CN103449360A - Photocatalytic hydrogen production system and hydrogen gas preparation method thereof - Google Patents
Photocatalytic hydrogen production system and hydrogen gas preparation method thereof Download PDFInfo
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- CN103449360A CN103449360A CN2012101720250A CN201210172025A CN103449360A CN 103449360 A CN103449360 A CN 103449360A CN 2012101720250 A CN2012101720250 A CN 2012101720250A CN 201210172025 A CN201210172025 A CN 201210172025A CN 103449360 A CN103449360 A CN 103449360A
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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
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Abstract
The invention discloses a photocatalytic hydrogen production system by utilizing a stabilizer. The system comprises a catalyst (polycarbonyl diiron dithiolate cluster compound), a photosensitizer (CdTe, CdSe, CdS quantum dots, and the like), a stabilizer (chitosan, beta-cyclodextrin, sodium polyacrylat, polyvinylpyrrolidone, sodium alginate, poly(N-isopropylacrylamide), polydimethyldiallylammonium chloride, benzalkonium chloride, octadecylmethyldihydroxyethyl ammonium bromide, etc.), an electronic sacrificial body (ascorbic acid), and a water-containing solvent. The photocatalytic hydrogen production system has the advantages of simple preparation, cheap and available components, high hydrogen yield efficiency, and good system stability, the hydrogen yield reaches 162 [mu]mol for a system with a total volume of 10 mL for one time, and the hydrogen conversion number is as high as 1615 calculated on the basis of catalyst. The hydrogen yield is only 7.5 [mu]mol in the same system in the absence of the stabilizer, and the hydrogen conversion number is only 57 calculated on the basis of catalyst.
Description
Technical field
The present invention relates to a kind of method of producing hydrogen system and preparing hydrogen, especially relate to a kind of method of using the Photocatalyzed Hydrogen Production system of stablizer and preparing hydrogen.
Background technology
Along with socioeconomic development, the mankind constantly increase the demand of the energy, but the fossil that the mankind mainly rely on can the convergence exhaustion.Hydrogen Energy is a kind of clean, efficient energy, and hydrogen can effectively be converted into electric energy and produce water as unique by product by fuel cell, has the incomparable advantage of fossil energy.Current industrial prepares hydrogen mainly by steam reformation, needs very high temperature and with the generation of greenhouse gases.And Photocatalyzed Hydrogen Production, the irradiation that usually utilizes sunlight is energy, at room temperature water can be reduced to hydrogen.Less energy-consumption, mild condition, environmental protection, prospect is very tempting.
People have developed some solar energy photocatalytic hydrogen manufacturing systems at present.Usually say, these systems all need photosensitizers, produce the components such as hydrogen catalyst and electronics sacrificial body.Wherein, the activity of product hydrogen catalyst is most important to the photolysis water hydrogen system.Some metal-sols, cobalt complex catalyzer, semiconductor material catalyzer and biological enzyme can be as producing hydrogen catalyst.With these catalyzer, compare, a kind of as in the biological enzyme agent of iron hydrogenase, have the advantage that catalytic decomposition aquatic products hydrogen efficiency is high, cost is low.But because the productive rate that extracts the virgin iron hydrogenase by algae bio body etc. is low, and the virgin iron hydrogenase can not stable existence in air, has restricted the large-scale application of virgin iron hydrogenase in the Photocatalyzed Hydrogen Production field.
In recent years, by the molecular structure of manual simulation's virgin iron hydrogenase, the synthetic iron hydrogenase active centre [Fe that contains
2s
2(CO)
6] the iron hydrogenase simulated compound of (many carbonyl diurethane iron two sulphur bunch) unit caused worldwide extensive concern.Since 2008, utilize the polycomponent catalysis of the compositions such as iron hydrogenase simulated compound, photosensitizers, electronics sacrificial body, proton donor produce hydrogen system and photosensitizers is reported in succession with the supramolecular system that iron hydrogenase simulated compound is connected by covalent linkage or non covalent bond.Such as: the Sun Licheng of China and Wang Mei etc. adopt iron hydrogenase simulated compound [{ (μ-SCH
2)
2n (CH
2c
6h
5) Fe
2(CO)
5(P (Pyr)
3)] be catalyzer, tris (bipyridine) ruthenium is photosensitizers, xitix is the three compositions system that electronics sacrificial body and proton donor form, in the mixed solvent of acetonitrile and water with radiation of visible light (wavelength is greater than 400nm), produced hydrogen (43 μ mol), 2.5 hours rear catalyst inactivations of system illumination, the hydrogen turnover number based on calculated (TON value) is that 4.3(is referring to Inorg.Chem.2008,47,2805-2810).Use further more efficient iridium (III) title complex [Ir (ppy) 2 (bpy)]
+for photosensitizers, take triethylamine as the electronics sacrificial body, this iron hydrogenase simulated compound in the solvent mixture of acetone and water illumination after 8 hours catalysis produce hydrogen 233 μ mol, the turnover number based on catalyzer up to 466(referring to Dalton.Trans.2010,39,1204-1206).The Sascha Ott of Sweden etc. adopts [(μ-Cl for another example
2bdt) Fe
2(CO)
6] (Cl
2bdt=3,6-dichlorobenzene-1,2-dithiolate) be catalyzer, tris (bipyridine) ruthenium is photosensitizers, and xitix is the three compositions system that electron donor(ED) and proton donor form, and in the mixed solvent of dimethyl formamide and water, with radiation of visible light (wavelength 455-850nm), has produced hydrogen (4.2 μ mol), system is at 2.5 hours rear catalyst inactivations of illumination, hydrogen turnover number based on calculated is greater than 200(referring to Chem.Eur.J.2010, and 16,60-63).And for example the J.N.H.Reek of Holland is connected to [(μ-CH by two zinc protoporphyrin unit by non covalent bond
2)
3fe
2(CO)
4(PPh
2py)
2] upper supermolecule type photocatalyst, the iPr of forming
2nEtHOAc is as electronics sacrificial body and proton source, in toluene solution, produced hydrogen (9.8 μ mol) with radiation of visible light (wavelength is greater than 530nm), hydrogen turnover number based on calculated is about 2, but this catalyzer occurs very soon to decompose inactivation (referring to Proc.Natl.Acad.Sci.U.S.A.2009 under illumination, 106,10460 – 10465).For structure and the principle of work in simulating nature circle iron hydrogenase active centre, we have open source literature once [(μ-CH to be linked to as the photosensitizers covalent linkage in many rhenium carbonyls title complex unit
2)
3fe
2(CO)
5(CN) constructed the molecule photocatalyst of the photic product hydrogen of first artificial simulation iron hydrogenase], using methyl alcohol as the electronics sacrificial body, acetic acid is as proton source, radiation of visible light in the mixed solvent of acetonitrile and water (wavelength is greater than 400nm) has produced hydrogen (0.28 μ mol), at the about system inactivation after 1 hour of illumination, hydrogen turnover number based on calculated is 0.14(Chem.Asian.J.2010,5,1796-1803).Further, by electronics sacrificial body ferrocene, many rhenium carbonyls of photosensitizers title complex and iron hydrogenase activity unit [Fe
2s
2(CO)
6connect into the photic product hydrogen catalyst of three components by covalent linkage, take xitix as the electronics sacrificial body, can realize visible ray (wavelength is greater than 400nm) catalysis product hydrogen (0.70 μ mol) in acetonitrile solvent, hydrogen turnover number based on calculated is 0.35(Chem.Commun., 2011,47,8406-8408).Also have open source literature to utilize the mode of self-assembly that photosensitizers and synthetic hydrogenase are introduced to water, the product hydrogen environment of nature hydrogenase has been reduced in simulation, realized the water photic product hydrogen of visible ray under driving (referring to Langmuir, 2010,26,9766-9771).And to utilize water-soluble many carbonyl diurethane iron two sulphur cluster compounds be the electronics sacrificial body for catalyzer, CdTe quantum dot for photosensitizers and xitix, pure water mutually in radiation of visible light within 10 hours, realized that the hydrogen turnover number based on calculated reaches 505 up to 786 μ mol hydrogen outputs.In addition, we have applied for the patent of the Photocatalyzed Hydrogen Production system that some contain many carbonyl diurethane iron two sulphur cluster compounds, comprise the preparation method of many carbonyl diurethane iron two sulphur cluster compounds and prepare the method (201010523037.4) of hydrogen; Contain many carbonyl diurethane iron two sulphur cluster compounds and the catalysis of CdSe quantum dot light and produce the method (201110099436.7) of hydrogen system, preparation method and hydrogen; Iron hydrogenase simulated compound and preparation method thereof, containing its Photocatalyzed Hydrogen Production system and prepare the method (201110251254.7) etc. of hydrogen.
Above-mentioned result of study shows, by the simulation to the virgin iron hydrogenase, under the visible light catalytic condition, can make hydrogen.But still there are some general problems in these systems: the first, catalyst system is not high at the illumination condition stability inferior.The most stable photochemical catalysis system of open source literature report is still made by our research group at present, and illumination lost catalytic activity after 10 hours; And most of photocatalysis hydrogen production systems lose catalytic activity after 1 hour in illumination.The second, the efficiency that hydrogen is produced in catalysis is not high.The maximum transforming numerical calculated based on iron hydrogenase simulated compound is 505, and the transforming numerical of most of systems is less than 5.The 3rd, for the catalytic activity of the stand-in that increase the iron hydrogenase and water-soluble, necessary chemically modified makes the quantitative change of iron hydrogenase simulated compound molecule large, and the structure trend is complicated, does not meet the requirement of Green Chemistry.The 4th, most systems are used precious metal as photosensitizers, make the cost of system increase.
Some tensio-active agents, polymkeric substance, oligosaccharide etc. can form and have the aggregate of specific form as vesica by reactive force between electrical charge rejection, steric hindrance, coordination, hydrogen bond and Van der Waals force equimolecular, make unstable component stable existence in solution, be called as " stablizer ".Stablizer is widely used in relevant industrial production and the scientific researches of subject such as chemistry, biology, physics.Compare with the method that increases the stability of compound by chemically modified, use not only succinct, the easy operation of step of technique of stablizer, and reduced widely production cost.But, by the effect of stablizer, make the Photocatalyzed Hydrogen Production system of iron hydrogenase simulated compound realize that the example continued, hydrogen is produced in catalysis efficiently have not been reported.
Summary of the invention
First technology that the present invention will solve is to provide a kind of Photocatalyzed Hydrogen Production system of using stablizer.
Second technical problem that the present invention will solve is to provide a kind of Photocatalyzed Hydrogen Production that uses stablizer
System prepares the method for hydrogen.
For solving above-mentioned first technical problem, a kind of Photocatalyzed Hydrogen Production system of using stablizer of the present invention comprises:
Stablizer;
Many carbonyl diurethane iron two sulphur cluster compounds;
The quantum dot that the thiohydracrylic acid of take is stablizer;
Xitix;
Organic solvent;
Water;
The pH value scope of described photocatalysis hydrogen production system is 2.8 ~ 4.5.
Further, described stablizer is chitosan, beta-cyclodextrin, sodium polyacrylate, polyvinylpyrrolidone, sodium alginate, PNIPAM, Poly Dimethyl Diallyl Ammonium Chloride, benzalkonium chloride or octadecyl dimethyl hydroxyethyl brometo de amonio; Structure is as follows successively:
The concentration of described stablizer is 3.00 * 10
-3mol/L～9.00 * 10
-2mol/L.
Further, the structure of described many carbonyl diurethane iron two sulphur cluster compounds is as follows:
Wherein, X is H or I; R
1for
n=4,5,6 ... 20;
R
2for
The concentration of described many carbonyl diurethane iron two sulphur cluster compounds is 1.00 * 10
-5mol/L ~ 2.50 * 10
-4mol/L.
It is further, described that to take the quantum dot that thiohydracrylic acid is stablizer be thiohydracrylic acid-CdTe, thiohydracrylic acid-CdSe or thiohydracrylic acid-CdS quantum dot; The size range of described quantum dot between 1.2～3.5nm, Cd
2+concentration is 2.0 * 10
-5mol/L～1 * 10
-3mol/L.
Further, the concentration of described xitix is 8.75 * 10
-2mol/L ~ 0.125mol/L.
Further, described organic solvent is methyl alcohol, ethanol, acetonitrile, tetrahydrofuran (THF) or dioxane; Particular methanol; Described organic solvent and water volume ratio are 3: 7～3: 2.
For solving above-mentioned second technical problem, the present invention is a kind of uses the Photocatalyzed Hydrogen Production system of stablizer to prepare the method for hydrogen, comprises the steps:
Be equipped with the aqueous solution of stablizer, add organic solvent, obtain solution A;
Add many carbonyl diurethane iron-sulfur cluster compound in solution A, obtain solution B;
Take to adding in solution B the quantum dot that thiohydracrylic acid is stablizer, obtain solution C;
Add xitix in solution C, obtain solution D;
It is that 2.8 ~ 4.5 rear visible rays that are more than or equal to 400nm with wavelength carry out illumination, gas spectrum monitoring sample that the pH value scope of solution D is reconciled; Described conciliation pH value comprises uses dilute hydrochloric acid and dilute sodium hydroxide; After illumination reaction completes, the sample hydrogen output calculated.
Further, described stablizer is chitosan, beta-cyclodextrin, sodium polyacrylate, polyvinylpyrrolidone, sodium alginate, PNIPAM, Poly Dimethyl Diallyl Ammonium Chloride, benzalkonium chloride, octadecyl dimethyl hydroxyethyl brometo de amonio; Structure is as follows successively:
The concentration of described stablizer is 3.00 * 10
-3mol/L～9.00 * 10
-2mol/L, and this concentration range internal stabilizer dissolving in solution is good.
Further, described organic solvent is methyl alcohol, ethanol, acetonitrile, tetrahydrofuran (THF) or dioxane; Particular methanol; In described organic solvent and stabiliser solution, the volume ratio of water is 3: 7～3: 2.
Further, the structure of described many carbonyl diurethane iron two sulphur cluster compounds is as follows:
Wherein, X is H or I; R
1for
n=4,5,6 ... 20;
R
2for
The iron hydrogenase stand-in that structure is more complicated contains many carbonyl diurethane iron two sulphur bunch not cannot, but because molecular weight is large, the synthesis technique complexity, economic worth is low; The concentration of described many carbonyl diurethane iron two sulphur cluster compounds is 1.00 * 10
-5mol/L ~ 2.50 * 10
-4mol/L, increases many carbonyl diurethane iron two sulphur cluster compound concentration the photocatalysis hydrogen production amount is increased, but the hydrogen turnover number based on calculated reduces.
Further, described photosensitizers is for take thiohydracrylic acid-CdTe, thiohydracrylic acid-CdSe or the thiohydracrylic acid-CdS quantum dot that thiohydracrylic acid is stablizer; The size range of described quantum dot between 1.2～3.5nm, Cd
2+concentration is 2.0 * 10
-5mol/L～1 * 10
-3mol/L.
Further, the concentration of described xitix is 8.75 * 10
-2mol/L ~ 0.125mol/L.
The present invention has following beneficial effect:
1, the present invention, by the effect of stablizer, makes script become stable to many carbonyl diurethane iron two sulphur cluster compound Photocatalyzed Hydrogen Production systems of photo-labile.
2, when guaranteeing that body series is stable, hydrogen generation efficiency improves, and hydrogen output increases.
3, composing system of the present invention is simple, and working method is easy.
4, the photosensitizers in system of the present invention does not adopt precious metal, and the system cost is lower.
Embodiment
Below with specific embodiment, the present invention is described in detail, but be not to concrete restriction of the present invention.
In the present invention, all concentration is the ultimate density in reaction system.
Light source is used the high voltage mercury lamp of 500W, is less than the UV-light of 400nm with the spectral filter elimination wavelength of 400nm, retains visible light part and irradiates sample.The hydrogen use gas spectrum that illumination produces detects (GC-14BShimadzu), and nitrogen is as carrier gas, and transcranial Doppler detector (TCD) is as detector.Sample is contained in Shi Lanke (Schlenk) test tube, sample nitrogen degasification 30 minutes for sealing before illumination, and the methane gas of reinjecting, as interior mark, seals illumination.By the amounts of hydrogen generated in gas spectrum monitoring sample, partly extract a certain amount of gas inject gas spectrum from test tube upper strata gas phase at regular intervals and detect, pass through H
2and CH
4working curve under this gas spectral condition calculates the hydrogen output of sample; The pH value of sample is adjusted to definite value by HCl or NaOH before illumination.
Embodiment 1
A kind of method of using the Photocatalyzed Hydrogen Production system of stablizer and preparing hydrogen: wherein, the concentration of many carbonyl diurethane iron two sulphur cluster compounds is 1.00 * 10
-5mol/L; The concentration of MPA-CdTe QDs is (with Cd
2+the amount meter) be 7.00 * 10
-5mol/L; Stablizer chitosan concentration (take chitosan monomer) is 3.00 * 10
-3mol/L; Xitix (H
2a) concentration is 8.75 * 10
-2mol/L; MPA-CdTe QDs is of a size of 3.4nm; The mixed solvent that solvent is the volume ratio first alcohol and water that is 1: 1; Population of samples amasss as 10mL; PH=3.8 before sample illumination.
The method of utilizing above-mentioned Photocatalyzed Hydrogen Production system to prepare hydrogen is: use λ > the radiation of visible light sample of 400nm, every illumination 2 hours, gas spectrum monitoring sample is once; In illumination after 28 hours, the about 3.63mL of sample hydrogen output calculated, the hydrogen turnover number (TON) calculated based on many carbonyl diurethane of catalyzer iron two sulphur cluster compounds is 1615; Sample continued to produce hydrogen in first 24 hours, and the explanation system is stable in the During Illumination of first 24 hours.
Described many carbonyl diurethane iron two sulphur cluster compounds are the compounds with following molecular structural formula:
Embodiment 2
A kind of method of using the Photocatalyzed Hydrogen Production system of stablizer and preparing hydrogen: wherein, the concentration of many carbonyl diurethane iron two sulphur cluster compounds is 1.00 * 10
-5mol/L; The concentration of MPA-CdTe QDs is (with Cd
2+the amount meter) be 7.00 * 10
-5mol/L; Stablizer chitosan concentration (take chitosan monomer) is 3.00 * 10
-3mol/L; Xitix (H
2a) concentration is 8.75 * 10
-2mol/L; MPA-CdTe QDs is of a size of 3.4nm; The mixed solvent that solvent is the volume ratio first alcohol and water that is 1: 1; Population of samples amasss as 10mL; PH=3.8 before sample illumination.
The method of utilizing above-mentioned Photocatalyzed Hydrogen Production system to prepare hydrogen is: use λ > the radiation of visible light sample of 400nm, every illumination 4 hours, gas spectrum monitoring sample is once; In illumination after 24 hours, the about 1.67mL(TON=748 of sample hydrogen output calculated); Sample continued to produce hydrogen in first 24 hours, and the explanation system is stable in the During Illumination of first 24 hours.
Described many carbonyl diurethane iron two sulphur cluster compound structural formulas are as follows:
Embodiment 3
A kind of method of using the Photocatalyzed Hydrogen Production system of stablizer and preparing hydrogen: wherein, the concentration of many carbonyl diurethane iron two sulphur cluster compounds is 1.00 * 10
-5mol/L; The concentration of MPA-CdTe QDs is (with Cd
2+the amount meter) be 7.00 * 10
-5mol/L; Stablizer chitosan concentration (take chitosan monomer) is 3.00 * 10
-3mol/L; Xitix (H
2a) concentration is 8.75 * 10
-2mol/L; MPA-CdTe QDs is of a size of 3.4nm; The mixed solvent that solvent is the volume ratio first alcohol and water that is 1: 1; Population of samples amasss as 10mL; PH=3.8 before sample illumination.
The method of utilizing above-mentioned Photocatalyzed Hydrogen Production system to prepare hydrogen is: use λ > the radiation of visible light sample of 400nm, every illumination 4 hours, gas spectrum monitoring sample is once; In illumination after 24 hours, the about 0.64mL(TON=286 of sample hydrogen output calculated); Sample continued to produce hydrogen in first 24 hours, and the explanation system is stable in the During Illumination of first 24 hours.
Described many carbonyl diurethane iron two sulphur cluster compound structural formulas are as follows:
Embodiment 4
A kind of method of using the Photocatalyzed Hydrogen Production system of stablizer and preparing hydrogen: wherein, the concentration of many carbonyl diurethane iron two sulphur cluster compounds is 3.50 * 10
-5mol/L; The concentration of MPA-CdTe QDs is (with Cd
2+the amount meter) be 1.40 * 10
-4mol/L; Stablizer chitosan concentration (take chitosan monomer) is 3.00 * 10
-3mol/L; Xitix (H
2a) concentration is 8.75 * 10
-2mol/L; MPA-CdTe QDs is of a size of 3.4nm; The mixed solvent that solvent is the volume ratio first alcohol and water that is 1: 1; Population of samples amasss as 10mL.Before sample illumination, the pH value is 2.8.
The method of utilizing above-mentioned Photocatalyzed Hydrogen Production system to prepare hydrogen is: use λ > the radiation of visible light sample of 400nm, every illumination 2 hours, gas spectrum monitoring sample is once; In illumination after 16 hours, the about 1.40mL(TON=248 of sample hydrogen output calculated); Sample continued to produce hydrogen in first 8 hours, and the explanation system is stable in the During Illumination of first 8 hours.
Described many carbonyl diurethane iron two sulphur cluster compounds are the compounds with following molecular structural formula:
Embodiment 5
A kind of method of using the Photocatalyzed Hydrogen Production system of stablizer and preparing hydrogen: wherein, the concentration of many carbonyl diurethane iron two sulphur cluster compounds is 1.00 * 10
-5mol/L; The concentration of MPA-CdTe QDs is (with Cd
2+the amount meter) be 7.00 * 10
-5mol/L; Stablizer chitosan concentration (take chitosan monomer) is 3.00 * 10
-3mol/L; Xitix (H
2a) concentration is 8.75 * 10
-2mol/L; MPA-CdTe QDs is of a size of 3.4nm; The mixed solvent that solvent is the volume ratio first alcohol and water that is 3: 7; Population of samples amasss as 10mL.Before sample illumination, the pH value is 3.8.
The method of utilizing above-mentioned Photocatalyzed Hydrogen Production system to prepare hydrogen is: use λ > the radiation of visible light sample of 400nm, every illumination 2 hours, gas spectrum monitoring sample is once; In illumination after 28 hours, the about 0.76mL(TON=339 of sample hydrogen output calculated); Sample continued to produce hydrogen in first 20 hours, and the explanation system is stable in the During Illumination of first 20 hours.
Described many carbonyl diurethane iron two sulphur cluster compounds are the compounds with following molecular structural formula:
Embodiment 6
A kind of method of using the Photocatalyzed Hydrogen Production system of stablizer and preparing hydrogen: wherein, the concentration of many carbonyl diurethane iron two sulphur cluster compounds is 1.00 * 10
-5mol/L; The concentration of MPA-CdTe QDs is (with Cd
2+the amount meter) be 7.00 * 10
-5mol/L; Stablizer chitosan concentration (take chitosan monomer) is 3.00 * 10
-3mol/L; Xitix (H
2a) concentration is 8.75 * 10
-2mol/L; MPA-CdTe QDs is of a size of 3.4nm; The mixed solvent that solvent is the volume ratio first alcohol and water that is 3: 2; Population of samples amasss as 10mL.Before sample illumination, the pH value is 3.8.
The method of utilizing above-mentioned Photocatalyzed Hydrogen Production system to prepare hydrogen is: use λ > the radiation of visible light sample of 400nm, every illumination 2 hours, gas spectrum monitoring sample is once; In illumination after 40 hours, the about 2.56mL(TON=1140 of sample hydrogen output calculated); Sample continued to produce hydrogen in first 36 hours, and the explanation system is stable in the During Illumination of first 36 hours.
Described many carbonyl diurethane iron two sulphur cluster compounds are the compounds with following molecular structural formula:
Embodiment 7
A kind of method of using the Photocatalyzed Hydrogen Production system of stablizer and preparing hydrogen: wherein, the concentration of many carbonyl diurethane iron two sulphur cluster compounds is 1.00 * 10
-5mol/L; The concentration of MPA-CdTe QDs is (with Cd
2+the amount meter) be 1.50 * 10
-4mol/L; Stablizer chitosan concentration (take chitosan monomer) is 3.00 * 10
-3mol/L; Xitix (H
2a) concentration is 8.75 * 10
-2mol/L; MPA-CdTe QDs is of a size of 3.4nm; The mixed solvent that solvent is the volume ratio first alcohol and water that is 1: 1; Population of samples amasss as 10mL; PH=3.8 before sample illumination.
The method of utilizing above-mentioned Photocatalyzed Hydrogen Production system to prepare hydrogen is: use λ > the radiation of visible light sample of 400nm, every illumination 2 hours, gas spectrum monitoring sample is once; In illumination after 10 hours, the about 1.04mL(TON=464 of sample hydrogen output calculated).
Described many carbonyl diurethane iron two sulphur cluster compounds are the compounds with following molecular structural formula:
Embodiment 8
A kind of method of using the Photocatalyzed Hydrogen Production system of stablizer and preparing hydrogen: wherein, the concentration of many carbonyl diurethane iron two sulphur cluster compounds is 1.00 * 10
-5mol/L; The concentration of MPA-CdTe QDs is (with Cd
2+the amount meter) be 7.00 * 10
-5mol/L; Stablizer chitosan concentration (take chitosan monomer) is 3.00 * 10
-3mol/L; Xitix (H
2a) concentration is 8.75 * 10
-2mol/L; MPA-CdTe QDs is of a size of 3.4nm; The mixed solvent that solvent is the volume ratio first alcohol and water that is 1: 1; Population of samples amasss as 10mL; PH=3.4 before sample illumination.
The method of utilizing above-mentioned Photocatalyzed Hydrogen Production system to prepare hydrogen is: use λ > the radiation of visible light sample of 400nm, every illumination 4 hours, gas spectrum monitoring sample is once; In illumination after 28 hours, the about 2.69mL(TON=1200 of sample hydrogen output calculated); Sample continued to produce hydrogen in first 24 hours, and the explanation system is stable in the During Illumination of first 24 hours.
Described many carbonyl diurethane iron two sulphur cluster compounds are the compounds with following molecular structural formula:
Embodiment 9
A kind of method of using the Photocatalyzed Hydrogen Production system of stablizer and preparing hydrogen: wherein, the concentration of many carbonyl diurethane iron two sulphur cluster compounds is 1.00 * 10
-5mol/L; The concentration of MPA-CdTe QDs is (with Cd
2+the amount meter) be 7.00 * 10
-5mol/L; Stablizer chitosan concentration (take chitosan monomer) is 3.00 * 10
-3mol/L; Xitix (H
2a) concentration is 8.75 * 10
-2mol/L; MPA-CdTe QDs is of a size of 3.4nm; The mixed solvent that solvent is the volume ratio first alcohol and water that is 1: 1; Population of samples amasss as 10mL; PH=4.5 before sample illumination.
The method of utilizing above-mentioned Photocatalyzed Hydrogen Production system to prepare hydrogen is: use λ > the radiation of visible light sample of 400nm, every illumination 2 hours, gas spectrum monitoring sample is once; In illumination after 10 hours, the about 0.50mL(TON=223 of sample hydrogen output calculated).Hydrogen is stablized and continued to produce to sample in During Illumination.
Described many carbonyl diurethane iron two sulphur cluster compounds are the compounds with following molecular structural formula:
Embodiment 10
A kind of method of using the Photocatalyzed Hydrogen Production system of stablizer and preparing hydrogen: wherein, the concentration of many carbonyl diurethane iron two sulphur cluster compounds is 1.00 * 10
-5mol/L; The concentration of MPA-CdTe QDs is (with Cd
2+the amount meter) be 7.00 * 10
-5mol/L; Stablizer chitosan concentration (take chitosan monomer) is 7.00 * 10
-3mol/L; Xitix (H
2a) concentration is 8.75 * 10
-2mol/L; MPA-CdTe QDs is of a size of 3.4nm; The mixed solvent that solvent is the volume ratio first alcohol and water that is 1: 1; Population of samples amasss as 10mL; PH=3.6 before sample illumination.
The method of utilizing above-mentioned Photocatalyzed Hydrogen Production system to prepare hydrogen is: use λ > the radiation of visible light sample of 400nm, every illumination 2 hours, gas spectrum monitoring sample is once; In illumination after 10 hours, the about 1.22mL(TON=544 of sample hydrogen output calculated).Hydrogen is stablized and continued to produce to sample in During Illumination.
Described many carbonyl diurethane iron two sulphur cluster compounds are the compounds with following molecular structural formula:
Embodiment 11
A kind of method of using the Photocatalyzed Hydrogen Production system of stablizer and preparing hydrogen: wherein, the concentration of many carbonyl diurethane iron two sulphur cluster compounds is 2.5 * 10
-4mol/L; The concentration of MPA-CdSe QDs is (with Cd
2+the amount meter) be 1.00 * 10
-3mol/L; Stablizer beta-cyclodextrin concentration is 9.00 * 10
-2mol/L; Xitix (H
2a) concentration is 0.125mol/L; MPA-CdSe QDs is of a size of 3.5nm; The mixed solvent that solvent is the volume ratio first alcohol and water that is 1: 1; Population of samples amasss as 10mL; PH=4.5 before sample illumination.
The method of utilizing above-mentioned Photocatalyzed Hydrogen Production system to prepare hydrogen is: use λ > the radiation of visible light sample of 400nm.Hydrogen is stablized and continued to produce to sample in During Illumination.
Described many carbonyl diurethane iron two sulphur cluster compounds are the compounds with following molecular structural formula:
Embodiment 12
A kind of method of using the Photocatalyzed Hydrogen Production system of stablizer and preparing hydrogen: wherein, the concentration of many carbonyl diurethane iron two sulphur cluster compounds is 2.5 * 10
-4mol/L; The concentration of MPA-CdS QDs is (with Cd
2+the amount meter) be 1.00 * 10
-3mol/L; Stablizer polyacrylic acid na concn is 9.00 * 10
-2mol/L; Xitix (H
2a) concentration is 0.125mol/L; MPA-CdSe QDs is of a size of 1.2nm; The mixed solvent that solvent is the volume ratio first alcohol and water that is 1: 1; Population of samples amasss as 10mL; PH=4.5 before sample illumination.
The method of utilizing above-mentioned Photocatalyzed Hydrogen Production system to prepare hydrogen is: use λ > the radiation of visible light sample of 400nm.Hydrogen is stablized and continued to produce to sample in During Illumination.
Described many carbonyl diurethane iron two sulphur cluster compounds are the compounds with following molecular structural formula:
Embodiment 13
Repeat embodiment 11, institute's difference only is, stablizer is polyvinylpyrrolidone, monomer concentration 1.00 * 10
-2mol/L; The concentration of MPA-CdS QDs is (with Cd
2+the amount meter) be 2.00 * 10
-5mol/L;
The structure of many carbonyl diurethane iron two sulphur cluster compounds is as follows:
wherein,
n is 4.
Organic solvent is ethanol.Before sample illumination, the pH value is 3.8.Hydrogen is stablized and continued to produce to sample in During Illumination.
Embodiment 14
Repeat embodiment 1, institute's difference only is, stablizer is sodium alginate, and monomer concentration is 3.00 * 10
-3mol/L.The structure of many carbonyl diurethane iron two sulphur cluster compounds is as follows:
Organic solvent is acetonitrile.Before sample illumination, the pH value is 3.8.Hydrogen is stablized and continued to produce to sample in During Illumination.
Embodiment 15
Repeat embodiment 11, institute's difference only is, stablizer is PNIPAM, and monomer concentration is 1.00 * 10
-2mol/L.Before sample illumination, the pH value is 3.8.The structure of many carbonyl diurethane iron two sulphur cluster compounds is as follows:
Organic solvent is tetrahydrofuran (THF).Before sample illumination, the pH value is 3.8.Hydrogen is stablized and continued to produce to sample in During Illumination.
Embodiment 16
Repeat embodiment 1, institute's difference only is, stablizer is Poly Dimethyl Diallyl Ammonium Chloride, and monomer concentration is 3.00 * 10
-3mol/L.The structure of many carbonyl diurethane iron two sulphur cluster compounds is as follows:
Organic solvent is dioxane.Before sample illumination, the pH value is 3.8.Hydrogen is stablized and continued to produce to sample in During Illumination.
Embodiment 17
Repeat embodiment 11, institute's difference only is, stablizer is Benzalkonii Chloridum, and concentration is 3.00 * 10
-3mol/L.
The structure of many carbonyl diurethane iron two sulphur cluster compounds is as follows:
Before sample illumination, the pH value is 3.8.Hydrogen is stablized and continued to produce to sample in During Illumination.
Embodiment 18
Repeat embodiment 11, institute's difference only is, stablizer is octadecyl dimethyl hydroxyethyl brometo de amonio, and concentration is 3.00 * 10
-3mol/L.The structure of many carbonyl diurethane iron two sulphur cluster compounds is as follows:
wherein, R
2for
Before sample illumination, the pH value is 3.8.Hydrogen is stablized and continued to produce to sample in During Illumination.
Embodiment 19
Repeat embodiment 11, institute's difference only is, the structure of many carbonyl diurethane iron two sulphur cluster compounds is as follows:
Before sample illumination, the pH value is 3.8.Hydrogen is stablized and continued to produce to sample in During Illumination.
Embodiment 20
Repeat embodiment 1, institute's difference only is, the structure of many carbonyl diurethane iron two sulphur cluster compounds is as follows:
Embodiment 21
Repeat embodiment 1, institute's difference only is, the structure of many carbonyl diurethane iron two sulphur cluster compounds is as follows:
Comparative Examples 1
A kind of system of the Photocatalyzed Hydrogen Production without stablizer and prepare the method for hydrogen: wherein, the concentration of many carbonyl diurethane iron two sulphur cluster compounds is 1.00 * 10
-5mol/L; The concentration of MPA-CdTe QDs is (with Cd
2+the amount meter) be 7.00 * 10
-5mol/L; Xitix (H
2a) concentration is 8.75 * 10
-2mol/L; MPA-CdTe QDs is of a size of 3.4nm; The mixed solvent that solvent is the volume ratio first alcohol and water that is 1: 1; Population of samples amasss as 10mL; PH=3.8 before sample illumination.
The method of utilizing above-mentioned Photocatalyzed Hydrogen Production system to prepare hydrogen is: use λ > the radiation of visible light sample of 400nm, every illumination 2 hours, gas spectrum monitoring sample is once; In illumination, after 28 hours, the sample hydrogen output calculated is 5.7 μ mol approximately, and the hydrogen turnover number based on calculated is 57.
Described many carbonyl diurethane iron two sulphur cluster compounds are the compounds with following molecular structural formula:
Comparative Examples 1 explanation does not have the Photocatalyzed Hydrogen Production system of stablizer can't realize continuing, producing efficiently hydrogen.And, in embodiment 1, system illumination still continues catalysis in 24 hours and produces hydrogen; The system cumulative volume of take can reach 162 μ mol as the each hydrogen output of 10mL, and the hydrogen turnover number based on calculated is up to 1615.Unique difference of Comparative Examples 1 and embodiment 1 is that Comparative Examples 1 does not have stablizer and embodiment 1 has added the stablizer chitosan.In the Comparative Examples 1 of not adding stablizer, hydrogen output and the hydrogen turnover number based on calculated are all well below embodiment 1.This absolutely proves in the present invention, and the Photocatalyzed Hydrogen Production system of adding stablizer is more superior than traditional product hydrogen system that there is no stablizer.
Obviously, the above embodiment of the present invention is only for example of the present invention clearly is described, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here can't give all embodiments exhaustive.Every still row in protection scope of the present invention of apparent variation that technical scheme of the present invention amplifies out or change that belong to.
Claims (12)
1. a Photocatalyzed Hydrogen Production system of using stablizer, is characterized in that, comprising:
Stablizer;
Many carbonyl diurethane iron two sulphur cluster compounds;
The quantum dot that the thiohydracrylic acid of take is stablizer;
Xitix;
Organic solvent;
Water;
The pH value scope of described photocatalysis hydrogen production system is 2.8 ~ 4.5.
2. Photocatalyzed Hydrogen Production system according to claim 1, it is characterized in that, described stablizer is chitosan, beta-cyclodextrin, sodium polyacrylate, polyvinylpyrrolidone, sodium alginate, PNIPAM, Poly Dimethyl Diallyl Ammonium Chloride, benzalkonium chloride or octadecyl dimethyl hydroxyethyl brometo de amonio; Structure is as follows successively:
The concentration of described stablizer is 3.00 * 10
-3mol/L～9.00 * 10
-2mol/L.
3. Photocatalyzed Hydrogen Production system according to claim 1, is characterized in that, the structure of described many carbonyl diurethane iron two sulphur cluster compounds is as follows:
Wherein, X is H or I; R
1for
n=4,5,6 ... 20;
R
2for
The concentration of described many carbonyl diurethane iron two sulphur cluster compounds is 1.00 * 10
-5mol/L ~ 2.50 * 10
-4mol/L.
4. Photocatalyzed Hydrogen Production system according to claim 1, is characterized in that, described to take the quantum dot that thiohydracrylic acid is stablizer be thiohydracrylic acid-CdTe, thiohydracrylic acid-CdSe or thiohydracrylic acid-CdS quantum dot; The size range of described quantum dot between 1.2～3.5nm, Cd
2+concentration is 2.0 * 10
-5mol/L～1 * 10
-3mol/L.
5. Photocatalyzed Hydrogen Production system according to claim 1, is characterized in that, the concentration of described xitix is 8.75 * 10
-2mol/L ~ 0.125mol/L.
6. Photocatalyzed Hydrogen Production system according to claim 1, is characterized in that, described organic solvent is methyl alcohol, ethanol, acetonitrile, tetrahydrofuran (THF) or dioxane; The volume ratio of described organic solvent and water is 3: 7～3: 2.
7. a Photocatalyzed Hydrogen Production system of using stablizer prepares the method for hydrogen, it is characterized in that, comprises the steps:
Be equipped with the aqueous solution of stablizer, add organic solvent, obtain solution A;
Add many carbonyl diurethane iron-sulfur cluster compound in solution A, obtain solution B;
Take to adding in solution B the quantum dot that thiohydracrylic acid is stablizer, obtain solution C;
Add xitix in solution C, obtain solution D;
It is that 2.8 ~ 4.5 rear visible rays that are more than or equal to 400nm with wavelength carry out illumination that the pH value scope of solution D is reconciled.
8. method according to claim 7, it is characterized in that, described stablizer is chitosan, beta-cyclodextrin, sodium polyacrylate, polyvinylpyrrolidone, sodium alginate, PNIPAM, Poly Dimethyl Diallyl Ammonium Chloride, benzalkonium chloride or octadecyl dimethyl hydroxyethyl brometo de amonio; Structure is as follows successively:
The concentration of described stablizer is 3.00 * 10
-3mol/L～9.00 * 10
-2mol/L.
9. method according to claim 7, is characterized in that, described organic solvent is methyl alcohol, ethanol, acetonitrile, tetrahydrofuran (THF) or dioxane; In described organic solvent and the stablizer aqueous solution, the volume ratio of water is 3: 7～3: 2.
10. method according to claim 7, is characterized in that, the structure of described many carbonyl diurethane iron two sulphur cluster compounds is as follows:
Wherein, X is H or I; R
1for
n=4,5,6 ... 20;
R
2for
The concentration of many carbonyl diurethane iron two sulphur cluster compounds is 1.00 * 10
-5~ 2.50 * 10
-4mol/L mol/L.
11. method according to claim 7, is characterized in that, described to take the quantum dot that thiohydracrylic acid is stablizer be thiohydracrylic acid-CdTe, thiohydracrylic acid-CdSe or thiohydracrylic acid-CdS quantum dot; The size range of described quantum dot between 1.2～3.5nm, Cd
2+concentration is 2.0 * 10
-5mol/L～1 * 10
-3mol/L.
12. method according to claim 7, is characterized in that, the concentration of described xitix is 8.75 * 10
-2mol/L ~ 0.125mol/L.
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| CN108754662A (en) * | 2018-05-16 | 2018-11-06 | 福州大学 | The preparation method of covalent class triazine structure light emitting organic semi polymer nanofiber and its Photocatalyzed Hydrogen Production application |
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| CN112774694A (en) * | 2021-01-06 | 2021-05-11 | 江苏大学 | Preparation method and application of functional carbon quantum dot modified Ag-In-Zn-S quantum dot |
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| CN107790185B (en) * | 2017-10-23 | 2020-05-05 | 南京大学 | Iron-sulfur cluster-apoferritin compound and preparation method and application thereof |
| CN108754662A (en) * | 2018-05-16 | 2018-11-06 | 福州大学 | The preparation method of covalent class triazine structure light emitting organic semi polymer nanofiber and its Photocatalyzed Hydrogen Production application |
| CN108754662B (en) * | 2018-05-16 | 2020-09-01 | 福州大学 | Preparation method of covalent triazine-structure light-emitting organic semiconductor polymer nanofiber and application of covalent triazine-structure light-emitting organic semiconductor polymer nanofiber in photocatalytic hydrogen production |
| CN112517045A (en) * | 2020-12-24 | 2021-03-19 | 河北工业大学 | Preparation method of iron @ BCN ceramic for photocatalytic hydrogen production |
| CN112517045B (en) * | 2020-12-24 | 2022-08-09 | 河北工业大学 | Preparation method of iron @ BCN ceramic for photocatalytic hydrogen production |
| CN112774694A (en) * | 2021-01-06 | 2021-05-11 | 江苏大学 | Preparation method and application of functional carbon quantum dot modified Ag-In-Zn-S quantum dot |
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