the development of highly sensitive and fast-response enzymatic biosensors is made possible. However, a question that needs to be addressed is whether or not improving the anodic response to glucose detection leads to a higher overall performance of enzymatic biofuel cell (eBFC). Thus, here we first synthesized N-graphene via a catalyst-free single-step thermal process, and made use of it as the biocatalyst support in a membraneless eBFC to identify its role in altering the performance characteristics. Our findings demonstrate that the electron accepting nitrogen sites in the graphene structure enhances the electron transfer efficiency between the mediator (redox polymer), redox active site of the enzymes, and electrode surface. Moreover, the best performance in terms of power output and current density of eBFCs was observed when the bioanode was modified with highly doped N-graphene.

Keywords

enzymatic fuel cell / nitrogen-doped graphene / reduced graphene oxide / catalyst-free synthesis

参考文献

[1] Rasmussen M, Abdellaoui S, Minteer S D. Enzymatic biofuel cells: 30 years of critical advancements. Biosensors & Bioelectronics, 2016, 76: 91–102

[2] Meredith M T, Minteer S D. Biofuel cells: enhanced enzymatic bioelectrocatalysis. Annual Review of Analytical Chemistry (Palo Alto, Calif.), 2012, 5(1): 157–179

[3] Yazdi A A, D’Angelo L, Omer N, Windiasti G, Lu X, Xu J. Carbon nanotube modification of microbial fuel cell electrodes. Biosensors & Bioelectronics, 2016, 85: 536–552

[4] Pankratov D, Sundberg R, Sotres J, Maximov I, Graczyk M, Suyatin D B, González-Arribas E, Lipkin A, Montelius L, Shleev S. Transparent and flexible, nanostructured and mediatorless glucose/oxygen enzymatic fuel cells. Journal of Power Sources, 2015, 294: 501–506

[5] Milton R D, Lim K, Hickey D P, Minteer S D. Employing FAD-dependent glucose dehydrogenase within a glucose/oxygen enzymatic fuel cell operating in human serum. Bioelectrochemistry (Amsterdam, Netherlands), 2015, 106(Pt A): 56–63

[6] Zhang L, Chen L, Zhou X, Liu Z. Towards high-voltage aqueous metal-ion batteries beyond 1.5 V: the zinc/zinc hexacyanoferrate system. Advanced Energy Materials, 2015, 5(2): 1400930

[7] Ogawa Y, Takai Y, Kato Y, Kai H, Miyake T, Nishizawa M. Stretchable biofuel cell with enzyme-modified conductive textiles. Biosensors & Bioelectronics, 2015, 74: 947–952

[8] Neto S A, Milton R D, Hickey D P, Andrade A R D, Minteer S D. Membraneless enzymatic ethanol/O₂ fuel cell: transitioning from an air-breathing Pt-based cathode to a bilirubin oxidase-based biocathode. Journal of Power Sources, 2016, 324: 208–214

[9] Qu L, Liu Y, Baek J B, Dai L. Nitrogen-doped graphene as efficient metal-free electrocatalyst for oxygen reduction in fuel cells. ACS Nano, 2010, 4(3): 1321–1326

[10] Ito Y, Cong W, Fujita T, Tang Z, Chen M. High catalytic activity of nitrogen and sulfur co-doped nanoporous graphene in the hydrogen evolution reaction. Angewandte Chemie International Edition, 2015, 54(7): 2131–2136

[11] Lin Z, Waller G H, Liu Y, Liu M, Wong C P. Simple preparation of nanoporous few-layer nitrogen-doped graphene for use as an efficient electrocatalyst for oxygen reduction and oxygen evolution reactions. Carbon, 2013, 53: 130–136

[12] Wang H, Maiyalagan T, Wang X. Review on recent progress in nitrogen-doped graphene: synthesis, characterization, and its potential applications. ACS Catalysis, 2012, 2(5): 781–794

[13] Wang Y, Shao Y, Matson D W, Li J, Lin Y. Nitrogen-doped graphene and its application in electrochemical biosensing. ACS Nano, 2010, 4(4): 1790–1798

[14] Thomas T J, Ponnusamy K E, Chang N M, Galmore K, Minteer S D. Effects of annealing on mixture-cast membranes of Nafion® and quaternary ammonium bromide salts. Journal of Membrane Science, 2003, 213(1–2): 55–66

[15] Akers N L, Moore C M, Minteer S D. Development of alcohol/O₂ biofuel cells using salt-extracted tetrabutylammonium bromide/Nafion membranes to immobilize dehydrogenase enzymes. Electrochimica Acta, 2005, 50(12): 2521–2525

[16] Dawn A, Shiraki T, Haraguchi S, Sato H, Sada K, Shinkai S. Transcription of chirality in the organogel systems dictates the enantiodifferentiating photodimerization of substituted anthracene. Chemistry (Weinheim an der Bergstrasse, Germany), 2010, 16(12): 3676–3689

[17] Minson M, Meredith M T, Shrier A, Giroud F, Hickey D, Glatzhofer D T, Minteer S D. High performance glucose/O₂ biofuel cell: effect of utilizing purified laccase with anthracene-modified multi-walled carbon nanotubes. Journal of the Electrochemical Society, 2012, 159(12): G166–G170

[18] Milton R D, Giroud F, Thumser A E, Minteer S D, Slade R C T. Bilirubin oxidase bioelectrocatalytic cathodes: the impact of hydrogen peroxide. Chemical Communications, 2014, 50(1): 94–96

[19] Merchant S A, Tran T O, Meredith M T, Cline T C, Glatzhofer D T, Schmidtke D W. High-sensitivity amperometric biosensors based on ferrocene-modified linear poly(ethylenimine). Langmuir, 2009, 25(13): 7736–7742

[20] Merchant S A, Meredith M T, Tran T O, Brunski D B, Johnson M B, Glatzhofer D T, Schmidtke D W. Effect of mediator spacing on electrochemical and enzymatic response of ferrocene redox polymers. Journal of Physical Chemistry C, 2010, 114(26): 11627–11634

[21] Milton R D, Giroud F, Thumser A E, Minteer S D, Slade R C T. Hydrogen peroxide produced by glucose oxidase affects the performance of laccase cathodes in glucose/oxygen fuel cells: FAD-dependent glucose dehydrogenase as a replacement. Physical Chemistry Chemical Physics, 2013, 15(44): 19371–19379

[22] Meredith M T, Kao D Y, Hickey D, Schmidtke D W, Glatzhofer D T. High current density ferrocene-modified linear poly(ethylenimine) bioanodes and their use in biofuel cells. Journal of the Electrochemical Society, 2011, 158(2): B166–B174

[23] Lin Z, Song M K, Ding Y, Liu Y, Liu M, Wong C P. Facile preparation of nitrogen-doped graphene as a metal-free catalyst for oxygen reduction reaction. Physical Chemistry Chemical Physics, 2012, 14(10): 3381–3387

[24] Sheng Z H, Shao L, Chen J J, Bao W J, Wang F B, Xia X H. Catalyst-free synthesis of nitrogen-doped graphene via thermal annealing graphite oxide with melamine and its excellent electrocatalysis. ACS Nano, 2011, 5(6): 4350–4358

[25] Das A, Pisana S, Chakraborty B, Piscanec S, Saha S K, Waghmare U V, Novoselov K S, Krishnamurthy H R, Geim A K, Ferrari A C, Sood A K. Monitoring dopants by Raman scattering in an electrochemically top-gated graphene transistor. Nature Nanotechnology, 2008, 3(4): 210–215

[26] Jia Y, Zhang L, Du A, Gao G, Chen J, Yan X, Brown C L, Yao X. Defect graphene as a trifunctional catalyst for electrochemical reactions. Advanced Materials, 2016, 28(43): 9532–9538

[27] Wei D, Liu Y, Wang Y, Zhang H, Huang L, Yu G. Synthesis of N-doped graphene by chemical vapor deposition and its electrical properties. Nano Letters, 2009, 9(5): 1752–1758

[28] Karyakin A A. Prussian blue and its analogues: electrochemistry and analytical applications. Electroanalysis, 2001, 13(10): 813–819

[29] Zhao W, Xu J J, Shi C G, Chen H Y. Multilayer membranes via layer-by-layer deposition of organic polymer protected Prussian blue nanoparticles and glucose oxidase for glucose biosensing. Langmuir, 2005, 21(21): 9630–9634

[30] Karyakin A A, Gitelmacher O V, Karyakina E E. Prussian blue-based first-generation biosensor. A sensitive amperometric electrode for glucose. Analytical Chemistry, 1995, 67(14): 2419–2423

[31] Yazdi A A, Preite R, Milton R D, Hickey D P, Minteer S D, Xu J. Rechargeable membraneless glucose biobattery: towards solid-state cathodes for implantable enzymatic devices. Journal of Power Sources, 2017, 343: 103–108

Acknowledgments

We highly thank Dr. Shelley D. Minteer and Dr. David P. Hickey (University of Utah) and Dr. Ross D. Milton (Stanford University) for kindly providing us with An-MWCNT and for their guidelines and support. This work also made use of instruments in the Electron Microscopy Service (EMS), at the Research Resources Center, University of Illinois at Chicago.

版权

2018 Higher Education Press and Springer-Verlag GmbH Germany, part of Springer Nature