CN103484364B - Nanometer device for solar biological hydrogen production - Google Patents

Abstract

The invention provides a nanometer device for solar biological hydrogen production. The nanometer device for solar biological hydrogen production is characterized by comprising a metal substrate, a photoinduced electron donor, an alpha-helix polypeptide monomolecular film and hydrogenase. With the nanometer device for solar biological hydrogen production and a method for producing hydrogen with the device, hydrogen gas can be effectively produced through solar energy, reaction energy does not need to be provided by mineral fuel, and the purposes of no pollution and efficient hydrogen production can be achieved.

Description

A nano-device for solar biohydrogen production

technical field

The invention relates to a nano-device for preparing hydrogen, in particular to a nano-device for preparing hydrogen through a biological method by utilizing solar energy.

Background technique

Due to the shortage of crude oil supply in the world and the increasingly serious problems of environmental pollution, hydrogen has attracted widespread attention as a green energy because of its renewable, pollution-free, and high energy release during combustion.

At present, the industrial hydrogen production methods can be roughly divided into the following two types according to the different raw materials used: 1) Hydrogen production from fossil fuels; 2) Hydrogen production from electrolysis of water. Among them, fossil fuel hydrogen production uses coal, oil and natural gas as raw materials to produce hydrogen, which is the main method for producing hydrogen today. This method has a mature technology in our country, and the industrial production equipment is relatively perfect. However, the production of hydrogen from non-renewable energy sources limits the development of this method in the future. Another kind of hydrogen production by electrolysis of water is also one of the widely used and mature technologies. The method uses water as a raw material, and the process of producing hydrogen is a reverse reaction in which hydrogen and oxygen are combusted to generate water. The efficiency of electrolyzing water to produce hydrogen is generally 75-85%. The process is simple and pollution-free, but consumes a lot of electricity. Therefore, there is an urgent need for a new efficient, pollution-free and energy-saving method to prepare hydrogen.

Contents of the invention

The invention provides a novel nano-device for effectively preparing hydrogen through a biological method by using solar energy. It aims to solve the problems of current hydrogen production methods in terms of environmental pollution, energy consumption, and hydrogen production efficiency.

In order to solve the above problems, the present invention provides a nano-device for solar biohydrogen production, including: a metal substrate, a photoinduced electron donor, an oriented α-helical polypeptide monomolecular film, and hydrogenase;

Preferably, the photoinduced electron donor and the oriented α-helical polypeptide monomolecular film are fixed on the surface of the metal substrate by a self-assembly method, and the hydrogenase is fixed on the surface of the monomolecular film;

Preferably, the hydrogenase is immobilized on the surface of the monomolecular membrane through a condensation reaction with the N-terminal amino group of the polypeptide molecule;

Preferably, the metal substrate is an electrode of a nanogenerator;

Preferably, the nanogenerator is a piezoelectric nanogenerator, a triboelectric nanogenerator or a piezoelectric and triboelectric hybrid nanogenerator;

Preferably, the piezoelectric nanogenerator includes: a polymer substrate, a first electrode, a piezoelectric material layer and a second electrode;

Preferably, the polymer substrate is polyethylene terephthalate or polyimide film;

Preferably, the piezoelectric material layer is a piezoelectric material nanowire array or an oriented piezoelectric material film;

Preferably, the two electrode materials in the piezoelectric nanogenerator, triboelectric nanogenerator and triboelectric and piezoelectric hybrid nanogenerator can be the same or different, and are all selected from gold, silver, copper and nickel;

Preferably, the two electrode materials are the same, and both are gold;

Preferably, the photoinduced electron donor is a series of mercaptans containing a ferrocene structure, and the general structural formula is: n=2-10;

Preferably, the molecular sequence of the polypeptide is a series of amino acid sequences capable of forming an α-helical structure, and the number of amino acids is 8-24;

Preferably, the C-terminus of the amino acid is grafted with an organic sulfide such as thiol, thioether or disulfide at the molecular end containing an amino group;

Preferably, the general formula of the mercaptan is n=2-10, the general formula of the thioether is n=2-10, the general formula of the disulfide is n=2-10;

Preferably, the hydrogenase is an iron-only hydrogenase.

The present invention also provides a method for preparing an oriented α-helical polypeptide monomolecular film, which is characterized in that it comprises the following steps: immersing a metal electrode of a nanogenerator in a film-forming solution containing α-helical polypeptide molecules, and When the nanogenerator applies external stress to positively charge the electrode, the monomolecular film is formed on the surface of the metal electrode through a self-assembly reaction;

Preferably, the nanogenerator is a piezoelectric nanogenerator, a triboelectric nanogenerator or a piezoelectric and triboelectric hybrid nanogenerator;

Preferably, the concentration of the α-helical polypeptide molecule in the film-forming solution is 0.1mM-10mM;

Preferably, the solvent used in the film-forming solution is selected from water or an organic solvent, and the organic solvent is selected from N,N-dimethylformamide, trifluoroethanol, methanol, ethanol, propanol, isopropanol , dimethyl sulfoxide, etc.;

Preferably, the self-assembly reaction time is 6-24 hours.

The present invention also provides a preparation method of the aforementioned solar biohydrogen production nano-device, which is characterized in that it comprises the following steps:

(1) Using the aforementioned method for preparing an oriented α-helical polypeptide monomolecular film, prepare the oriented α-helical polypeptide monomolecular film on a metal electrode of the nanogenerator, and the film-forming solution simultaneously contains the The photoinduced electron donor;

(2) immersing the electrode assembled with the monomolecular film in the nanogenerator in an aqueous solution containing the hydrogenase molecule for reaction, thereby immobilizing the hydrogenase molecule on the surface of the monomolecular film;

Preferably, the molar concentration ratio of the photoelectron donor to the polypeptide molecule in the film-forming solution is 0.1-10;

Preferably, the concentration of the hydrogenase in the aqueous solution is preferably 0.05-1 unit/mL;

Preferably, the hydrogenase aqueous solution also contains a condensation reaction catalyst, which is 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride and 1-hydroxybenzotriazole ;

Preferably, the concentration of the catalyst in the aqueous solution is 5-50 mM, preferably 10 mM.

The present invention also provides a method for producing hydrogen using the aforementioned solar biohydrogen production nano-device, which is characterized in that it includes the following steps: immersing the electrode assembled with a polypeptide monomolecular film in the aforementioned nano-device in water, and immersing the nano-generator An external force is applied to negatively charge the electrode, and hydrogen gas is produced under the irradiation of sunlight.

Utilizing the solar biological hydrogen production nano-device provided by the present invention and the hydrogen production method using the device can effectively produce hydrogen through solar energy, without providing reaction energy by fossil fuels, and can achieve the purpose of pollution-free and efficient hydrogen production.

Description of drawings

Fig. 1 is a kind of typical structure schematic diagram of solar energy biological hydrogen production nano-device of the present invention;

Fig. 2 is another kind of typical structure schematic diagram of solar biohydrogen production nano-device of the present invention;

Fig. 3 is a kind of typical structural representation of piezoelectric nanogenerator in the present invention;

Fig. 4 is a schematic diagram of a method for preparing an oriented α-helical polypeptide monomolecular film in a solar biohydrogen device in the present invention;

Fig. 5 is a schematic diagram of the working principle of the solar bio-hydrogen production device in the present invention.

Detailed ways

In order to fully understand the purpose, features and effects of the present invention, the present invention will be described in detail with the following specific embodiments, but the present invention is not limited thereto.

The invention provides a nano-device for preparing hydrogen by utilizing solar energy and reducing protons by biological enzymes. The above-mentioned solar hydrogen production device can solve the problems of energy consumption and environmental pollution in the current hydrogen production process.

The present invention firstly provides a solar biohydrogen production device (see Figure 1), including: a metal substrate 10, a photo-induced electron donor 2, an oriented α-helical polypeptide monomolecular film 3 and a hydrogenase 4, which contains a photo-induced electron donor 2 The oriented α-helical polypeptide monomolecular film 3 is fixed on the metal substrate 10, and the hydrogenase 4 is fixed on the surface of the α-helical polypeptide monomolecular film 3 through reaction. In this device, the electrons required by the hydrogenase 4 to reduce protons are the photoinduced electrons provided by the photoinduced electron donor 2 after ultraviolet irradiation; the oriented α-helical polypeptide monomolecular film 3 plays the role of effectively transferring electrons in one direction. Compared with the general biohydrogen production system, the hydrogenase 4 is dispersed in the solution without immobilization in the general biohydrogen production system. The sub-donor 2 is integrated on one device, so the probability of obtaining electrons is higher and the efficiency of hydrogen production is higher.

In the present invention, the photoinduced electron donor 2 and the α-helical polypeptide molecule can form an aligned monomolecular film on the surface of the metal substrate 10 through a conventional self-assembly method, and the hydrogenase 4 undergoes a condensation reaction with the N-terminal amino group of the polypeptide molecule through the carboxyl group, Thereby immobilized on the surface of the α-helical polypeptide monomolecular membrane 3 . Although this device solves the problem of integration and immobilization of hydrogenase 4 and photoelectron donor 2, there are still problems such as poor orientation consistency of α-helical polypeptide monomolecular film 3, and the efficiency of one-way conducting electrons needs to be improved.

Therefore, on this basis, the present invention also provides a more preferred nano-device for solar biohydrogen production, as shown in Figure 2, including: nanogenerator 1, photoelectron donor 2, oriented α-helical polypeptide single molecule Membrane 3 and Hydrogenase 4. Wherein, the photoinduced electron donor 2 and the oriented α-helical polypeptide monomolecular film 3 are fixed on the surface of the metal electrode of the nanogenerator 1 by self-assembly; the hydrogenase 4 undergoes a condensation reaction with the N-terminal amino group of the polypeptide through the carboxyl group Immobilized on the surface of α-helical polypeptide monolayer 3. It can be seen that the main difference between this embodiment and the structure shown in FIG. 1 is that a metal electrode of the nanogenerator 1 is used instead of the metal substrate to fix the oriented α-helical polypeptide monomolecular film. Although the structure changes little, this embodiment shows very obvious advantages: First, the nanogenerator 1 can generate electricity under the action of external stress and form an electric field between the two electrodes. During this process, the nanogenerator The metal electrode used to form the self-assembled film has a positive charge, which can generate electrostatic attraction with the C-terminal of the α-helical polypeptide molecule, so that the C-terminal of the polypeptide molecule can selectively self-assemble on the surface of the metal electrode, effectively Promotes the formation of the α-helical polypeptide molecular orientation monomolecular film with the same dipole moment direction; The metal electrode of the monomolecular film is negatively charged, which causes electrostatic repulsion between the photoinduced electrons and the electrode, which can accelerate the movement of electrons, thereby improving the reduction efficiency and hydrogen production. It can be seen that the use of the nanogenerator 1 has a very positive impact on the preparation of the oriented α-helical polypeptide monomolecular film and the hydrogen production process, thereby effectively improving the performance of the solar biohydrogen production device of the present invention.

The nanogenerator 1 in the present invention can be a triboelectric nanogenerator, a piezoelectric nanogenerator or a triboelectric and piezoelectric hybrid nanogenerator.

The preparation method and principle of the device will be introduced below by taking the nanogenerator 1 as a piezoelectric nanogenerator as an example with reference to the accompanying drawings.

A typical structural schematic diagram of the above-mentioned piezoelectric nanogenerator is shown in FIG. 3 , including: a polymer substrate 5 , a first electrode 6 , a piezoelectric material layer 7 and a second electrode 8 .

The first and second electrodes are not only used as the two electrodes of the generator, but also as the substrate for the assembly of the polypeptide molecule and the photoelectron donor 2 to form a film, so metal is preferably used, more preferably gold, silver, copper or nickel, especially Gold electrodes are preferred. The materials of the first electrode and the second electrode can be the same or different, preferably both are the same.

The polymer substrate is polyethylene terephthalate or polyimide (English name Kapton) film.

The piezoelectric material layer 7 is preferably a micron or nanostructure made of piezoelectric material, such as nanowires, micron or nanofilms, etc., preferably zinc oxide nanowires and zinc oxide films, more preferably oriented zinc oxide films. At the same time, the ZnO nanowire array perpendicular to the electrode also has a similar effect to the oriented piezoelectric material film, so it can also be used in the present invention.

Fig. 4 shows a schematic diagram of the working principle of the nanogenerator during the preparation of the device of the present invention. As shown in Figure 4, the second electrode 8 of nanogenerator 1 is immersed in the film-forming solution that contains photoinduced electron donor 2 and α-helical polypeptide molecule 9, and external force is applied to nanogenerator 1 to make it bend, because The piezoelectric effect of the zinc oxide thin film of the piezoelectric material will form a piezoelectric potential when bending occurs, so that the first electrode 5 and the second electrode 8 are respectively charged with equal and opposite electric charges. The C-terminus 9a of the α-helical polypeptide molecule 9 is modified with an organosulfide, and the photoelectron donor 2 also contains a thiol group. An electrostatic attraction can be formed between the C-terminus 9a of the α-helical polypeptide molecule 9 and the positive charge generated on the second electrode 8 of the nanogenerator 1, so that the polypeptide molecule tends to selectively pass through the organosulfide modified on the C-terminus 9a. self-assembled to the surface of the second electrode 8, while the N-terminal 9b is located on the upper surface of the self-assembled film, forming a monomolecular film of α-helical polypeptide with consistent orientation. It can be seen that because of the use of nanogenerator 1, the α-helical antiparallel structure formed due to the polypeptide dipole-dipole interaction in the traditional self-assembly process is eliminated.

Wherein, the polypeptide is a series of amino acid sequences capable of forming an α-helical structure; the number of amino acids is preferably 8-24. The C-terminal graft molecule of the amino acid contains amino thiol, thioether or disulfide at the end, or organic sulfides such as lipoamide. Wherein, the general formula of the thiol is , n=2-10; The general formula of the thioether is , n=2-10. The general formula of the disulfide is n=2-10.

The photoinduced electron donor is a mercaptan containing a ferrocene structure, and the general structural formula is: n=2-10.

The preparation process of the device of the present invention includes two steps of assembling an aligned polypeptide monomolecular film containing a photoinduced electron donor on the surface of a nanogenerator electrode and modifying hydrogenase on the film. The specific process is as follows:

1. Preparation of oriented α-helical polypeptide monomolecular film containing photoelectron donor: 1) Prepare a mixed solution of photoelectron donor and polypeptide. The solvent can be water or an organic solvent according to the amino acid sequence of the polypeptide. The organic solvent is preferably N,N-dimethylformamide, trifluoroethanol, methanol, ethanol, propanol, isopropanol, dimethylsulfoxide and the like. The concentration of the polypeptide in the solution is preferably 0.1mM-10mM, and the molar concentration ratio of the photoinduced electron donor to the polypeptide is preferably 0.1-10. 2) Immerse the second electrode 8 of the nanogenerator 1 in the above mixed solution, and then generate electricity for the piezoelectric nanometer The machine 1 applies external stress to make the electrodes positively charged, and maintains for a certain period of time to make the polypeptide molecules and the photoinduced electron donors self-assemble on the metal electrodes of the nanogenerator 1 through a chemical reaction, forming a polypeptide monomolecular film with the same orientation; the immersion time, That is, the self-assembly reaction time is preferably 6-24 hours.

In order to form an electrostatic attraction with the C-terminus of the polypeptide molecule that exhibits negative charge, the second electrode 8 of the nanogenerator 1 needs to be positively charged. Therefore, the positively charged electrode must be immersed in the polypeptide mixture during actual operation, which can be realized by adjusting the external stress application method of the piezoelectric nanogenerator.

2. Modifying hydrogenase on the surface of the self-assembled membrane. The electrode assembled with the polypeptide monomolecular film in the nanogenerator 1 is immersed in the aqueous solution containing the hydrogenase molecule, and a condensation reaction can occur between the carboxyl group in the hydrogenase and the N-terminus of the polypeptide molecule, so that the surface of the self-assembled film Modify the upper layer of hydrogenase. The catalysts for this condensation reaction are preferably 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and 1-hydroxybenzotriazole. The concentration of the hydrogenase in the aqueous solution is preferably 0.05-1 unit/mL, and the concentration of the catalyst is 5-50 mM, preferably 10 mM. The hydrogenase is preferably an iron-only hydrogenase.

In addition to piezoelectric nanogenerators, there is also a triboelectric nanogenerator in the prior art, which is mainly composed of two electrodes and two friction layers that can produce contact-separation friction or sliding friction between the two electrodes . Under the action of external force, this generator can generate electrical signals by promoting the contact-separation friction or sliding friction of two friction layers. Although the structure of the triboelectric nanogenerator is slightly different from that of the piezoelectric nanogenerator, both of them can generate electrical signals under the action of external stress and output them through two electrodes, so the device of the present invention can also use triboelectric An electric nanogenerator or a piezoelectric and triboelectric hybrid nanogenerator is used instead of the aforementioned piezoelectric nanogenerator, and its use method and working principle are the same as those of the previous embodiments. The difference from the piezoelectric nanogenerator is that the charging properties of the electrode layer need to be adjusted by changing the relative friction characteristics of the two friction layer materials. The general principle is that when the generator is working normally, the electrode layer connected to the friction layer that is easy to lose electrons in friction is positively charged, and the electrode layer connected to the friction layer that is easy to get electrons in friction is negatively charged. . Technicians can make adjustments according to this principle during actual operation.

In order to improve the electrical output performance of the nanogenerator, preferably, the triboelectric nanogenerator comprises: a first electrode; a first polymer insulating layer; an intermediate film; a second polymer insulating layer; and a second electrode. The intermediate film is a polymer insulating layer with a micro-nano concave-convex structure on one side and a smooth side. The side surface with the concave-convex structure is in contact with the first high molecular polymer insulation layer, and the surface without the concave-convex structure is fixed to the second high molecular polymer.

A typical triboelectric and piezoelectric hybrid nanogenerator structure includes: a first electrode; a first polymer insulating layer; an intermediate film, one side of which is designed with a micro-nano concave-convex structure, and the side with the concave-convex structure is in contact with the The first high molecular polymer insulating layer is in contact; the second high molecular polymer insulating layer, the surface of the intervening film with no concave-convex structure is fixed on the second high molecular polymer insulating layer; the second electrode; the first piezoelectric material layer, vertical (zinc oxide nanowire array) or orientation (zinc oxide thin film) is grown on the first electrode; the third polymer insulating layer is covered on the first piezoelectric material layer; the third electrode is located on the second Three polymer insulating layers; the second piezoelectric material layer (zinc oxide nanowire array) or orientation (zinc oxide film) covers the second electrode; the fourth polymer insulating layer covers the second piezoelectric material layer On the electrical material layer; the fourth electrode is located on the surface of the fourth polymer insulating layer.

For triboelectric nanogenerators and triboelectric and piezoelectric hybrid nanogenerators, the same electrode materials as piezoelectric nanogenerators can be used, that is, the two electrode materials are the same or different, selected from gold, silver, copper, nickel, etc., Preferably both electrodes are identical and are gold.

Fig. 5 shows the working principle of the solar bio-hydrogen production nano-device in the present invention.

When in use, the electrode of the solar biohydrogen production nano-device assembled with the polypeptide monomolecular film is immersed in water. By sunlight, the photoelectron donor 2 provides photoelectrons 10 , and the dipole moments of the photoelectrons grow α-helical polypeptide molecules along the orientation, which can be transferred from the surface of the second electrode 8 to the hydrogenase 4 . Simultaneously, stress can be applied to the nanogenerator 1 to make it deform, so that the electrode assembled with the polypeptide monomolecular film 3 , the photoinduced electron donor 2 and the hydrogenase 4 is negatively charged. A mutually repulsive electrostatic interaction is generated between the photoinduced electrons 10 generated by the light and the electrode, and the generated photoinduced electrons are promoted to move from the surface of the second electrode 8 to the hydrogenase 4 . Finally, through the coupling effect of orientation dipole moment and electrostatic repulsion, hydrogenase 4 can effectively obtain photoinduced electrons, and then reduce protons in water to produce hydrogen.

It can be seen that in order to enhance the consistency of the orientation of the monomolecular film in the process of preparing the oriented polypeptide monomolecular film, the present invention requires that the electrode as the self-assembled substrate must be positively charged, but if the electrode must be positively charged during the use of the device. Electrostatic repulsion with photoinduced electrons requires that the electrode must have a negative charge. In order to achieve this goal, for piezoelectric nanogenerators, the direction of stress on the piezoelectric material can be adjusted by changing the way the external force is applied, such as changing it from a stretched state to a compressed state, so that the corresponding electrodes can From being positively charged to being negatively charged; and for triboelectric nanogenerators, it is possible to adjust the material type or surface modification of the two friction layers to change the current generated on the electrodes in contact with the two friction layers. The electrical properties of the surface charge.

Of course, the most preferred solution of the present invention is that the electrical properties of the nanogenerator electrodes are adjustable during the monomolecular film preparation and hydrogen production process, but if the electrical properties of the electrodes are not adjustable due to certain conditions, such as external stress The way of application is fixed, and the present invention can still be implemented. Because, if the electrode can only be positively charged, it can play a role in the preparation of the monomolecular film, thereby improving the orientation consistency of the monomolecular film, thereby significantly improving the hydrogen production efficiency; and if the electrode can only carry If the negative charge is negative, then even if the orientation of the monomolecular film is not good enough, the efficiency of hydrogen production can be improved by repelling photo-induced electrons during the hydrogen production process. Therefore, these two schemes all belong to the protection scope of the present invention.

The solar piezoelectric nano-hydrogen production device of the present invention utilizes renewable solar energy to prepare hydrogen, and the raw materials used have good environmental affinity and are pollution-free. And the nanogenerator is used to effectively improve the efficiency of electron transfer in one direction, thereby increasing the hydrogen production rate.

The specific embodiments described above have further described the purpose, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above descriptions are only specific embodiments of the present invention, and are not intended to limit the present invention. Within the spirit and principles of the present invention, any modifications, equivalent replacements, improvements, etc., shall be included in the protection scope of the present invention.

Claims (23)

1. a sun power biological hydrogen production nano-device, it is characterized in that comprising: metal substrate, photoinduced electron donor, orientations-helical polypeptide unimolecular film and hydrogenase, described photoinduced electron donor and described orientations-helical polypeptide unimolecular film are fixed on the surface of described metal substrate by self-assembly method, described hydrogenase is fixed on the surface of described unimolecular film by carboxyl and described peptide molecule N-terminal amino group generation condensation reaction, and described metal substrate is an electrode of nano generator.

2. device as claimed in claim 1, is characterized in that described nano generator is piezoelectric nano generator, triboelectricity nano generator or piezoelectricity and triboelectricity mixing nano generator.

3. device as claimed in claim 2, is characterized in that described piezoelectric nano generator comprises: high molecular polymer substrate, the first electrode, piezoelectric material layer and the second electrode.

4. device as claimed in claim 3, is characterized in that described high molecular polymer substrate is polyethylene terephthalate or polyimide film.

5. device as claimed in claim 3, is characterized in that described piezoelectric material layer is piezoelectric nano-wire array or orientation piezoelectric material film.

6. the device as described in any one of claim 2-5, it is characterized in that described piezoelectric nano generator, triboelectricity nano generator and triboelectricity all can be identical or different with two electrode materialss in piezoelectricity mixing nano generator, and be all selected from gold and silver, copper and mickel.

7. device as claimed in claim 6, is characterized in that described two electrode materialss are identical, and is gold.

8. the device as described in claim 1-5 or 7 any one, it is characterized in that described photoinduced electron donor is a series of mercaptan containing ferrocene structure, general structure is: n=2-10.

9. device as claimed in claim 8, it is characterized in that the molecular sequences of described polypeptide is a series of aminoacid sequences that can form α-helixstructure, described amino acid no is 8-24.

10. device as claimed in claim 9, is characterized in that, the amino acid C-terminal of peptide molecule is grafted with molecular end and contains amino mercaptan, thioether or disulfide.

11. devices as claimed in claim 10, is characterized in that the general formula of described mercaptan is n=2-10, the general formula of described thioether is n=2-10, the general formula of described disulfide is n=2-10.

12. devices as claimed in claim 8, is characterized in that described hydrogenase is Fe-only hydrogenase.

The preparation method of 13. 1 kinds of orientations-helical polypeptide unimolecular films, it is characterized in that comprising following steps: nano generator metal electrode is immersed in the film-forming soln containing alpha-helix peptide molecule, and when applying extraneous stress to described nano generator and making described electrode band positive electricity, form described unimolecular film by self-assembling reaction at described surface of metal electrode, the amino acid C-terminal grafting molecules end of alpha-helix peptide molecule contains amino mercaptan, thioether, disulfide or Thioctamide.

14. methods as claimed in claim 13, is characterized in that, described nano generator is piezoelectric nano generator, triboelectricity nano generator or piezoelectricity and triboelectricity mixing nano generator.

15. methods as claimed in claim 13, is characterized in that the concentration of alpha-helix peptide molecule described in described film-forming soln is 0.1mM-10mM.

16. methods as claimed in claim 13, it is characterized in that the solvent used in described film-forming soln is selected from water or organic solvent, described organic solvent is selected from DMF, TFE, methyl alcohol, ethanol, propyl alcohol, Virahol, dimethyl sulfoxide (DMSO).

17. methods as claimed in claim 13, is characterized in that the described self-assembling reaction time is 6-24 hour.

18. 1 kinds of methods preparing sun power biological hydrogen production nano-device described in any one of claim 1-12, is characterized in that comprising following steps:

(1) preparation method of the orientations-helical polypeptide unimolecular film as described in any one of claim 13-17 is used, described orientations-helical polypeptide unimolecular film prepared by a metal electrode of described nano generator, and simultaneously containing described photoinduced electron donor in described film forming liquid;

(2) electrode being assembled with described unimolecular film in described nano generator is immersed in the aqueous solution containing described hydrogenase molecule and reacts, thus described hydrogenase molecule is fixed on the surface of described unimolecular film.

19. methods as claimed in claim 18, is characterized in that the molar concentration rate of photoinduced electron donor and described peptide molecule described in described film-forming soln is 0.1-10.

20. methods as claimed in claim 18, is characterized in that the preferred 0.05-1unit/mL of described hydrogenase concentration in aqueous.

21. methods as claimed in claim 18, is characterized in that described catalyzer is 1-ethyl-(3-dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate and I-hydroxybenzotriazole also containing condensation catalyst in the described hydrogenase aqueous solution.

22. methods as claimed in claim 21, is characterized in that the concentration of described catalyzer in the described aqueous solution is 5-50mM.

23. 1 kinds of methods utilizing the hydrogen manufacturing of sun power biological hydrogen production nano-device, it is characterized in that comprising following steps: the electrode being assembled with described polypeptide monomolecular film in the nano-device described in any one of claim 1-12 is immersed in water, and this electrode band negative electricity is made to described nano generator applying external force, under the irradiation of sunlight, hydrogen is had to produce.