本文以乙醇脱氢酶(ADH)和胆红素氧化酶(BOD)为生物催化剂,以碳纳米管为电极材料,构筑了全酶型乙醇/氧气生物燃料电池. 将乙醇脱氢酶负载于单壁碳纳米管(SWCNT)上,采用亚甲基绿(MG)为NADH的电化学催化剂,实现乙醇的生物电化学催化氧化,制备了生物燃料电池ADH/MG/SWCNT/GC的电极(阳极). 同时,将胆红素氧化酶固定于单壁碳纳米管上,通过其直接电子转移,实现了氧气的生物电化学催化还原,制得生物燃料电池的BOD/SWCNT/GC阴极. 据此构筑了全酶型的无膜生物燃料电池,在空气饱和40 mmol·L-1乙醇磷酸缓冲溶液中该电池开路电压为0.53 V,最大输出功率密度为11 μW·cm-2. 以商品化伏特酒作为燃料,该生物燃料电池最大输出功率为3.7 μW·cm-2.
This study demonstrates the performance of a new type alcohol/O2 biofuel cell assembled by using alcohol dehydrogenase (ADH) and bilirubin oxidase (BOD) as the biocatalysts of the bioanode and the biocathode for the bioelectrocatalytic oxidation of alcohol and reduction of oxygen, respectively. To construct the bioanode and the biocathode, single-walled carbon nanotubes (SWCNTs) were used. In the bioanode, SWCNTs were used as the supporting materials for both methylene green (MG) which was used as the electrocatalyst for the oxidation of NADH and ADH. The as-constructed MG/ADH/SWCNTs-based bioanode exhibits a good activity toward the bioelectrocatalytic oxidation of ethanol. In the biocathode, the use of SWCNTs essentially facilities the direct electron transfer of BOD, and thereby enables the bioelectrocatalytic reduction of oxygen into water at a relatively high potential. An ethanol/O2 biofuel cell configuration was then assembled by utilizing the MG/ADH/SWCNTs as the bioanode and the BOD/SWCNTs as the biocathode. The biofuel cell gives a maximum power output of 11 μW·cm-2 in the presence of 40 mmol·L-1 ethanol as biofuel under ambient air in phosphate buffer (pH 7.0). Finally, we demonstrate that the ethanol/O2 biofuel cell could be powered by commercially available Vodak, giving a maximum power output of 3.7 μW·cm-2.
[1] Barton S C, Gallaway J, Atanassov P. Enzymatic biofuel cells for implantable and microscale devices[J]. Chemical Reviews, 2004, 104(10): 4867-4886.
[2] Willner I, Yan Y M, Willner B, et al. Integrated enzyme-based biofuel cells-A review[J]. Fuel Cells, 2009, 9(1): 7-24.
[3] Cooney M J, Svoboda V, Lan C, et al. Enzyme catalysed biofuel cells[J]. Energy & Environmental Science, 2008, 1(3): 320-337.
[4] Zhou M, Dong S J. Bioelectrochemical interface engineering: Toward the fabrication of electrochemical biosensors, biofuel bells, and self-powered logic biosensors[J]. Accounts of Chemical Research, 2011, 44(11): 1232-1243.
[5] Yan Y M, Zheng W, Su L, et al. Carbon-nanotube-based glucose/O2 biofuel cells[J]. Advanced Materials, 2006, 18(19): 2639-2643.
[6] Gao F, Yan Y M, Su L, et al. An enzymatic glucose/O2 biofuel cell: Preparation, characterization and performance in serum[J]. Electrochemistry Communications, 2007, 9(5): 989-996.
[7] Cheng H J, Yu P, Lu X L, et al. Biofuel cell-based self-powered biogenerators for online continuous monitoring of neurochemicals in rat brain[J]. Analyst, 2013, 138(1): 179-185.
[8] Cracknell J A, Vincent K A, Armstrong F A. Enzymes as working or inspirational electrocatalysts for fuel cells and electrolysis[J]. Chemical Reviews, 2008, 108(7): 2439-2461.
[9] Li X C, Zhou H J, Yu P, et al. A miniature glucose/O2 biofuel cell with single-walled carbon nanotubes-modified carbon fiber microelectrodes as the substrate[J]. Electrochemistry Communications, 2008, 10(6): 851-854.
[10] Logan B E, Hamelers B, Rozendal R A, et al. Microbial fuel cells: Methodology and technology[J]. Environmental Science & Technology, 2006, 40(17): 5181-5192.
[11] Katz E, Willner I, Kotlyar A B. A non-compartmentalized glucose vertical bar O2 biofuel cell by bioengineered electrode surfaces[J]. Journal of Electroanalytical Chemistry, 1999, 479(1): 64-68.
[12] Mano N, Mao F, Heller A. Characteristics of a miniature compartment-less glucose-O2 biofuel cell and its operation in a living plant[J]. Journal of the American Chemical Society, 2003, 125(21): 6588-6594.
[13] Halamkova L, Halamek J, Bocharova V, et al. Implanted biofuel cell operating in a living snail[J]. Journal of the American Chemical Society, 2012, 134(11): 5040-5043.
[14] Yan Y M, Yehezkeli O, Willner I. Integrated, electrically contacted NAD(P)(+)-dependent enzyme - carbon nanotube electrodes for biosensors and biofuel cell applications[J]. Chemistry-A European Journal, 2007, 12(36): 10168-10175.
[15] Yan Y M, Baravik I, Tel-Vered R, et al. An Ethanol/O2 biofuel cell based on an electropolymerized bilirubin oxidase/Pt nanoparticle bioelectrocatalytic O2-reduction cathode[J]. Advanced Materials, 2009, 21(42): 4275-4279.
[16] Yan Y M, Fang J M, Yang Z Y, et al. Photoelectrochemical oxidation of glucose for sensing and fuel cell applications[J]. Chemical Communications, 2013, 49(77): 8632-8634.
[17] Yan J, Zhou H J, Yu P, et al. Rational functionalization of carbon nanotubes leading to electrochemical devices with striking applications[J]. Advanced Materials, 2008, 20(15): 2899-2906.
[18] Han L, Bai L, Zhu C Z, et al. Improving the performance of a membraneless and mediatorless glucose-air biofuel cell with a TiO2 nanotube photoanode[J]. Chemical Communications, 2012, 48(49): 6103-6105.