CN105692547A - Hydrogen production nano-device, production method thereof, and hydrogen production method - Google Patents
Hydrogen production nano-device, production method thereof, and hydrogen production method Download PDFInfo
- Publication number
- CN105692547A CN105692547A CN201410682527.7A CN201410682527A CN105692547A CN 105692547 A CN105692547 A CN 105692547A CN 201410682527 A CN201410682527 A CN 201410682527A CN 105692547 A CN105692547 A CN 105692547A
- Authority
- CN
- China
- Prior art keywords
- hydrogen manufacturing
- alpha
- preferred
- nano
- manufacturing nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 CC(C)(CC(C)(C)S=*)N=I Chemical compound CC(C)(CC(C)(C)S=*)N=I 0.000 description 1
Classifications
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Landscapes
- Peptides Or Proteins (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Enzymes And Modification Thereof (AREA)
Abstract
The invention provides a hydrogen production nano-device, a production method thereof, and a hydrogen production method thereof. The hydrogen production nano-device comprises metal nano-particles, a photoinduced electron donor, alpha-helical peptides and organic metalloenzyme. The hydrogen production nano-device can use renewable solar energy to realize efficient and pollution-free hydrogen generation, all raw materials used in the invention have very good environment endophilicity and no pollution, and the macroscopic dipole moment characteristic of the alpha-helical peptides is used to improve the unidirectional electron delivery efficiency and improve the hydrogen yield, so the problems of environment pollution and energy consumption of present hydrogen production methods are effectively solved.
Description
Technical field
The present invention relates to a kind of nano-device preparing hydrogen, be specifically related to a kind of hydrogen manufacturing nano-device and preparation method thereof and a kind of hydrogen production process。
Background technology
Owing to world's oil supply is not enough and the problem such as environmental pollution increasingly serious, hydrogen is as a kind of green energy resource, and release energy when having renewable, pollution-free, burning advantages of higher, receives significant attention。At present, industrial hydrogen of preparing adopts mineral combustion or the method for electrolysis water mostly。The efficiency that both approaches prepares hydrogen is all significantly high, but the method for mineral combustion employs non-renewable energy resources, electrolysis water then subfam. Spiraeoideae is big so that their development is all limited to, be therefore badly in need of a kind of new can be efficient, pollution-free and save the method for the energy to prepare hydrogen。
Summary of the invention
The invention aims to overcome the drawbacks described above of prior art, it is provided that a kind of hydrogen manufacturing nano-device and preparation method thereof and a kind of hydrogen production process, this hydrogen manufacturing nano-device can utilize the free of contamination generation hydrogen of reproducible solar energy highly effective。
The present inventor has been surprisingly found that under study for action, including the hydrogen manufacturing nano-device of metal nanoparticle, photoinduced electron donor, alpha-helix polypeptide and organic metal enzyme, it is possible to utilize the free of contamination generation hydrogen of reproducible solar energy highly effective。
Therefore, to achieve these goals, first aspect, the invention provides a kind of hydrogen manufacturing nano-device, described hydrogen manufacturing nano-device includes metal nanoparticle, photoinduced electron donor, alpha-helix polypeptide and organic metal enzyme。
Second aspect, the preparation method that the invention provides a kind of hydrogen manufacturing nano-device, described method includes in the presence of solvent, the mixing of metal nanoparticle, photoinduced electron donor and alpha-helix polypeptide is carried out self-assembling reaction, then adds organic metalloenzyme in system and catalyst carries out condensation reaction。
The third aspect, the preparation method that the invention provides a kind of hydrogen manufacturing nano-device, described method includes in the presence of solvent, and alpha-helix polypeptide, organic metal enzyme and catalyst mix are carried out condensation reaction, then adds metal nanoparticle in system and photoinduced electron donor carries out self-assembling reaction。
Fourth aspect, the invention provides the hydrogen manufacturing nano-device that said method prepares。
5th aspect, the invention provides a kind of hydrogen production process, and described method includes being dissolved in above-mentioned hydrogen manufacturing nano-device can carrying in protogenic solution, and is irradiated under sunlight or ultraviolet light。
The hydrogen manufacturing nanometer device of the present invention can utilize the free of contamination generation hydrogen of reproducible solar energy highly effective, raw materials used it is respectively provided with good environment affinity, pollution-free, and utilize the characteristic that alpha-helix polypeptide has macroscopical dipole moment to improve the transmission efficiency of one direction electronics, improve hydrogen yield, the problem effectively solving the aspects such as the environmental pollution of existing hydrogen production process existence, energy resource consumption, has wide market application foreground。
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently。
Accompanying drawing explanation
Fig. 1 is the structural representation of a kind of embodiment of the hydrogen manufacturing nano-device of the present invention。
Fig. 2 is the operation principle schematic diagram of the hydrogen manufacturing nano-device of the present invention。
Description of reference numerals
1 metal nanoparticle；2 photoinduced electron donors；3 alpha-helix polypeptide；4 organic metal enzymes；
5 photoinduced electron。
Detailed description of the invention
Hereinafter the specific embodiment of the present invention is described in detail。It should be appreciated that detailed description of the invention described herein is merely to illustrate and explains the present invention, it is not limited to the present invention。
First aspect, the invention provides a kind of hydrogen manufacturing nano-device, and described hydrogen manufacturing nano-device includes metal nanoparticle, photoinduced electron donor, alpha-helix polypeptide and organic metal enzyme。
In the hydrogen manufacturing nano-device of the present invention, it is preferable that in situation, photoinduced electron donor and alpha-helix polypeptide are fixed on the surface of metal nanoparticle, form mixed monomolecular film, and organic metal enzyme is fixed on alpha-helix polypeptide。
In the hydrogen manufacturing nano-device of the present invention, for more effective generation hydrogen, it is preferable that in situation, in hydrogen manufacturing nano-device, the mol ratio of alpha-helix polypeptide, organic metal enzyme and photoinduced electron donor is 1:1-2:1-20, more preferably 1:1-1.5:5-15；In the alpha-helix polypeptide of 1mmol, the weight of metal nanoparticle is 0.05-200g, more preferably 0.2-50g, is further preferably 2-5g。
In the hydrogen manufacturing nano-device of the present invention, for metal nanoparticle, there is no particular limitation, it is possible to for the various metal nanoparticles that this area is common, it is preferable that in situation, metal nanoparticle is gold nano grain or silver nano-grain, more preferably gold nano grain。For the diameter of metal nanoparticle, there is no particular limitation, it is possible to fluctuates in wider scope, it is preferable that in situation, the diameter of metal nanoparticle is 1-100nm, more preferably 5-50nm。
In the hydrogen manufacturing nano-device of the present invention, for the preparation method of metal nanoparticle, there is no particular limitation, it is possible to for various preparation methoies commonly used in the art, for instance can be prepared by reduction of sodium citrate method, the method is conventionally known to one of skill in the art, does not repeat them here。
In the hydrogen manufacturing nano-device of the present invention, for photoinduced electron donor, there is no particular limitation, can be the common various photoinduced electron donors in this area, under preferable case, photoinduced electron donor is the mercaptan containing ferrocene structure or the mercaptan containing tris (bipyridine) ruthenium structure, it is further preferred that the general structure of the mercaptan containing ferrocene structure isM is 1-10；The general structure of the mercaptan containing tris (bipyridine) ruthenium structure isN is 1-10。
In the hydrogen manufacturing nano-device of the present invention, photoinduced electron donor can pass through commercially available。
In the hydrogen manufacturing nano-device of the present invention, it is preferable that in situation, the aminoacid sequence of alpha-helix polypeptide is the aminoacid sequence that can form α-helixstructure, it is further preferred that amino acid whose quantity is 6-24。
In the hydrogen manufacturing nano-device of the present invention, it is preferable that in situation, alpha-helix polypeptide is amphiphilic polypeptide。
In the hydrogen manufacturing nano-device of the present invention, for the preparation method of alpha-helix polypeptide, there is no particular limitation, it is possible to for various preparation methoies commonly used in the art, for instance can be synthesized by conventional solid phase synthesis, this is conventionally known to one of skill in the art, does not repeat them here。
In the hydrogen manufacturing nano-device of the present invention, in order to make alpha-helix polypeptide better self-assemble on the surface of metal nanoparticle, under preferable case, the C-terminal graft of alpha-helix polypeptide has molecular end to contain the organic sulfur compound of amino or carboxyl, it is further preferred that the C-terminal graft of alpha-helix polypeptide has the organic sulfur compound that molecular end contains amino。Under preferable case, organic sulfur compound is thioctic acid, mercaptan, thioether or disulfide；It is further preferred that the general structure of mercaptan isW is 1-10；The general structure of thioether isY is 1-10；The general structure of disulfide isZ is 1-10。
What those skilled in the art should understand that is, foregoing graft can be realized by amino or the carboxyl generation condensation reaction that the molecular end of the carboxyl of the C-end of alpha-helix polypeptide or amino (can contain amino on the side chain of the C-end of alpha-helix polypeptide) and organic sulfur compound contains, the method is conventionally known to one of skill in the art, does not repeat them here。
In the hydrogen manufacturing nano-device of the present invention, organic metal enzyme can for the hydrogenase simulated compound of various synthetic commonly used in the art or the plant hydrogenase extracted by tissue engineering, under preferable case, organic metal enzyme is the [Fe containing ferrum ferrum active sites2S2] organo-metallic compound, or be [the FeNiS containing ferronickel active sites2] organo-metallic compound；It is further preferred that [Fe2S2] organo-metallic compound isA1 is 1-10, a2 is 1-10；[FeNiS2] organo-metallic compound isB1 is 1-10, b2 is 1-10。
In the hydrogen manufacturing nano-device of the present invention, what those skilled in the art should understand that is, organic metal enzyme is some the metalloid enzymes containing carboxyl, and carboxyl can fix, by the amino generation condensation reaction with alpha-helix peptide N-terminus, the end being modified at alpha-helix polypeptide。
In the hydrogen manufacturing nano-device of the present invention, organic metal enzyme can synthesize or by commercially available room by experiment。
Second aspect, the preparation method that the invention provides a kind of hydrogen manufacturing nano-device, the method includes in the presence of solvent, the mixing of metal nanoparticle, photoinduced electron donor and alpha-helix polypeptide is carried out self-assembling reaction, then adds organic metalloenzyme in system and catalyst carries out condensation reaction。
In the preparation method of the present invention, for solvent, there is no particular limitation, can be various solvents commonly used in the art, under preferable case, solvent is water or organic solvent, organic solvent is one or more in DMF, TFE, methanol, ethanol, propanol, isopropanol, dimethyl sulfoxide and chloroform。Can selecting corresponding solvent according to the aminoacid sequence of alpha-helix polypeptide, this is conventionally known to one of skill in the art, does not repeat them here。
In the preparation method of the present invention, it is preferable that in situation, to carry out the system of self-assembling reaction, the concentration of metal nanoparticle is 0.5-20mg/mL, more preferably 1-10mg/mL；The concentration of alpha-helix polypeptide is 0.1-10mM, more preferably 0.2-5mM；The mol ratio of alpha-helix polypeptide and photoinduced electron donor is 1:1-20, more preferably 1:5-15。
In the preparation method of the present invention, for the condition of self-assembling reaction, there is no particular limitation, it is possible to for various self assembly conditions commonly used in the art, it is preferable that in situation, the time of self-assembling reaction is 6-24h。
In the preparation method of the present invention, it is preferable that in situation, to carry out the system of condensation reaction, the concentration of organic metal enzyme is 0.1-10mM, more preferably 0.2-5mM；The concentration of catalyst is 0.1-20mM, more preferably 0.2-5mM, and further preferably, catalyst is DIPEA and I-hydroxybenzotriazole。
In the preparation method of the present invention, it is preferable that in situation, the mol ratio of alpha-helix polypeptide, DIPEA and I-hydroxybenzotriazole is 1:1:1。
In the preparation method of the present invention, for the condition of condensation reaction, there is no particular limitation, it is possible to for various condensation reaction conditions commonly used in the art, it is preferable that in situation, the time of condensation reaction is 6-24h。
In the preparation method of the present invention, the description for metal nanoparticle, photoinduced electron donor, alpha-helix polypeptide and organic metal enzyme all can refer to corresponding record above, does not repeat them here。
In the preparation method of the present invention, it is also possible to including the step of removal of solvents, described solvent is water or organic solvent, in such cases, hydrogen manufacturing nano-device is the solid forms such as powder。For by the method for removal of solvents, there is no particular limitation, it is possible to for various methods commonly used in the art, for instance can being rotation steaming method, this be conventionally known to one of skill in the art, does not repeat them here。
In the preparation method of the present invention, it is also possible to including the step removed by catalyst, for the method removed by catalyst, there is no particular limitation, can be various methods commonly used in the art, can being such as dialysis, this be conventionally known to one of skill in the art, does not repeat them here。
The third aspect, the preparation method that the invention provides a kind of hydrogen manufacturing nano-device, the method includes in the presence of solvent, and alpha-helix polypeptide, organic metal enzyme and catalyst mix are carried out condensation reaction, then adds metal nanoparticle in system and photoinduced electron donor carries out self-assembling reaction。
In the preparation process in accordance with the present invention, the description for solvent, metal nanoparticle, photoinduced electron donor, alpha-helix polypeptide and organic metal enzyme all can refer to corresponding record above, does not repeat them here。
In the preparation process in accordance with the present invention, it is preferable that in situation, to carry out the system of condensation reaction, the concentration of alpha-helix polypeptide is 0.1-10mM, more preferably 0.2-5mM；The concentration of organic metal enzyme is 0.1-10mM, more preferably 0.2-5mM；The concentration of catalyst is 0.1-20mM, more preferably 0.2-5mM, and further preferably, described catalyst is DIPEA and I-hydroxybenzotriazole。
In the preparation method of the present invention, it is preferable that in situation, the mol ratio of alpha-helix polypeptide, DIPEA and I-hydroxybenzotriazole is 1:1:1。
In the preparation method of the present invention, for the condition of condensation reaction, there is no particular limitation, it is possible to for various condensation reaction conditions commonly used in the art, it is preferable that in situation, the time of condensation reaction is 6-24h。
In the preparation method of the present invention, it is preferable that in situation, to carry out the system of self-assembling reaction, the concentration of metal nanoparticle is 0.5-20mg/mL, more preferably 1-10mg/mL；The mol ratio of alpha-helix polypeptide and photoinduced electron donor is 1:1-20, more preferably 1:5-15。
In the preparation method of the present invention, for the condition of self-assembling reaction, there is no particular limitation, it is possible to for various self assembly conditions commonly used in the art, it is preferable that in situation, the time of self-assembling reaction is 6-24h。
In the preparation method of the present invention, it is also possible to include step solvent, catalyst removed, specifically describe the corresponding record that all can refer to above, do not repeat them here。
Fourth aspect, the invention provides the hydrogen manufacturing nano-device that said method prepares。
5th aspect, a kind of method that the invention provides hydrogen manufacturing, the method includes that above-mentioned hydrogen manufacturing nano-device is dissolved in (or being scattered in) and can carry in protogenic solution, and is irradiated under sunlight or ultraviolet light。
In the method for the hydrogen manufacturing of the present invention, for carrying protogenic solution, there is no particular limitation, it is possible to various can carry protogenic solution for commonly used in the art, it is preferable that in situation, using the teaching of the invention it is possible to provide the solution of proton is water or aqueous ascorbic acid。Preferably, the concentration of aqueous ascorbic acid is 0.1-5M, more preferably 0.5-2M。
In the method for the hydrogen manufacturing of the present invention, it is preferable that in situation, being dissolved in after can carrying protogenic solution, the concentration of hydrogen manufacturing nano-device is 0.5-10mg/mL, more preferably 1-5mg/mL。
In the method for the hydrogen manufacturing of the present invention, namely there is bubble to produce after sunlight or irradiation under ultraviolet ray 30min, be hydrogen through gas chromatographic detection。
Embodiment
The present invention is further illustrated for below example, but and is not so limited the present invention。
Hereinafter preparing in example, embodiment and comparative example, if no special instructions, reagent used is all commercially available。
Solid-phase synthesis peptides instrument is purchased from CSBIO company, and model is CS136XT。
Gold nano grain is prepared by reduction of sodium citrate method, and concrete grammar includes: the gold chloride electromagnetic agitation of 100mL0.1 weight % is heated to boiling, adds the citric acid of 5mL1 weight %, obtain the gold nano grain solution of 5.5mg/mL。
Silver nano-grain is prepared by traditional sodium citrate one stage reduction method, and concrete grammar includes: by 100mL7.0 × 10-3The sodium citrate solution of M adds in 250mL flask, adds the silver nitrate of 1mL0.1M, obtain the silver nanoparticle solution of 10mg/mL after being heated with stirring to boiling。
Preparation example 1
This prepares example for the preparation of alpha-helix polypeptide is described。
The Clear-acid resin (Clear-AcidResin, purchased from PeptideInstituteInc.) of 0.5g and 5mL dichloromethane are placed in Solid-phase synthesis peptides instrument, shake 24 hours。With N, after dinethylformamide (DMF) cleans resin, DMF solution 1mL and 0.7mM1 by DMF solution 3mL, 0.7mMN-hydroxyl-7-azo BTA of 0.7mMFmoc-leucine (purchased from PeptideInstituteInc.), join in Solid-phase synthesis peptides instrument after the DMF solution 1mL mixing of 3-DIC, and with above-mentioned mixed with resin, concussion reaction 2 hours, amino generation condensation reaction on leucic carboxyl and resin, and Fmoc-leucine is fixed on above-mentioned resin。After having reacted, resin DMF cleans, and adds piperidines/DMF mixed solution (volume ratio of piperidines and DMF is 2:8) 5mL, removes the Fmoc being with on leucine amino and protects base, and the protective reaction time is 1 hour。After deprotection, with DMF washing resin until cleanout fluid acid-base value is consistent with DMF acid-base value。Then according to the order of aminoacid sequence (LeuLysGluLysHisLysGluLeuGluLysGluHisGluLysGluLeuGluLysHi sLysGluLys, referring to SEQIDNO.1) carry out peptide condensation reaction, the amino acid whose carboxyl of every later and previous amino acid whose amino condensation, obtain the polypeptide of amino acid needed sequence on resin。By 0.7mM mercaptan(w is 4, purchased from WAKO company) the DMF solution of DMF solution 3mL, 0.7mMN-hydroxyl-7-azo BTA and 0.7mM1, add in Solid-phase synthesis peptides instrument after the DMF solution 1mL mixing of 3-DIC, carboxyl on the C-terminal lysines of this polypeptide and the amino generation condensation reaction of mercaptan, connect sulfide on the C-end of polypeptide。Through above operation, resin synthesizes the polypeptide of the end modified mercaptan of C-。After having reacted, cleaning aforementioned polypeptides binding resin with DMF, at 25 DEG C, vacuum drying is after 48 hours, moves in round-bottomed flask。Under ice bath environment, in round-bottomed flask resin, add 95 weight % trifluoroacetic acid aqueous solution 10mL of cooling, react 1 hour at 25 DEG C to excise polypeptide from resin。Filtering, separation resin and solution, filtrate reduced in volume is to 2mL。Add 100mL ether, precipitate out white depositions。Under 4000rpm rotating speed, centrifugal 5min is easily separated, and precipitate obtains white powder through lyophilization, namely obtains amphiphilic alpha-helix polypeptide, and the chemical formula of this amphiphilic alpha-helix polypeptide is as follows。
Preparation example 2
According to the method for preparation example 1, the difference is that, carry out peptide condensation reaction according to the order (LeuSerSerLeuLeuSerLeuLeuSerSerLeuLeuSerLeuLeuSerSerLeuLe uSerLeu, referring to SEQIDNO.2) of aminoacid sequence, and use thioether(y is 4, purchased from WAKO company) substitutes mercaptan
Preparation example 3
According to the method for preparation example 1, the difference is that, carry out peptide condensation reaction according to the order (LeuLysGluLysLysGluLeuGluLysGluGluLysGluLeuGluLysLysGluLy s, referring to SEQIDNO.3) of aminoacid sequence, and use disulfide(z is 6, purchased from WAKO company) substitutes mercaptan
Preparation example 4
Method according to preparation example 1, the difference is that, carry out peptide condensation reaction according to the order (LeuSerSerLeuLeuSerLeuLeuSerSerLeuLeuSerLeuLeuSerSerLeuLe uSerLeuLys, referring to SEQIDNO.4) of aminoacid sequence, and substitute mercaptan with thioctic acidIn such cases, the carboxyl generation condensation reaction of the amino on the C-terminal lysines side chain of this polypeptide and thioctic acid, the C-end of polypeptide connects sulfide。
Embodiment 1
The present embodiment is for hydrogen manufacturing nano-device that the present invention is described and preparation method thereof。
In the aforesaid gold nano grain solution of 100mL, addition 5mL contains 2.5mmol and contains the mercaptan of ferrocene structure(m is 6, purchased from SIGMA company) and 0.25mmol prepare the alcoholic solution of the alpha-helix polypeptide that example 1 prepares, and react 12h, then add 0.25mmol organic metal enzyme in system(a1 is 4, purchased from WAKO company), 0.25mmolN, N-diisopropylethylamine and 0.25mmol1-hydroxybenzotriazole, mix 12h。Rotation is evaporated off ethanol, obtains hydrogen manufacturing nano-device。
As shown in Figure 1, embodiment 1 prepares hydrogen manufacturing nano-device and includes metal nanoparticle 1, photoinduced electron donor 2, alpha-helix polypeptide 3 and organic metal enzyme 4, wherein, photoinduced electron donor 2 and alpha-helix polypeptide 3 are fixed on the surface of metal nanoparticle 1, and organic metal enzyme 4 is modified on alpha-helix polypeptide 3 by condensation reaction is fixing。
The operation principle schematic diagram of the hydrogen manufacturing nano-device of the present embodiment is as shown in Figure 2。In this hydrogen manufacturing nano-device, organic metal enzyme 4 is used for reducing proton, by sunlight or UV Light, photoinduced electron donor 2 provides photoinduced electron 5, and photoinduced electron 5 is delivered on organic metal enzyme 4 along the dipole moment of alpha-helix polypeptide 3 by metal nanoparticle 1 surface one direction。In this process, the movement of photoinduced electron 5 is accelerated by the impact of alpha-helix polypeptide 3 dipole。Finally, cause organic metal enzyme 4 can effectively obtain photoinduced electron 5, and then reduction can carry the proton that protogenic solution provides, and prepares hydrogen。
Embodiment 2
The present embodiment is for hydrogen manufacturing nano-device that the present invention is described and preparation method thereof。
In the aforesaid silver nanoparticle solution of 100mL, addition 5mL contains 2.5mmol and contains the mercaptan of tris (bipyridine) ruthenium structure(n is 6, purchased from SIGMA company) and 0.5mmol prepare the alcoholic solution of the alpha-helix polypeptide that example 2 prepares, and react 6h, then add 0.5mmol organic metal enzyme in system(a2 is 4, purchased from WAKO company), 0.12mmolN, N-diisopropylethylamine and 0.12mmol1-hydroxybenzotriazole, mix 24h。Rotation is evaporated off ethanol, and removes DIPEA and I-hydroxybenzotriazole with dialyzer dialysis, obtains hydrogen manufacturing nano-device。
The structure of the hydrogen manufacturing nano-device that the present embodiment prepares and embodiment 1 are identical, and operation principle and embodiment 1 identical。
Embodiment 3
The present embodiment is for hydrogen manufacturing nano-device that the present invention is described and preparation method thereof。
1mL chloroform adds 0.2mmol and prepares alpha-helix polypeptide, the 0.25mmol organic metal enzyme that example 3 prepares(b1 is 4, purchased from WAKO company), 0.1mmolN, N-diisopropylethylamine and 0.1mmol1-hydroxybenzotriazole, mix 24h。Then above-mentioned solution is joined in the aforesaid gold nano grain solution of 100mL, and in mixed solution, add the mercaptan of 3mmol tris (bipyridine) ruthenium structure(n is 4, purchased from WAKO company), mixes 6h。Rotation is evaporated off dechlorination and imitates, and removes DIPEA and I-hydroxybenzotriazole with dialyzer dialysis, obtains hydrogen manufacturing nano-device。
The structure of the hydrogen manufacturing nano-device that the present embodiment prepares and embodiment 1 are identical, and operation principle and embodiment 1 identical。
Embodiment 4
The present embodiment is for hydrogen manufacturing nano-device that the present invention is described and preparation method thereof。
In the aforesaid gold nano grain solution of 100mL, addition 5mL contains 2.5mmol and contains the mercaptan of ferrocene structure(m is 6, purchased from SIGMA company) and 0.25mmol prepare the alcoholic solution of the alpha-helix polypeptide that example 4 prepares, and mix 10h, then add 0.25mmol organic metal enzyme in system(b2 is 4, purchased from WAKO company), 0.25mmolN, N-diisopropylethylamine and 0.25mmol1-hydroxybenzotriazole, mix 10h。Rotation is evaporated off ethanol, obtains hydrogen manufacturing nano-device。
The structure of the hydrogen manufacturing nano-device that the present embodiment prepares and embodiment 1 are identical, and operation principle and embodiment 1 identical。
Application examples
The hydrogen manufacturing nano-device prepared by embodiment 1-4 respectively is dissolved in water or aqueous ascorbic acid, and is irradiated under sunlight or ultraviolet light, and with whether gas chromatographic detection has hydrogen to generate。Corresponding condition and result are referring to table 1。
Table 1
The hydrogen manufacturing nanometer device of the present invention can utilize the free of contamination generation hydrogen of reproducible solar energy highly effective, raw materials used it is respectively provided with good environment affinity, pollution-free, and utilize the characteristic that alpha-helix polypeptide has macroscopical dipole moment to improve the transmission efficiency of one direction electronics, improve hydrogen yield, the problem effectively solving the aspects such as the environmental pollution of existing hydrogen production process existence, energy resource consumption。
The preferred embodiment of the present invention described in detail above; but, the present invention is not limited to the detail in above-mentioned embodiment, in the technology concept of the present invention; technical scheme can being carried out multiple simple variant, these simple variant belong to protection scope of the present invention。
It is further to note that, each concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, it is possible to be combined by any suitable mode, in order to avoid unnecessary repetition, various possible compound modes are no longer illustrated by the present invention separately。
Additionally, can also carry out combination in any between the various different embodiment of the present invention, as long as it is without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally。
Claims (22)
1. a hydrogen manufacturing nano-device, it is characterised in that described hydrogen manufacturing nano-device includes metal nanoparticle, photoinduced electron donor, alpha-helix polypeptide and organic metal enzyme。
2. hydrogen manufacturing nano-device according to claim 1, wherein, described photoinduced electron donor and described alpha-helix polypeptide are fixed on the surface of described metal nanoparticle, and described organic metal enzyme is fixed on described alpha-helix polypeptide。
3. hydrogen manufacturing nano-device according to claim 1 and 2, wherein, in hydrogen manufacturing nano-device, the mol ratio of described alpha-helix polypeptide, described organic metal enzyme and described photoinduced electron donor is 1:1-2:1-20, it is preferred to 1:1-1.5:5-15；In the alpha-helix polypeptide of 1mmol, the weight of described metal nanoparticle is 0.05-200g, it is preferred to 0.2-50g, more preferably 2-5g。
4. hydrogen manufacturing nano-device according to claim 1, wherein, described metal nanoparticle is gold nano grain or silver nano-grain, it is preferred to gold nano grain；The diameter of described metal nanoparticle is 1-100nm, it is preferred to 5-50nm。
5. hydrogen manufacturing nano-device according to claim 1, wherein, described photoinduced electron donor is the mercaptan containing ferrocene structure or the mercaptan containing tris (bipyridine) ruthenium structure, it is preferable that the general structure of the described mercaptan containing ferrocene structure isM is 1-10；The general structure of the described mercaptan containing tris (bipyridine) ruthenium structure isN is 1-10。
6. hydrogen manufacturing nano-device according to claim 1, wherein, the aminoacid sequence of described alpha-helix polypeptide is the aminoacid sequence that can form α-helixstructure, and described amino acid whose quantity is preferably 6-24。
7. the hydrogen manufacturing nano-device according to claim 1 or 6, wherein, described alpha-helix polypeptide is amphiphilic polypeptide。
8. hydrogen manufacturing nano-device according to claim 7, wherein, the C-terminal graft of described alpha-helix polypeptide has the organic sulfur compound that molecular end contains amino or carboxyl, and described organic sulfur compound is preferably thioctic acid, mercaptan, thioether or disulfide；It is further preferred that the general structure of described mercaptan isW is 1-10；The general structure of described thioether isY is 1-10；The general structure of described disulfide isZ is 1-10。
9. hydrogen manufacturing nano-device according to claim 1, wherein, described organic metal enzyme is the [Fe containing ferrum ferrum active sites2S2] organo-metallic compound, or be [the FeNiS containing ferronickel active sites2] organo-metallic compound；Preferably, described [Fe2S2] organo-metallic compound isA1 is 1-10, a2 is 1-10；Described [FeNiS2] organo-metallic compound isB1 is 1-10, b2 is 1-10。
10. the preparation method of a hydrogen manufacturing nano-device, it is characterized in that, described method includes in the presence of solvent, the mixing of metal nanoparticle, photoinduced electron donor and alpha-helix polypeptide is carried out self-assembling reaction, then adds organic metalloenzyme in system and catalyst carries out condensation reaction。
11. method according to claim 10, wherein, described solvent is water or organic solvent, and described organic solvent is one or more in DMF, TFE, methanol, ethanol, propanol, isopropanol, dimethyl sulfoxide and chloroform。
12. method according to claim 10, wherein, to carry out the system of self-assembling reaction, the concentration of described metal nanoparticle is 0.5-20mg/mL, it is preferred to 1-10mg/mL；The concentration of described alpha-helix polypeptide is 0.1-10mM, it is preferred to 0.2-5mM；The mol ratio of described alpha-helix polypeptide and described photoinduced electron donor is 1:1-20, it is preferred to 1:5-15。
13. method according to claim 12, wherein, the time of described self-assembling reaction is 6-24h。
14. method according to claim 10, wherein, to carry out the system of condensation reaction, the concentration of described organic metal enzyme is 0.1-10mM, it is preferred to 0.2-5mM；The concentration of described catalyst is 0.1-20mM, it is preferred to 0.2-5mM, it is further preferred that described catalyst is DIPEA and I-hydroxybenzotriazole。
15. method according to claim 14, wherein, the time of described condensation reaction is 6-24h。
16. the preparation method of a hydrogen manufacturing nano-device, it is characterized in that, described method includes in the presence of solvent, and alpha-helix polypeptide, organic metal enzyme and catalyst mix are carried out condensation reaction, then adds metal nanoparticle in system and photoinduced electron donor carries out self-assembling reaction。
17. method according to claim 16, wherein, to carry out the system of condensation reaction, the concentration of described alpha-helix polypeptide is 0.1-10mM, it is preferred to 0.2-5mM；The concentration of described organic metal enzyme is 0.1-10mM, it is preferred to 0.2-5mM；The concentration of described catalyst is 0.1-20mM, it is preferred to 0.2-5mM, it is further preferred that described catalyst is DIPEA and I-hydroxybenzotriazole。
18. method according to claim 16, wherein, to carry out the system of self-assembling reaction, the concentration of described metal nanoparticle is 0.5-20mg/mL, it is preferred to 1-10mg/mL；The mol ratio of described alpha-helix polypeptide and described photoinduced electron donor is 1:1-20, it is preferred to 1:5-15。
19. the hydrogen manufacturing nano-device that in claim 10-18, method described in any one prepares。
20. the method for a hydrogen manufacturing, it is characterised in that described method includes being dissolved in the hydrogen manufacturing nano-device described in any one in claim 1-9 and 19 can carrying in protogenic solution, and is irradiated under sunlight or ultraviolet light。
21. method according to claim 20, wherein, described can to carry protogenic solution be water or aqueous ascorbic acid, it is preferable that the concentration of described aqueous ascorbic acid is 0.1-5M, more preferably 0.5-2M。
22. the method according to claim 20 or 21, wherein, after can carrying protogenic solution described in being dissolved in, the concentration of described hydrogen manufacturing nano-device is 0.5-10mg/mL, it is preferred to 1-5mg/mL。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410682527.7A CN105692547B (en) | 2014-11-24 | 2014-11-24 | A kind of hydrogen manufacturing nano-device and preparation method thereof and a kind of hydrogen production process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410682527.7A CN105692547B (en) | 2014-11-24 | 2014-11-24 | A kind of hydrogen manufacturing nano-device and preparation method thereof and a kind of hydrogen production process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105692547A true CN105692547A (en) | 2016-06-22 |
| CN105692547B CN105692547B (en) | 2019-04-12 |
Family
ID=56941301
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410682527.7A Active CN105692547B (en) | 2014-11-24 | 2014-11-24 | A kind of hydrogen manufacturing nano-device and preparation method thereof and a kind of hydrogen production process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105692547B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109160926A (en) * | 2018-06-29 | 2019-01-08 | 中北大学 | Iron iron hydrogenates the preparation and application of enzyme mimics and its carbon nanotube composite analogy object |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103484364A (en) * | 2013-09-17 | 2014-01-01 | 国家纳米科学中心 | Nanometer device for solar biological hydrogen production |
| CN103526202A (en) * | 2013-09-30 | 2014-01-22 | 国家纳米科学中心 | Method for preparing oriented polypeptide monomolecular film and product thereof |
-
2014
- 2014-11-24 CN CN201410682527.7A patent/CN105692547B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103484364A (en) * | 2013-09-17 | 2014-01-01 | 国家纳米科学中心 | Nanometer device for solar biological hydrogen production |
| CN103526202A (en) * | 2013-09-30 | 2014-01-22 | 国家纳米科学中心 | Method for preparing oriented polypeptide monomolecular film and product thereof |
Non-Patent Citations (1)
| Title |
|---|
| REBECCA ANN GRIMME ET AL.: "Maximizing H2 production in Photosystem I/dithiol molecular wire/platinum nanoparticle bioconjugates", 《DALTON TRANSACTIONS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109160926A (en) * | 2018-06-29 | 2019-01-08 | 中北大学 | Iron iron hydrogenates the preparation and application of enzyme mimics and its carbon nanotube composite analogy object |
| CN109160926B (en) * | 2018-06-29 | 2020-11-03 | 中北大学 | Preparation and application of iron-iron hydrogenase simulant and carbon nano tube composite simulant thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105692547B (en) | 2019-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Su et al. | A combination of “thiol− ene” click chemistry and surface initiated atom transfer radical polymerization: Fabrication of boronic acid functionalized magnetic graphene oxide composite for enrichment of glycoproteins | |
| Dong et al. | pH-responsive lignin-based magnetic nanoparticles for recovery of cellulase | |
| CN104558321B (en) | Mercaptan-alkene clicking chemistry method prepares the method for POSS/ polymethylacrylic acid dimethylaminoethyl organic/inorganic hybridization material | |
| Zhang et al. | Preparation and characterization of iminodiacetic acid-functionalized magnetic nanoparticles and its selective removal of bovine hemoglobin | |
| US8377891B2 (en) | Process for synthesis of cyclic octapeptide | |
| CN105289513A (en) | Magnetic graphene oxide adsorbent modified by citric acid for removing Hg<2+> ions and preparation method of magnetic graphene oxide adsorbent | |
| CN105457601A (en) | Preparation and application of folic acid modified magnetic graphene oxide adsorbent | |
| CN104785197A (en) | Preparation method of mixed hemi-micelle solid phase extractant based on Fe3O4 magnetic nanoparticles | |
| CN111978369B (en) | Method for preparing polypeptide | |
| CN109174049B (en) | Preparation method and application of imprinted porous lithium/rubidium ion adsorption material | |
| CN104437280A (en) | Preparation method of organic/inorganic hybridized magnetic nano flower | |
| Ghasemi et al. | Covalent binding and in-situ immobilization of lipases on a flexible nanoporous material | |
| CN105692547A (en) | Hydrogen production nano-device, production method thereof, and hydrogen production method | |
| CN104926924A (en) | Method for stabilizing polypeptide alpha-spiral secondary structure by using chiral sulfonium salt side chain | |
| CN108435134A (en) | The preparation and its application of egg white-graphene oxide self-assembled compound material | |
| Gong et al. | Stable metal–organic frameworks for PEC water splitting | |
| Matsuura et al. | Glutathione nanosphere: self-assembly of conformation-regulated trigonal-glutathiones in water | |
| CN1613755A (en) | Method for carbon nanometer tube with chemical decoration | |
| CN102643420A (en) | Poly alkyl ether compound with strange end group and double functional groups and application thereof | |
| CN106699841B (en) | Self-assembled polypeptide nanorod and preparation method thereof | |
| CN105289514A (en) | Preparation and application of magnetic graphene oxide adsorbent modified by hydroxy ethylidene diphosphate | |
| CN107722294A (en) | Microwave reaction method Fast back-projection algorithm MIL 88A type metal-organic framework materials | |
| CN113173882B (en) | Pyridyl amphiphilic and bielectric compound and application thereof | |
| CN105289512A (en) | Oxalic acid-modified magnetic graphene oxide adsorbent for removing heavy metal ions and preparation method of adsorbent | |
| CN104478994A (en) | Fullerene single-addition line peptide as well as preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |