CN101834301A - Biochemical nano generator and preparation method thereof - Google Patents
Biochemical nano generator and preparation method thereof Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention discloses a biochemical nano generator and a preparation method thereof. The preparation method comprises the following steps of: selecting a substrate with an insulating layer on the surface, wherein the substrate is provided with an anode area and a cathode areas of a battery; then bridging a prepared proton conducted nanowire over the node and cathode areas; evaporating a silica layer for separating the node area from the cathode area, and then adding a catalyst into the node and cathode areas dropwise; and finally, adding a fuel and an oxidant to obtain the nano generator. The prepared nano generator comprises the substrate which is provided with the cathode area of the battery and the anode area of the battery; the proton conducted nanowire is bridged over the cathode area of the battery and the anode area of the battery; the cathode area of the battery and the anode area of the battery are both provided with leading-out leads; and the biochemical nano generator is taken as a one-dimensional proton transmission channel, the conductivity of the proton is 3 to 4 orders of magnitude higher than that of the traditional commercial proton exchanging film.
Description
Technical field
The present invention relates to a kind of biological nano device, particularly a kind of biochemical nano generator and preparation method thereof.
Background technology
Progress along with nanometer science and technology, utilize the special performance of nano material, developed the nano-device of a large amount of various functions, medical monitor, cancer cell molecule detecting sensor, photoelectric sensor etc. in nano biological sensor, field effect transistor, the real-time body have been arranged.But these nano-devices all need the supply of extra power to work, and existing energy Source size is all bigger, and this just makes development nanometer energy become the task of top priority.Finally need to realize the nanometer energy and nano-device are integrated on the same chip, become a global function nanosystems (Nano-System) of collecting rice functional unit, nanometer energy unit, nanometer communication unit.Therefore, the research of the nanometer energy has just received great concern.The research of the nanometer energy is also at the early-stage in the world at present, the existing nanometer energy mainly contains the nanometer piezoelectric generator that the Wang Zhonglin of U.S. Georgia Tech professor seminar utilizes the piezoelectric property of zinc oxide nanowire to make, mainly mechanical vibrational energy is converted into electric energy, article see for details " Qin; Y.; Wang, X.D.﹠amp; Wang, Z.L.Microfibre-nanowire hybrid structure for energy scavenging.Nature 451,809-U5 (2008); Wang, X.D., Song, J.H., Liu, J.﹠amp; Wang, Z.L.Direct-current nanogenerator driven by ultrasonicwaves.Science 316,102-105 (2007) ", but the power of this generator is big not enough, remains further to be improved; The nano solar battery that the Lieber of Harvard University professor seminar utilizes the silicon nanowires of single " coaxial cable structure (core-shell) " to make, mainly luminous energy is converted into electric energy, article sees " Tian; B.Z.et al.Coaxial siliconnanowires as solar cells and nanoelectronic power sources.Nature 449; 885-U8 (2007) " for details, and successfully use these nanometer energy to be the nano-device energy supply, but the occasion of this solar cell application is comparatively limited, there is not the place of light just can't use at some, as the work of just having no idea in the organism.
Summary of the invention
In order to overcome the defective of above-mentioned prior art, the object of the present invention is to provide a kind of biochemical nano generator and preparation method thereof, biochemical nano generator is based on single nano-wire and nano-wire array, have the proton transport passage of the proton conduction nano wire of proton transport structure as one dimension, proton conductivity is than the high 3-4 of a proton conductivity order of magnitude of present commercial proton exchange membrane.
In order to achieve the above object, technical scheme of the present invention is achieved in that
A kind of biochemical nano generator, comprise a substrate 4, substrate 4 is provided with cell cathode district 2 and anode region 3, and lead 5 in the cell cathode district 2 and anode region 3 of substrate 4, is all drawn on cell cathode district 2 and the anode region 3 respectively in the two ends of proton conduction nano wire 1.
Described proton conduction nano wire 1 diameter is in 50nm arrives the 20um scope, length reaches Centimeter Level, the proton conductivity of this proton conduction body is than the high 3-4 of a proton conductivity order of magnitude of present commercial proton exchange membrane, and is index along with reducing of nanowire diameter and increases.
Must there be a layer insulating on described substrate 4 surfaces.
A kind of preparation method of biochemical nano generator may further comprise the steps:
One, select the surface that the substrate 4 of insulating barrier is arranged, substrate 4 can be a semi-conducting material, as silicon chip or Si/SiO
2Can be the high molecule plastic material, as polycarbonate or polymetylmethacrylate; Can be ceramic material also, as alumina wafer, and substrate 4 be provided with cell cathode district 2 and anode region 3;
Two, preparation proton conduction nano wire 1, with the solution of proton exchange membrane and high-molecular polythene solution by being made into mixed solution at 4: 1, the solution of proton exchange membrane is Nafion or Dow solution, and high-molecular polythene solution is polyethylene pyrrole Lopa Nationality alkane ketone PVP or PVAC polyvinylalcohol;
Three, the mixed solution in the step 2 is utilized electrospinning silk or template aux. pressure injection method obtain proton conduction nano wire 1, proton conduction nano wire 1 is connected across in the cell cathode district 2 and anode region 3 in the substrate 4;
Four, evaporation layer of silicon dioxide floor between cell cathode district 2 and anode region 3 distinguishes cell cathode district 2 and anode region 3;
Five, cathod catalyst is dripped in cell cathode district 2, anode catalyst drips in anode region 3, the amount that drips will make dried catalyst molecule be adsorbed on proton conduction nano wire 2 and cell cathode district 2 and anode region 3 surfaces, wherein cathod catalyst is Pt/C, PtRu/C or biological oxidation enzyme, and anode catalyst is Pt/C, glucose oxidase or bilirubin enzyme;
Six, add fuel in anode region 3, cell cathode district 2 adds oxidants, can obtain the nano generator that can generate electricity, and described fuel adopts methyl alcohol, hydrogen or glucose solution, and oxidant adopts oxygen, air or potassium permanganate.
Electrical spinning method described in the step 3 is: the mixed solution that step 2 is prepared places in the syringe, with internal diameter is 0.7mm, the 7# standard needle that the tip polishes is connected with positive extremely high tension generator, required voltage is 5～30kV, the flow of solution is controlled by syringe pump, and flow is 0.1ml/h～10ml/h, and the fixed distance of spinning is 10～20cm, when not requiring acquisition orientation proton conduction nano wire 1, use the aluminium foil of ground connection to be receiving system; When requiring to obtain orientation proton conduction nano wire 1, the pair of parallel electrode that adopts ground connection is as receiving system.
Template aux. pressure injection method described in the step 3 is: the mixed solution that step 2 is prepared, be pressed in the hole of anodic oxidation aluminium formwork 30～100nm, drying at room temperature 10-30 hour then, volatilize fully until solvent, remove anodic oxidation aluminium formwork, obtain proton conduction nano wire 1.
The nano generator that the present invention is prepared has excellent performance, and open circuit voltage can reach 430mV, and maximum current density reaches 4.33 μ A/ μ m
2, maximum power density reaches 0.44 μ W/ μ m
2Simultaneously, we have also showed this nano biological Chemically generation machine that utilizes, and set up the feasibility of the self energizing nanosystems in the implantable.Can be used for measuring the pH transducer and the glucose sensor of the pH value and the blood sugar concentration of blood of human body, under the driving of this nano biological Chemically generation machine, all can well work.We have also showed and utilize this nano biological Chemically generation machine to obtain energy from environment equally, continue to drive the feasibility of abiotic nano-device.
This nano biological Chemically generation machine is to obtaining the research of energy from environment, in order to drive biological nano device, wireless senser, or even mobile electronic device, set up the self energizing nanosystems a kind of new method is provided, all very big application prospect will arranged aspect biology, environmental monitoring, defense technology even the personal electric device.
Description of drawings
Accompanying drawing is the structure principle chart of biochemical nano generator of the present invention.
Embodiment
The present invention will be further described below in conjunction with drawings and Examples, but these embodiment are not the restriction to summary of the invention, and just schematically explanation.
With reference to accompanying drawing, a kind of biochemical nano generator, comprise a substrate 4, substrate 4 is provided with cell cathode district 2 and anode region 3, lead 5 in the cell cathode district 2 and anode region 3 of substrate 4, is all drawn on cell cathode district 2 and the anode region 3 respectively in the two ends of proton conduction nano wire 1.
Embodiment one
Present embodiment may further comprise the steps:
One, select the surface that the substrate 4 of insulating barrier is arranged, substrate 4 is semi-conducting materials, i.e. Si/SiO
2Silicon chip, and substrate 4 is provided with on cell cathode district 2 and the anode region 3;
Two, preparation proton conduction nano wire 1, and the solution and the high-molecular polythene solution of proton exchange membrane was made into mixed solution by 4: 1, and the solution of proton exchange membrane is Nafion, and high-molecular polythene solution is PVAC polyvinylalcohol;
Three, the mixed solution in the step 2 is utilized the electrospinning silk obtain diameter and be 100nm proton conduction nano wire 1, proton conduction nano wire 1 is connected across in the cell cathode district 2 and anode region 3 in the substrate 4;
Four, evaporation layer of silicon dioxide floor between cell cathode district 2 and anode region 3 distinguishes cell cathode district 2 and anode region 3;
Five, cathod catalyst is dripped in cell cathode district 2, anode catalyst drips in anode region 3, the amount that drips will make dried catalyst molecule be adsorbed on proton conduction nano wire 2 and cell cathode district 2 and anode region 3 surfaces, wherein cathod catalyst is PtRu/C, and anode catalyst is Pt/C;
Six, add fuel in anode region 3, cell cathode district 2 adds oxidants, can obtain the nano generator that can generate electricity, and described fuel adopts methyl alcohol, and oxidant adopts oxygen.
At room temperature, the worth biochemical nano generator of present embodiment can successfully be worked.
Embodiment two
Present embodiment may further comprise the steps:
One, select the surface that the substrate 4 of insulating barrier is arranged, substrate 4 is high molecule plastic materials, i.e. polycarbonate, and substrate 4 is provided with on cell cathode district 2 and the anode region 3;
Two, preparation proton conduction nano wire 1, and the solution and the high-molecular polythene solution of proton exchange membrane was made into mixed solution by 4: 1, and the solution of proton exchange membrane is Dow solution, and high-molecular polythene solution is polyethylene pyrrole Lopa Nationality alkane ketone PVP;
Three, the mixed solution in the step 2 is utilized template aux. pressure injection method obtain diameter and be 100nm proton conduction nano wire 1, proton conduction nano wire 1 is connected across in the cell cathode district 2 and anode region 3 in the substrate 4;
Four, evaporation layer of silicon dioxide floor between cell cathode district 2 and anode region 3 distinguishes cell cathode district 2 and anode region 3;
Five, cathod catalyst is dripped in cell cathode district 2, anode catalyst drips in anode region 3, the amount that drips will make dried catalyst molecule be adsorbed on proton conduction nano wire 2 and cell cathode district 2 and anode region 3 surfaces, wherein cathod catalyst is that the biological oxidation enzyme is a laccase, and anode catalyst is a glucose oxidase;
Six, add fuel in anode region 3, cell cathode district 2 adds oxidants, can obtain the nano generator that can generate electricity, and described fuel adopts glucose solution, and oxidant adopts oxygen.
At room temperature, the worth biochemical nano generator of present embodiment can successfully be worked.
Embodiment three
Present embodiment may further comprise the steps:
One, select the surface that the substrate 4 of insulating barrier is arranged, substrate 4 is ceramic materials, i.e. alumina wafer, and substrate 4 is provided with on cell cathode district 2 and the anode region 3;
Two, preparation proton conduction nano wire 1, and the solution and the high-molecular polythene solution of proton exchange membrane was made into mixed solution by 4: 1, and the solution of proton exchange membrane is Dow solution, and high-molecular polythene solution is polyethylene pyrrole Lopa Nationality alkane ketone PVP;
Three, the mixed solution in the step 2 is utilized electrical spinning method obtain diameter and be 1000nm proton conduction nano wire 1, proton conduction nano wire 1 is connected across in the cell cathode district 2 and anode region 3 in the substrate 4;
Four, evaporation layer of silicon dioxide floor between cell cathode district 2 and anode region 3 distinguishes cell cathode district 2 and anode region 3;
Five, cathod catalyst is dripped in cell cathode district 2, anode catalyst drips in anode region 3, the amount that drips will make dried catalyst molecule be adsorbed on proton conduction nano wire 2 and cell cathode district 2 and anode region 3 surfaces, wherein cathod catalyst is Pt/C, and anode catalyst is the bilirubin enzyme;
Six, add fuel in anode region 3, cell cathode district 2 adds oxidants, can obtain the nano generator that can generate electricity, and described fuel adopts hydrogen, and oxidant adopts air.
At room temperature, the worth biochemical nano generator of present embodiment can successfully be worked.
Embodiment four
Present embodiment may further comprise the steps:
One, select the surface that the substrate 4 of insulating barrier is arranged, substrate 4 is semi-conducting materials, i.e. Si/SiO
2, and substrate 4 is provided with on cell cathode district 2 and the anode region 3;
Two, preparation proton conduction nano wire 1, and the solution and the high-molecular polythene solution of proton exchange membrane was made into mixed solution by 4: 1, and the solution of proton exchange membrane is Nafion, and high-molecular polythene solution is polyethylene pyrrole Lopa Nationality alkane ketone PVP;
Three, the mixed solution in the step 2 is utilized template aux. pressure injection method obtain diameter and be 500nm proton conduction nano wire 1, proton conduction nano wire 1 is connected across in the cell cathode district 2 and anode region 3 in the substrate 4;
Four, evaporation layer of silicon dioxide floor between cell cathode district 2 and anode region 3 distinguishes cell cathode district 2 and anode region 3;
Five, cathod catalyst is dripped in cell cathode district 2, anode catalyst drips in anode region 3, the amount that drips will make dried catalyst molecule be adsorbed on proton conduction nano wire 2 and cell cathode district 2 and anode region 3 surfaces, wherein cathod catalyst is PtRu/C, and anode catalyst is Pt/C;
Six, add fuel in anode region 3, cell cathode district 2 adds oxidants, can obtain the nano generator that can generate electricity, and described fuel adopts methyl alcohol, and oxidant adopts potassium permanganate.
At room temperature, the worth biochemical nano generator of present embodiment can successfully be worked.
Claims (10)
1. biochemical nano generator, it is characterized in that, comprise a substrate (4), substrate (4) is provided with cell cathode district (2) and anode region (3), lead (5) in the cell cathode district (2) and anode region (3) of substrate (4), is all drawn on cell cathode district (2) and the anode region (3) respectively in the two ends of proton conduction nano wire (1).
2. a kind of biochemical nano generator according to claim 1 is characterized in that, in the 20um scope, length reaches Centimeter Level to described proton conduction nano wire 1 diameter at 50nm.
3. a kind of biochemical nano generator according to claim 1 is characterized in that, there is a layer insulating on described substrate 4 surfaces.
4. the preparation method of a biochemical nano generator is characterized in that, may further comprise the steps: one, select the surface that the substrate 4 of insulating barrier is arranged, substrate 4 can be a semi-conducting material, as silicon chip or Si/SiO
2, and substrate 4 is provided with on cell cathode district 2 and the anode region 3; Can be the high molecule plastic material, as polycarbonate or polymetylmethacrylate; Can be ceramic material also, as alumina wafer; Two, preparation proton conduction nano wire 1, with the solution of proton exchange membrane and high-molecular polythene solution by being made into mixed solution at 4: 1, the solution of proton exchange membrane is Nafion or Dow solution, and high-molecular polythene solution is polyethylene pyrrole Lopa Nationality alkane ketone PVP or PVAC polyvinylalcohol; Three, the mixed solution in the step 2 is utilized electrospinning silk or template aux. pressure injection method obtain proton conduction nano wire 1, proton conduction nano wire 1 is connected across in the cell cathode district 2 and anode region 3 in the substrate 4; Four, evaporation layer of silicon dioxide floor between cell cathode district 2 and anode region 3 distinguishes cell cathode district 2 and anode region 3; Five, cathod catalyst is dripped in cell cathode district 2, anode catalyst drips in anode region 3, the amount that drips will make dried catalyst molecule be adsorbed on proton conduction nano wire 2 and cell cathode district 2 and anode region 3 surfaces, wherein cathod catalyst is Pt/C, PtRu/C or biological oxidation enzyme (as laccase), and anode catalyst is Pt/C, glucose oxidase or bilirubin enzyme; Six, add fuel in anode region 3, cell cathode district 2 adds oxidants, can obtain the nano generator that can generate electricity, and described fuel adopts methyl alcohol, hydrogen or glucose solution, and oxidant adopts oxygen, air or potassium permanganate.
5. the preparation method of a kind of biochemical nano generator according to claim 4, it is characterized in that, electrical spinning method described in the step 3 is: the mixed solution for preparing is placed in the syringe, with internal diameter is 0.7mm, the 7# standard needle that the tip polishes is connected with positive extremely high tension generator, required voltage is 5～30kV, the flow of solution is controlled by syringe pump, flow is 0.1ml/h～10ml/h, the fixed distance of spinning is 10～20cm, when not requiring acquisition orientation proton conduction nano wire 1, use the aluminium foil of ground connection to be receiving system; When requiring to obtain orientation proton conduction nano wire 1, the pair of parallel electrode that adopts ground connection is as receiving system.
6. the preparation method of a kind of biochemical nano generator according to claim 4, it is characterized in that, template aux. pressure injection method described in the step 3 is: with the solution for preparing, be pressed in the hole of anodic oxidation aluminium formwork 30～100nm, drying at room temperature 10-30 hour then, volatilize fully until solvent, remove anodic oxidation aluminium formwork, can obtain proton conduction nano wire 1.
7. the preparation method of a kind of biochemical nano generator according to claim 4 is characterized in that, may further comprise the steps: one, select the surface that the substrate 4 of insulating barrier is arranged, substrate 4 is semi-conducting materials, i.e. Si/SiO
2Silicon chip, and substrate 4 is provided with on cell cathode district 2 and the anode region 3; Two, preparation proton conduction nano wire 1, and the solution and the high-molecular polythene solution of proton exchange membrane was made into mixed solution by 4: 1, and the solution of proton exchange membrane is Nafion, and high-molecular polythene solution is PVAC polyvinylalcohol; Three, the mixed solution in the step 2 is utilized the electrospinning silk obtain diameter and be 100nm proton conduction nano wire 1, proton conduction nano wire 1 is connected across in the cell cathode district 2 and anode region 3 in the substrate 4; Four, evaporation layer of silicon dioxide floor between cell cathode district 2 and anode region 3 distinguishes cell cathode district 2 and anode region 3; Five, cathod catalyst is dripped in cell cathode district 2, anode catalyst drips in anode region 3, the amount that drips will make dried catalyst molecule be adsorbed on proton conduction nano wire 2 and cell cathode district 2 and anode region 3 surfaces, wherein cathod catalyst is PtRu/C, and anode catalyst is Pt/C; Six, add fuel in anode region 3, cell cathode district 2 adds oxidants, can obtain the nano generator that can generate electricity, and described fuel adopts methyl alcohol, and oxidant adopts oxygen.
8. the preparation method of a kind of biochemical nano generator according to claim 4, it is characterized in that, may further comprise the steps: one, select the surface that the substrate 4 of insulating barrier is arranged, substrate 4 is high molecule plastic materials, be polycarbonate, and substrate 4 is provided with on cell cathode district 2 and the anode region 3; Two, preparation proton conduction nano wire 1, and the solution and the high-molecular polythene solution of proton exchange membrane was made into mixed solution by 4: 1, and the solution of proton exchange membrane is Dow solution, and high-molecular polythene solution is polyethylene pyrrole Lopa Nationality alkane ketone PVP; Three, the mixed solution in the step 2 is utilized template aux. pressure injection method obtain diameter and be 100nm proton conduction nano wire 1, proton conduction nano wire 1 is connected across in the cell cathode district 2 and anode region 3 in the substrate 4; Four, evaporation layer of silicon dioxide floor between cell cathode district 2 and anode region 3 distinguishes cell cathode district 2 and anode region 3; Five, cathod catalyst is dripped in cell cathode district 2, anode catalyst drips in anode region 3, the amount that drips will make dried catalyst molecule be adsorbed on proton conduction nano wire 2 and cell cathode district 2 and anode region 3 surfaces, wherein cathod catalyst is that the biological oxidation enzyme is a laccase, and anode catalyst is a glucose oxidase; Six, add fuel in anode region 3, cell cathode district 2 adds oxidants, can obtain the nano generator that can generate electricity, and described fuel adopts glucose solution, and oxidant adopts oxygen.
9. the preparation method of a kind of biochemical nano generator according to claim 4, it is characterized in that, may further comprise the steps: one, select the surface that the substrate 4 of insulating barrier is arranged, substrate 4 is ceramic materials, be alumina wafer, and substrate 4 is provided with on cell cathode district 2 and the anode region 3; Two, preparation proton conduction nano wire 1, and the solution and the high-molecular polythene solution of proton exchange membrane was made into mixed solution by 4: 1, and the solution of proton exchange membrane is Dow solution, and high-molecular polythene solution is polyethylene pyrrole Lopa Nationality alkane ketone PVP; Three, the mixed solution in the step 2 is utilized electrical spinning method obtain diameter and be 1000nm proton conduction nano wire 1, proton conduction nano wire 1 is connected across in the cell cathode district 2 and anode region 3 in the substrate 4; Four, evaporation layer of silicon dioxide floor between cell cathode district 2 and anode region 3 distinguishes cell cathode district 2 and anode region 3; Five, cathod catalyst is dripped in cell cathode district 2, anode catalyst drips in anode region 3, the amount that drips will make dried catalyst molecule be adsorbed on proton conduction nano wire 2 and cell cathode district 2 and anode region 3 surfaces, wherein cathod catalyst is Pt/C, and anode catalyst is the bilirubin enzyme; Six, add fuel in anode region 3, cell cathode district 2 adds oxidants, can obtain the nano generator that can generate electricity, and described fuel adopts hydrogen, and oxidant adopts air.
10. the preparation method of a kind of biochemical nano generator according to claim 4 is characterized in that, may further comprise the steps: one, select the surface that the substrate 4 of insulating barrier is arranged, substrate 4 is semi-conducting materials, i.e. Si/SiO
2, and substrate 4 is provided with on cell cathode district 2 and the anode region 3; Two, preparation proton conduction nano wire 1, and the solution and the high-molecular polythene solution of proton exchange membrane was made into mixed solution by 4: 1, and the solution of proton exchange membrane is Nafion, and high-molecular polythene solution is polyethylene pyrrole Lopa Nationality alkane ketone PVP; Three, the mixed solution in the step 2 is utilized template aux. pressure injection method obtain diameter and be 500nm proton conduction nano wire 1, proton conduction nano wire 1 is connected across in the cell cathode district 2 and anode region 3 in the substrate 4; Four, evaporation layer of silicon dioxide floor between cell cathode district 2 and anode region 3 distinguishes cell cathode district 2 and anode region 3; Five, cathod catalyst is dripped in cell cathode district 2, anode catalyst drips in anode region 3, the amount that drips will make dried catalyst molecule be adsorbed on proton conduction nano wire 2 and cell cathode district 2 and anode region 3 surfaces, wherein cathod catalyst is PtRu/C, and anode catalyst is Pt/C; Six, add fuel in anode region 3, cell cathode district 2 adds oxidants, can obtain the nano generator that can generate electricity, and described fuel adopts methyl alcohol, and oxidant adopts potassium permanganate.
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