CN101931083A - High-efficiency enzymatic biological fuel battery cathode and preparation method thereof - Google Patents
High-efficiency enzymatic biological fuel battery cathode and preparation method thereof Download PDFInfo
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- CN101931083A CN101931083A CN2009100867256A CN200910086725A CN101931083A CN 101931083 A CN101931083 A CN 101931083A CN 2009100867256 A CN2009100867256 A CN 2009100867256A CN 200910086725 A CN200910086725 A CN 200910086725A CN 101931083 A CN101931083 A CN 101931083A
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Abstract
The invention discloses a high-efficiency enzymatic biological fuel battery cathode and a preparation method thereof. The biological fuel battery cathode comprises a substrate electrode, a carbon nano-material layer coated on the substrate electrode and an enzymatic layer coated on the carbon nano-material layer, wherein the enzymatic layer comprises the following a material a) and b): a) laccase or bilirubin oxidase, b) the laccase or the bilirubin oxidase, which is cross-linked by a cross linking agent. Compared with an ordinary enzymatic biological fuel battery cathode, the enzymatic biological fuel battery cathode of the invention has higher oxygen catalytic reduction efficiency.
Description
Technical field
The present invention relates to a kind of high-efficiency enzymatic biological fuel battery cathode and preparation method thereof.
Background technology
Enzymatic biological fuel battery is a kind of novel energy technology of utilizing enzyme the chemical energy of biological substance (as glucose and oxygen etc.) to be changed into electric energy as catalyst, at the miniature energy field of implantable (as biology sensor, man-made organ, pacemaker power supply etc.) very application prospects (Yan et al., Carbon-Nanotube-Based Glucose/O arranged
2Biofuel Cells.Adv.Mater.2006,18,2639-2643; Gao et al., An enzymatic glucose/O
2Biofuel cell:Preparation, characterization andperformance in serum, Electrochem.Commun.2007,9,989-996).Because use enzyme as the bioelectrochemistry catalyst, the electrochemical properties of enzyme has key effect for the performance of enzymatic biological fuel battery.For example, when using electron mediator (Fei et al., A Biopolymer Composite that Catalyzes theReduction of Oxygen to Water.Chem.Mater., 2007,19,1565-1570; Mano et al., ALaccase-Wiring Redox Hydrogel for Efficient Catalysis of O
2Electroreduction.J.Phys.Chem.B 2006,110, and when 11180-11187) coming to carry out electron exchange between " assistance " enzyme and the electrode, the output potential of enzyme electrode just only depends on employed electron mediator; Yet when endonuclease capable and electrode carried out the direct electron exchange, the output potential of enzyme electrode can produce higher output potential near the formula current potential at the electro-chemical activity center of enzyme in theory.Because when laccase reduces at catalytic oxygen, have that the catalytic oxidation-reduction current potential is higher, enzymatic activity is higher, catalytic efficiency is than advantages such as height, becomes one of the most frequently used biocatalyst of current enzymatic biological fuel battery cathode.Although people generally utilize the Direct Electrochemistry character of laccase to construct the negative electrode of enzymatic biological fuel battery oxygen reduction, yet, the current efficiency of the negative electrode of prepared oxygen reduction is lower, become " bottleneck " of restriction biological fuel cell power output size, can't satisfy the demand of current biological fuel cell development.
Summary of the invention
The purpose of this invention is to provide a kind of high-efficiency enzymatic biological fuel battery cathode and preparation method thereof.
Biofuel battery cathode provided by the present invention comprises basal electrode, is coated on the carbon nanomaterial layer on the described basal electrode and is coated on enzyme layer on the described carbon nanomaterial layer; Described enzyme layer comprise following a) or b) material: a) laccase or bilirubin oxidase, b) through the crosslinked laccase of crosslinking agent or through the crosslinked bilirubin oxidase of crosslinking agent.
In described carbon nanomaterial layer, the content of carbon nanomaterial is every square centimeter of 20-200 μ g on the basal electrode; Described carbon nanomaterial can be a kind of in carbon nano-tube, carbon nano-fiber and the Nano carbon balls.
In described enzyme layer, described laccase or the bilirubin oxidase content of every square centimeter of basal electrode relatively are 3-20U.Described laccase is from fungi.
Also can select crosslinking agent for use for the stability that increases the enzyme layer and carry out fixing between the enzyme, described crosslinking agent specifically can be glutaraldehyde, hexamethylene diamine, maleic anhydride or bisazo benzene, is preferably glutaraldehyde.With the glutaraldehyde is example, and with respect to every square centimeter of basal electrode, its use amount is the glutaraldehyde solution 0.5-4 μ l of mass fraction 1-10%.
The present invention has no special requirements to the size of carbon nanomaterial, and in general, the diameter of described carbon nano-fiber and carbon nano-tube is 1～100nm, is preferably 1～50nm, and average length is 0.5～50 μ m, is preferably 0.5～20 μ m; The diameter of described Nano carbon balls is 50～500nm.
The method of the above-mentioned high-efficiency enzymatic biological fuel battery cathode of preparation provided by the present invention may further comprise the steps:
1) carbon nanomaterial is scattered in carries out sonicated in the organic solvent, obtain the carbon nanomaterial suspension-turbid liquid, described suspension-turbid liquid is coated on the basal electrode, drying forms the carbon nanomaterial layer;
2) will contain following a), b) or c) solution of material be coated on the carbon nanomaterial layer, dry back forms the enzyme layer on the carbon nanomaterial layer, promptly obtain described biofuel battery cathode; Described a) is laccase or bilirubin oxidase, described b) be laccase and crosslinking agent, described c) be bilirubin oxidase and crosslinking agent.
The organic solvent of described step 1) specifically can be dimethyl formamide, acetone, ethanol, N-N-methyl-2-2-pyrrolidone N-or acetonitrile, is preferably dimethyl formamide.The concentration of carbon nanomaterial is every milliliter of 1-5mg in the described suspension-turbid liquid.The time that described sonicated is carried out can be 0.1-2 hour.
Among the present invention, when used carbon nanomaterial is carbon nano-fiber and carbon nano-tube, before using, need carbon nano-fiber and carbon nano-tube are carried out the metallic catalyst of purifying when removing preparation.When used carbon nanomaterial is Nano carbon balls, can directly use without special processing.
Concrete purification process is as follows: used acid is nitric acid or the hydrochloric acid of 1～5M during purifying, and temperature is 10～120 ℃, and the purifying time is 1～10 hour.
Used laccase is the laccase behind the purifying among the present invention.In order to increase the activity of laccase, available organic solvent activates laccase, and described organic solvent can be dimethyl formamide, acetone, ethanol or N-N-methyl-2-2-pyrrolidone N-or acetonitrile, is preferably acetone, acetonitrile or ethanol.
The present invention utilizes carbon nanomaterial to quicken electron transport between laccase and the electrode, realized the Direct Electrochemistry of laccase, and by multiple organic reagent influence laccase on electrode towards, a kind of enzymatic biological fuel battery cathode that makes up efficient catalytic oxidation-reduction and preparation method thereof is provided.Cell cathode of the present invention has excellent catalytic effect to oxygen.
The present invention forms the carbon nanomaterial layer as realizing the efficient media of laccase direct electrochemistry by scattered carbon nanomaterial suspension-turbid liquid being coated on the basal electrode surface, then the laccase behind the purifying is coated on after organic solvent is handled and forms the enzyme layer on the carbon nanomaterial layer, also select crosslinking agent for use for the stability that increases the enzyme layer and carry out the preparation of fixedly finishing biofuel battery cathode between the enzyme.This negative electrode has been realized the efficient catalytic reduction of laccase to oxygen in the cushioning liquid of pH6, the result is better than the laccase handled without the organic solvent electrochemical catalysis to hydrogen reduction.
Description of drawings
Fig. 1 is the structural representation of high-efficiency enzymatic biological fuel battery cathode, wherein, and 1 expression carbon nano-fiber or carbon nano-tube, 2 expression Nano carbon balls, 3 expression laccase or bilirubin oxidases, 4 expression basal electrodes;
Fig. 2 is the high-efficiency enzymatic biological fuel battery cathode hydrogen reduction cyclic voltammetric schematic diagram among the embodiment 2.
Embodiment
The purifying of embodiment 1, laccase
With 50mg laccase (Trametes Versicolor E.C.1.10.3.2,23.76U/mg) be dissolved in 500 μ L0.1M phosphate buffer solutions (pH6.0) and move in the bag filter, this bag filter is dipped in middle stirring of fresh 0.1M phosphate buffer solution (pH6.0) dialysed 4 hours, move in another fresh 0.1M phosphate buffer solution (pH6.0) again and stirred 4 hours, so the circulation dialysis is 1-2 days.Solution adds ammonium sulfate until saturated in bag then, has precipitation to separate out, then with this suspension-turbid liquid under 5000 rev/mins rotating speed centrifugal 10 minutes; The gained precipitation is dissolved in about 500 μ L0.1M phosphate buffer solutions (pH6.0), saturated with ammonium sulfate again, there is precipitation to separate out again; The centrifugal again precipitation that obtains, and gained precipitation is dissolved in 300 μ L0.1M phosphate buffer solutions (pH6.0) puts into dialysis tubing centrifugally under 5000 rev/mins rotating speed concentrates 5 minutes, and the gained concentrate is stored in the refrigerator standby.
The preparation of embodiment 2, high-efficiency enzymatic biological fuel battery cathode
With the 2mg carbon nano-tube (nanometer port, Shenzhen Co., Ltd, diameter＜2nm) in 0.5mL ethanol continuous ultrasound (ultrasound intensity is about 1w/cm
2, supersonic frequency is 40kHz) and 1 hour, dispersion treatment forms the suspension-turbid liquid of every milliliter of 4mg, gets on the glass carbon substrate electrode that 3 μ L suspension-turbid liquids are coated on 0.07 square centimeter, at air drying, forms the carbon nanomaterial layer.Laccase needs purifying before use, and its concrete steps as described in example 1 above.With the 100 μ L concentration of gained behind the purifying is 1000U/ml laccase (Trametes Versicolor E.C.1.10.3.2,23.76U/mg) solution mixes with 20 μ L ethanol and obtain containing 100U laccase mixed liquor, getting 1.5 μ L laccase mixed liquors is coated on the carbon nanomaterial layer, promptly get the enzyme layer in drying at room temperature, finish the high-efficiency enzymatic biological fuel battery cathode preparation.
This electrode and the common laccase negative electrode hydrogen reduction performance in saturated pH 6 phosphate buffer solutions of air or nitrogen is shown in Fig. 2, wherein, common laccase negative electrode and high-efficiency enzymatic biological fuel battery cathode hydrogen reduction cyclic voltammetry curve in pH 6 solution of rule among the figure, solid line being represented the saturation of the air respectively, dotted line is represented the background curves of above-mentioned two kinds of electrodes in the saturated pH of nitrogen 6 solution.As seen from the figure, high-efficiency enzymatic biological fuel battery cathode not only is better than common laccase negative electrode on a spike potential, on the hydrogen reduction faradic currents, exceed several times than the latter especially, illustrate that high-efficiency enzymatic biological fuel battery cathode catalytic oxidation-reduction efficient is higher, this helps improving the power output of biological fuel cell.
The preparation of embodiment 3, high-efficiency enzymatic biological fuel battery cathode
(Institute of Chemistry, Academia Sinica is synthetic with l mg Nano carbon balls, diameter 0.5 μ m, list of references: Macromolecular Chemistry and Physics 207 (18): 1633-1639) in the 1mL dimethyl formamide continuous ultrasound (ultrasound intensity is about 1w/cm
2, supersonic frequency is 40kHz) and 0.1 hour, dispersion treatment forms the suspension-turbid liquid of every milliliter of 1mg, gets on the glass carbon substrate electrode that 3.5 μ L suspension-turbid liquids are coated on 0.07 square centimeter, at air drying, forms the carbon nanomaterial layer; With 60 μ L concentration is 1000U/ml bilirubin oxidase (BOD, E.C.1.10.3.2, from Myrothecium verrucaria) solution mixes the mixed liquor that obtains containing the 60U bilirubin oxidase with 20 μ L acetone, getting 1.8 μ L bilirubin oxidase mixed liquors is coated on the carbon nanomaterial layer, promptly get the enzyme layer in drying at room temperature, finish the high-efficiency enzymatic biological fuel battery cathode preparation.
The preparation of embodiment 4, high-efficiency enzymatic biological fuel battery cathode
(Institute of Chemistry, Academia Sinica is synthetic with the 1mg Nano carbon balls, diameter 0.5 μ m, list of references: Macromolecular Chemistry and Physics 207 (18): 1633-1639) in the 1mL dimethyl formamide continuous ultrasound (ultrasound intensity is about 1w/cm
2, supersonic frequency is 40kHz) and 0.1 hour, dispersion treatment forms the suspension-turbid liquid of every milliliter of 1mg, gets on the glass carbon substrate electrode that 1.4 μ L suspension-turbid liquids are coated on 0.07 square centimeter, at air drying, forms the carbon nanomaterial layer; With 60 μ L concentration is 1000U/ml bilirubin oxidase (BOD, E.C.1.10.3.2, from Myrothecium verrucaria) solution mixes the mixed liquor that obtains containing the 60U bilirubin oxidase with 20 μ L acetone, getting 0.28 μ L bilirubin oxidase mixed liquor is coated on the carbon nanomaterial layer, promptly get the enzyme layer in drying at room temperature, finish the high-efficiency enzymatic biological fuel battery cathode preparation.
The preparation of embodiment 5, high-efficiency enzymatic biological fuel battery cathode
(Institute of Chemistry, Academia Sinica is synthetic with the 1mg Nano carbon balls, diameter 0.5 μ m, list of references: Macromolecular Chemistry and Physics 207 (18): 1633-1639) in the 1mL dimethyl formamide continuous ultrasound (ultrasound intensity is about 1w/cm
2, supersonic frequency is 40kHz) and 0.1 hour, dispersion treatment forms the suspension-turbid liquid of every milliliter of 1mg, gets on the glass carbon substrate electrode that 14 μ L suspension-turbid liquids are coated on 0.07 square centimeter, at air drying, forms the carbon nanomaterial layer; With 60 μ L concentration is 1000U/ml bilirubin oxidase (BOD, E.C.1.10.3.2, from Myrothecium verrucaria) solution mixes the mixed liquor that obtains containing the 60U bilirubin oxidase with 20 μ L acetone, getting 1.87 μ L bilirubin oxidase mixed liquors is coated on the carbon nanomaterial layer, promptly get the enzyme layer in drying at room temperature, finish the high-efficiency enzymatic biological fuel battery cathode preparation.
Claims (10)
1. biofuel battery cathode comprises basal electrode, is coated on the carbon nanomaterial layer on the described basal electrode and is coated on enzyme layer on the described carbon nanomaterial layer; Described enzyme layer comprise following a) or b) material: a) laccase or bilirubin oxidase, b) through the crosslinked laccase of crosslinking agent or through the crosslinked bilirubin oxidase of crosslinking agent.
2. biofuel battery cathode according to claim 1 is characterized in that: described carbon nanomaterial is a kind of in carbon nano-tube, carbon nano-fiber and the Nano carbon balls.
3. biofuel battery cathode according to claim 1 and 2 is characterized in that: in the described carbon nanomaterial layer, the content of carbon nanomaterial is 20-200 μ g on every square centimeter of basal electrode; In the described enzyme layer, described laccase or bilirubin oxidase are every square centimeter of 3-20U with respect to the content of basal electrode.
4. according to arbitrary described biofuel battery cathode among the claim 1-3, it is characterized in that: described crosslinking agent is glutaraldehyde, hexamethylene diamine, maleic anhydride or bisazo benzene, is preferably glutaraldehyde.
5. according to arbitrary described biofuel battery cathode among the claim 2-4, it is characterized in that: the diameter of described carbon nano-fiber and carbon nano-tube is 1～100nm, is preferably 1～50nm, and average length is 0.5～50 μ m, is preferably 0.5～20 μ m; The diameter of described Nano carbon balls is 50～500nm.
6. prepare the method for arbitrary described biofuel battery cathode among the claim 1-5, may further comprise the steps:
1) carbon nanomaterial described in the biofuel battery cathode described in the claim 1-5 is scattered in carries out sonicated in the organic solvent, obtain the carbon nanomaterial suspension-turbid liquid, described suspension-turbid liquid is coated on the basal electrode, drying forms the carbon nanomaterial layer;
2) will contain following a), b) or c) solution of material be coated on the carbon nanomaterial layer, dry back forms the enzyme layer on the carbon nanomaterial layer, promptly obtain described biofuel battery cathode; Described a) is laccase described in the biofuel battery cathode or bilirubin oxidase described in the claim 1-5, described b) be laccase described in the biofuel battery cathode and crosslinking agent described in the claim 1-5, described c) be bilirubin oxidase and crosslinking agent described in the biofuel battery cathode described in the claim 1-5.
7. method according to claim 6 is characterized in that: described carbon nanomaterial is carbon nano-fiber and carbon nano-tube, and the carbon nanomaterial in the described step 1) is through purifying.
8. according to claim 6 or 7 described methods, it is characterized in that: the organic solvent of described step 1) is dimethyl formamide, acetone, ethanol, N-N-methyl-2-2-pyrrolidone N-or acetonitrile, is preferably dimethyl formamide; The concentration of carbon nanomaterial is every milliliter of 1-5mg in the described suspension-turbid liquid.
9. according to arbitrary described method among the claim 6-8, it is characterized in that: laccase described step 2) is the laccase through the organic solvent activation.
10. method according to claim 9 is characterized in that: described organic solvent is dimethyl formamide, acetone, ethanol, N-N-methyl-2-2-pyrrolidone N-or acetonitrile, is preferably acetone, acetonitrile or ethanol.
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