CN102744104A - Photocatalytic hydrogen production system containing [Fe2S2(CO)6] compound and CdSe quantum dots, preparation method thereof and hydrogen production method thereof - Google Patents
Photocatalytic hydrogen production system containing [Fe2S2(CO)6] compound and CdSe quantum dots, preparation method thereof and hydrogen production method thereof Download PDFInfo
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Abstract
The invention discloses a photocatalytic hydrogen production system containing a [Fe2S2(CO)6] compound, wherein the system concretely comprises the [Fe2S2(CO)6] compound, CdSe quantum dots, ascorbic acid and a water-containing solvent. The photocatalytic hydrogen generation system has a high hydrogen generation efficiency and a high stability. The hydrogen generation amount can reach 129mumol each time each 10ml of the total volume of the system, the hydrogen conversion number calculated based on a catalyst reaches 1286, and components composing the system are cheap and can be easily obtained.
Description
Technical field
The present invention relates to a kind of photocatalysis produces hydrogen system, its preparation method and utilizes the photocatalysis system to prepare the method for hydrogen; Especially relating to a kind of photocatalysis that contains many carbonyl two iron, two sulphur cluster compounds and CdSe quantum dot produces the preparation method of hydrogen system, many carbonyls two iron two sulphur cluster compounds and utilizes the photocatalysis system to prepare the method for hydrogen.
Background technology
Utilizing decomposing water with solar energy to prepare hydrogen is one of optimal method that solves the human energy crisis that is faced, because related solar energy is inexhaustible in the entire reaction course, and tellurian water reserve is abundant, with low cost.Product after hydrogen is utilized as energy carrier is a water, process cleaning and environmental protection as a result, and water can get into next light decomposition water process again, constitutes closed energy circulation.
People have been developed the photochemical catalyst that several big type of solar energy photodissociation water, for example Pt colloidal sol catalyst, Co composition catalyst, semi-conducting material catalyst and biological enzyme agent etc. at present.A kind of as in the biological enzyme agent of iron hydrogenase has the advantage that catalytic decomposition aquatic products hydrogen efficiency is high, cost is low.The iron hydrogenase is a kind of low organized enzyme that waits in the algae bio body that is prevalent in, and has the activity that efficient catalytic reduction proton produces hydrogen.Because extract the productive rate of native iron hydrogenase through algae bio body etc. low, and the native iron hydrogenase can not stable existence in air, has therefore restricted the native iron hydrogenase produces the hydrogen field in photocatalysis large-scale application.
In recent years, through the molecular structure of manual simulation's native iron hydrogenase, the synthetic iron hydrogenase activated centre [Fe that contains
2S
2(CO)
6] the iron hydrogenase simulated compound of (many carbonyl two iron two sulphur bunch) unit caused worldwide extensive concern.Since 2008, utilize the multicomponent catalysis of compositions such as iron hydrogenase simulated compound, sensitising agent, electronics sacrificial body, proton donor to produce hydrogen system and sensitising agent is reported through the supramolecular system that covalent bond or non-covalent bond are connected with iron hydrogenase simulated compound in succession.For example: 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 catalyst, tris (bipyridine) ruthenium is a sensitising agent, ascorbic acid is the three compositions system that electronics sacrificial body and proton donor are formed; 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 are 4.3 (referring to Inorg.Chem.2008 based on the hydrogen turnover number (TON value) of calculated; 47,2805-2810).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) is catalyst, and tris (bipyridine) ruthenium is a sensitising agent; Ascorbic acid is the three compositions system that electron donor and proton donor are formed; Dimethyl formamide (be called for short later on: DMF) with in the mixed solvent of water produced hydrogen (4.2 μ mol) with radiation of visible light (wavelength 455-850nm), system is at 2.5 hours rear catalyst inactivations of illumination, based on the hydrogen turnover number of calculated greater than 200 (referring to Chem.Eur.J.2010; 16,60-63).And for example the J.N.H.Reek of Holland is connected to [(μ-CH with two zinc protoporphyrin unit through non-covalent bond
2)
3Fe
2(CO)
4(PPh
2Py)
2] last supermolecule type photochemical catalyst, the NiPr of forming
2EtHOAc 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), be about 2, inactivation has taken place to decompose (referring to Proc.Natl.Acad.Sci.U.S.A.2009 but this catalyst is very fast under illumination based on the hydrogen turnover number of calculated; 106,10460-10465).For the structure and the operation principle in simulating nature circle iron hydrogenase activated centre, we have open source literature once [(μ-CH to be linked as the sensitising agent covalent bond in many rhenium carbonyls complex unit
2)
3Fe
2(CO)
5(CN)] constructed the molecule photochemical catalyst of the photic product hydrogen of first manual simulation's iron hydrogenase on; As the electronics sacrificial body, acetate is as proton source with methyl alcohol, and 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 illumination system inactivation after about 1 hour; Based on the hydrogen turnover number of calculated be 0.14 (referring to Chem.Asian.J.2010,5,1796-1803).Also have open source literature to utilize the mode of self assembly that sensitising agent and artificial synthesizing hydrogenated enzyme are introduced water; The product hydrogen environment of nature hydrogenase has been reduced in simulation, realized the water photic product hydrogen of visible light under driving (referring to Langmuir, 2010; 26,9766-9771).
Above-mentioned result of study is significant for development photocatalysis hydrogen production system; But the following problem of most of system ubiquities: first; Catalyst is unstable under illumination condition; The photocatalysis hydrogen production system all loses catalytic activity in illumination after 3 hours, and most of photocatalysis hydrogen production system promptly loses catalytic activity in illumination after 1 hour; The second, the efficient that hydrogen is produced in catalysis is not high, and the maximum TON value of calculating based on iron hydrogenase simulated compound is 200, and system is constructed in the mixed solvent of DMF and water, and the highest hydrogen output has only 4.2 μ mol, at illumination system inactivation after 2.5 hours; The TON value of most of systems is less than 5; The 3rd, most systems use noble metal as sensitising agent, make the cost of system increase.
Quantum dot is the inorganic semiconductor particles with nano-scale, has the extinction wide ranges, and absorbance is big; The luminescent quantum productive rate is high; Characteristics such as preparation is simple, and is with low cost, quantum dot has had application widely as a kind of sensitising agent in fields such as bioprobe, solar energy photoelectric conversion in recent years.Recently; We synthesize a kind of water-soluble many carbonyl two iron two sulphur simulation hydrogenase molecules, utilize this molecule and CdTe quantum dot and ascorbic acid to form pure water photocatalysis product hydrogen system mutually, and this system can highly effective hydrogen yield under visible light radiation; In 10 hours illumination process, can produce hydrogen 786 μ mol; The hydrogen turnover number that obtains with calculated be 505 (Angew.Chem.Int.Ed.2011,50,3193-3197).
Summary of the invention
The technical problem that the present invention will solve provides a kind of photocatalysis that contains many carbonyl two iron two sulphur cluster compounds and produces hydrogen system.It is high that hydrogen system hydrogen generation efficiency is produced in this photocatalysis, and the stability of system is high, is that the each hydrogen output of 10ml can reach 129 μ mol in the system cumulative volume, and (be called for short: TON) reach 1286, the system constituent is cheap and easy to get based on the hydrogen turnover number of calculated.
Another technical problem that the present invention will solve provides a kind of preparation method of water-soluble many carbonyl two iron two sulphur cluster compounds.Many carbonyls two iron two sulphur cluster compounds through this preparation method makes can be water-soluble.
Another technical problem that the present invention will solve provides a kind of method of utilizing photocatalysis product hydrogen system to prepare hydrogen.
For solving above-mentioned first technical problem, hydrogen system is produced in a kind of photocatalysis that contains many carbonyl two iron two sulphur cluster compounds of the present invention, comprising:
Many carbonyl two iron two sulphur cluster compounds,
The CdSe quantum dot,
Ascorbic acid (abbreviate as: H2A) and
Aqueous solvent.
Further, said CdSe quantum dot is to be stabilizing agent with the mercaptopropionic acid.
Further, the size of said CdSe quantum dot is about 1.70～1.80nm; The concentration of CdSe quantum dot (in the quality in system of CdSe quantum dot) is 1.00 * 10
-2Can dissolve the Cmax of CdSe quantum dot in g/L～system.
Further, the concentration of said ascorbic acid in photocatalysis product hydrogen system is>=1 * 10
-3Mol/L; When ascorbic acid reaches capacity concentration in hydrogen system is produced in photocatalysis after, continue to increase be not cannot, do not have economic worth only in theory.Therefore actual more preferably is selected as 1 * 10
-3Mol/L～ascorbic acid produces the saturated concentration in the hydrogen system in photocatalysis.
Further, water-soluble many carbonyls two iron two sulphur cluster compounds are the compounds with following molecular structural formula (I):
Further, said water-soluble many carbonyl two iron two sulphur cluster compounds produce concentration>=1 * 10 in the hydrogen system in photocatalysis
-5Mol/L; When water-soluble many carbonyl two iron two sulphur cluster compounds reach capacity concentration in hydrogen system is produced in photocatalysis after, continue to increase be not cannot, do not have economic worth only in theory.Therefore actual more preferably is selected as 1 * 10
-5Mol/L～water-soluble many carbonyl two iron two sulphur cluster compounds produce the saturated concentration in the hydrogen system in photocatalysis.
Further, said solvent is a water.
Further, the pH value scope of said photocatalysis product hydrogen system is 2.0～7.0.
Further, said water-insoluble many carbonyl two iron two sulphur cluster compounds are the compounds with following molecular structure:
Wherein, L is carbonyl or isocyano group benzene, and X is hydrogen atom or fluorine atom or methoxyl group or nitro or carbethoxyl group.
Further, said water-insoluble many carbonyl two iron two sulphur cluster compounds produce concentration>=1 * 10 in the hydrogen system in photocatalysis
-4Mol/L; When water-insoluble many carbonyl two iron two sulphur cluster compounds reach capacity concentration in hydrogen system is produced in photocatalysis after, continue to increase its content and be not cannot, do not have economic worth only in theory; Therefore actual more preferably is selected as 1 * 10
-4Mol/L～water-insoluble many carbonyl two iron two sulphur cluster compounds produce the saturated concentration in the hydrogen system in photocatalysis.
Further, said solvent is acetonitrile and water; Said acetonitrile and water volume ratio are 3: 7.
For solving above-mentioned second technical problem; The preparation method of water-soluble many carbonyls two iron two sulphur cluster compounds of formula of the present invention (I); Comprise the steps: this method be utilize carboxyl and amino condensation reaction with many branching contain four contract the triethylene glycol monomethyl ether chain hydrophilic radical be incorporated on many carbonyl two iron two sulphur bunch, generate and have the proton active water-soluble many carbonyl two iron two sulphur cluster compounds of catalytic reduction.
Concrete steps are following:
1) with 0.08～0.12g Compound C
15H
10Fe
2INO
5S
2(being called for short S1 later on) is dissolved in 20～30ml oxolane with 0.45～0.50g 4-acetylenylbenzene formic acid, adds 7～9ml anhydrous triethylamine again, and the argon gas degasification added 0.015～0.020g Pd (PPh more than 25 minutes after degasification finishes
3)
2Cl
2With 0.008～0.010g CuI, refluxed 5～7 hours, after monitoring reaction finishes, separate with silicagel column, dash pouring with the mixed solution of ethanol/methylene=1/10 (v/v) and obtain product S 2;
2) in 45～55ml DMF, add 7.50～7.70g Compound C
28H
48O
14(being called for short S3 later on), 2.55～2.65g, one end by tertbutyloxycarbonyl (abbreviate as later on: Boc) protection propane diamine, 7.75～7.80g hexafluorophosphoric acid BTA-1-base-oxygen base tripyrrole alkyl phosphorus (abbreviate as later on: PyBOP) with 18～22ml triethylamine; The stirring at room mixed liquor is more than 1 hour; Then mixed liquor is poured in 140～160ml water,, kept organic layer with dichloromethane extraction 2～4 times; Again with saturated aqueous common salt extraction 7～9 times; To remove the DMF in the mixed system, keep organic layer, add Na
2SO
4Dry; Concentrate the mixed solution contain product, silicagel column separates, and dashes pouring with the mixed solution of ethanol/methylene=1/100 (v/v) and obtains product S 4;
3) get 0.35～0.40g S4 and dissolve in 25～35ml carrene, add 8～12ml trifluoroacetic acid stirring at room simultaneously more than 1 hour, then reaction system is moved in the ice bath, in system, drip triethylamine and transfer alkalescence to up to system; In reaction system, add 12～18ml DMF, 0.28～0.32gS2 and 0.29～0.33g PyBOP, stirring at room more than 1 hour after; Reaction mixture is changed in 140～160ml water,, keep organic layer with dichloromethane extraction 2～4 times; Again with saturated common salt washing 7～9 times; To remove the DMF in the mixed system, keep organic layer, add Na
2SO
4Dry; Concentrate the mixed solution contain product, silicagel column separates, and dashes pouring with the mixed solution of ethanol/methylene=1/20 (v/v) and obtains product;
Wherein, the molecular structural formula of S1 is following:
Wherein, the molecular structural formula of S3 is following:
For solving above-mentioned the 3rd technical problem, the present invention is a kind of to utilize photocatalysis to produce the method that hydrogen system prepares hydrogen, comprises the steps: to use the radiation of visible light photocatalysis of λ＞400nm to produce hydrogen system, gas spectrum monitoring sample; After illumination reaction is accomplished, the sample hydrogen output that calculates.
The present invention has following beneficial effect: it is high that the hydrogen system hydrogen generation efficiency is produced in photocatalysis of the present invention; The stability of system is high; In the system cumulative volume is that the 10ml hydrogen output is up to 129 μ mol, reaches 1286 based on the hydrogen turnover number of calculated, and the system constituent is cheap and easy to get.
Description of drawings
Fig. 1. water-soluble many carbonyl two iron two sulphur cluster compounds
1The HNMR collection of illustrative plates;
Fig. 2. the retention time of illumination sample on the gas spectrum;
Fig. 3. the illumination sample ligand than: Sample 1: the water-soluble concentration that manys carbonyl two iron two sulphur cluster compounds: 1.00 * 10
-5M; CdSe quantum dot concentration: 4.02 * 10
-2G/L; Ascorbic acid (H
2A) concentration: 0.1M; Initial pH=4.00 (black line); Sample 2: the concentration of water-soluble many carbonyl two iron two sulphur cluster compounds: 1.00 * 10
-5M; CdSe quantum dot concentration: 4.02 * 10
-2G/L; Ascorbic acid (H
2A) concentration: 0.1M; Initial pH=7.03 (red line); Sample 3: the concentration of water-soluble many carbonyl two iron two sulphur cluster compounds: 1.00 * 10
-4M; CdSe quantum dot concentration: 4.02 * 10
-2G/L; Ascorbic acid (H
2A) concentration: 0.1M; Initial pH=4.00 (blue line); Sample 4: the concentration of water-soluble many carbonyl two iron two sulphur cluster compounds: 1.00 * 10
-4M; CdSe quantum dot concentration: 4.02 * 10
-2G/L; Ascorbic acid (H
2A) concentration: 0.1M; Initial pH=6.57 (green line); Population of samples is long-pending to be 10ml; Visible light (under the irradiation of λ＞400nm), with the amounts of hydrogen that generates in the gas spectrum monitoring sample, every illumination 2 hours, gas spectrum monitoring sample once.Pass through H
2And CH
4Working curve under this gas spectral condition calculates sample hydrogen output graph of a relation over time;
Fig. 4. the synthetic route chart of the water-soluble many carbonyl two iron two sulphur cluster compounds of the present invention.
The specific embodiment
Come the present invention is elaborated with specific embodiment below, but be not concrete restriction of the present invention.
Light source uses the high-pressure sodium lamp of 500W, and with the optical filter elimination wavelength of the 400nm ultraviolet light less than 400nm, the reservation visible light partly shines sample.The hydrogen usefulness gas spectrum that illumination produces detects (day beautiful GC-7890II), and nitrogen is as carrier gas, and transcranial Doppler detector (TCD) is as detector.Sample is contained in Shi Lanke (Schlenk) test tube, and the sample sealing was with nitrogen degasification 30 minutes before the illumination, and the methane gas of reinjecting 500 μ L seal illumination as interior mark.With the amounts of hydrogen that generates in the gas spectrum monitoring sample, gas phase partly extracts the detection of a certain amount of gas injection gas spectrum from the test tube upper strata at regular intervals, 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 Na0H before illumination.
Hydrogen system is produced in a kind of photocatalysis that contains many carbonyl two iron two sulphur cluster compounds: wherein, the concentration of water-soluble many carbonyl two iron two sulphur cluster compounds is 1.00 * 10
-5M; Be that (be called for short: concentration MPA-CdSe QDs) is 4.02 * 10 for the CdSe quantum dot of stabilizing agent with the mercaptopropionic acid
-2G/L; Ascorbic acid (H
2A) concentration is 1.00 * 10
-1M; The size of MPA-CdSe QDs is about 1.73nm; Solvent is a water; Population of samples is long-pending to be 10ml; PH=4.0 before the sample illumination.
The method of utilizing above-mentioned photocatalysis product hydrogen system to prepare hydrogen is: use the radiation of visible light sample of λ＞400nm, and every illumination 2 hours, gas spectrum monitoring sample is once; In illumination after 8 hours, the about 128.6 μ mol (TON=1286) of the sample hydrogen output that calculates; Sample continues to produce hydrogen in the first eight hour, the explanation system is stable in the illumination process of the first eight hour.
Said many carbonyls two iron two sulphur cluster compounds are the compounds with following molecular structural formula (I):
Hydrogen system is produced in a kind of photocatalysis that contains many carbonyl two iron two sulphur cluster compounds: wherein, the concentration of water-soluble many carbonyl two iron two sulphur cluster compounds is 1.00 * 10
-4M; The concentration of MPA-CdSe QDs is 8.02 * 10
-2G/L; Ascorbic acid (H
2A) concentration is 1.00 * 10
-2M; The size of MPA-CdSe QDs is about 1.70nm; Solvent is a water; Population of samples is long-pending to be 10ml; PH=2.0 before the sample illumination.
The method of utilizing above-mentioned photocatalysis product hydrogen system to prepare hydrogen is: use the radiation of visible light sample of λ＞400nm, and every illumination 2 hours, gas spectrum monitoring sample is once; After 8 hours, the sample hydrogen output that calculates is about 11.8 μ mol (TON=12) in illumination; Sample continued to produce hydrogen in the first six hour, and the explanation system is basicly stable in the illumination process of the first six hour.
Many carbonyls two iron two sulphur cluster compounds among said many carbonyls two iron, two sulphur cluster compounds and the embodiment 1 are same substances.
Hydrogen system is produced in a kind of photocatalysis that contains many carbonyl two iron two sulphur cluster compounds: wherein, the concentration of water-soluble many carbonyl two iron two sulphur cluster compounds is 1.00 * 10
-4M; The concentration of MPA-CdSe QDs is 8.02 * 10
-2G/L; Ascorbic acid (H
2A) concentration is 1.00 * 10
-2M; The size of MPA-CdSe QDs is about 1.80nm; Solvent is a water; Population of samples is long-pending to be 10ml; PH=3.0 before the sample illumination.
The method of utilizing above-mentioned photocatalysis product hydrogen system to prepare hydrogen is: use the radiation of visible light sample of λ＞400nm, and every illumination 2 hours, gas spectrum monitoring sample is once; After 8 hours, the sample hydrogen output that calculates is about 84.11 μ mol (TON=84) in illumination; Sample continued to produce hydrogen in the first six hour, and the explanation system is basicly stable in the illumination process of the first six hour.
Many carbonyls two iron two sulphur cluster compounds among said many carbonyls two iron, two sulphur cluster compounds and the embodiment 1 are same substances.
Hydrogen system is produced in a kind of photocatalysis that contains many carbonyl two iron two sulphur cluster compounds: wherein, the concentration of water-soluble many carbonyl two iron two sulphur cluster compounds is 1.00 * 10
-4M; The concentration of MPA-CdSe QDs is 8.02 * 10
-2G/L; Ascorbic acid (H
2A) concentration is 1.00 * 10
-2M; The size of MPA-CdSe QDs is about 1.70nm; Solvent is a water; Population of samples is long-pending to be 10ml; PH=4.0 before the sample illumination.
The method of utilizing above-mentioned photocatalysis product hydrogen system to prepare hydrogen is: use the radiation of visible light sample of λ＞400nm, and every illumination 2 hours, gas spectrum monitoring sample is once; After 8 hours, the sample hydrogen output that calculates is about 105.08 μ mol (TON=105) in illumination; Sample continued to produce hydrogen in the first six hour, and the explanation system is basicly stable in the illumination process of the first six hour.
Many carbonyls two iron two sulphur cluster compounds among said many carbonyls two iron, two sulphur cluster compounds and the embodiment 1 are same substances.
Embodiment 5
Hydrogen system is produced in a kind of photocatalysis that contains many carbonyl two iron two sulphur cluster compounds: wherein, the concentration of water-soluble many carbonyl two iron two sulphur cluster compounds is 1.00 * 10
-4M; The concentration of MPA-CdSe QDs is 8.02 * 10
-2G/L; Ascorbic acid (H
2A) concentration is 1.00 * 10
-2M; The size of MPA-CdSe QDs is about 1.73nm; Solvent is a water; Population of samples is long-pending to be 10ml; PH=5.0 before the sample illumination.
The method of utilizing above-mentioned photocatalysis product hydrogen system to prepare hydrogen is: use the radiation of visible light sample of λ＞400nm, and every illumination 2 hours, gas spectrum monitoring sample is once; After 8 hours, the sample hydrogen output that calculates is about 86.29 μ mol (TON=86) in illumination; Sample continued to produce hydrogen in the first six hour, and the explanation system is basicly stable in the illumination process of the first six hour.
Many carbonyls two iron two sulphur cluster compounds among said many carbonyls two iron, two sulphur cluster compounds and the embodiment 1 are same substances.
Embodiment 6
Hydrogen system is produced in a kind of photocatalysis that contains many carbonyl two iron two sulphur cluster compounds: wherein, the concentration of water-soluble many carbonyl two iron two sulphur cluster compounds is 1.00 * 10
-4M; The concentration of MPA-CdSe QDs is 8.02 * 10
-2G/L; Ascorbic acid (H
2A) concentration is 1.00 * 10
-2M; The size of MPA-CdSe QDs is about 1.73nm; Solvent is a water; Population of samples is long-pending to be 10ml; PH=6.1 before the sample illumination.
The method of utilizing above-mentioned photocatalysis product hydrogen system to prepare hydrogen is: use the radiation of visible light sample of λ＞400nm, and every illumination 2 hours, gas spectrum monitoring sample is once; After 8 hours, the sample hydrogen output that calculates is about 83.36 μ mol (TON=83) in illumination.Sample continued to produce hydrogen in the first six hour, and the explanation system is basicly stable in the illumination process of the first six hour.
Many carbonyls two iron two sulphur cluster compounds among said many carbonyls two iron, two sulphur cluster compounds and the embodiment 1 are same substances.
Embodiment 7
Hydrogen system is produced in a kind of photocatalysis that contains many carbonyl two iron two sulphur cluster compounds: wherein, the concentration of water-soluble many carbonyl two iron two sulphur cluster compounds is 1.00 * 10
-4M; The concentration of MPA-CdSe QDs is 8.02 * 10
-2G/L; Ascorbic acid (H
2A) concentration is 1.00 * 10
-2M; The size of MPA-CdSe QDs is about 1.73nm; Solvent is a water; Population of samples is long-pending to be 10ml; PH=7.1 before the sample illumination.
The method of utilizing above-mentioned photocatalysis product hydrogen system to prepare hydrogen is: use the radiation of visible light sample of λ＞400nm, and every illumination 2 hours, gas spectrum monitoring sample is once; After 8 hours, the sample hydrogen output that calculates is about 86.01 μ mol (TON=86) in illumination; Sample continued to produce hydrogen in the first six hour, and the explanation system is basicly stable in the illumination process of the first six hour.
Many carbonyls two iron two sulphur cluster compounds among said many carbonyls two iron, two sulphur cluster compounds and the embodiment 1 are same substances.
Hydrogen system is produced in a kind of photocatalysis that contains many carbonyl two iron two sulphur cluster compounds: wherein, the concentration of water-soluble many carbonyl two iron two sulphur cluster compounds is 4.00 * 10
-4M; The concentration of MPA-CdSe QDs is 8.04 * 10
-2G/L; Ascorbic acid (H
2A) concentration is 1.00 * 10
-2M; The size of MPA-CdSe QDs is about 1.73nm; Solvent is a water; Population of samples is long-pending to be 10ml; PH=4.0 before the sample illumination.
The method of utilizing above-mentioned photocatalysis product hydrogen system to prepare hydrogen is: use the radiation of visible light sample of λ＞400nm, and every illumination 2 hours, gas spectrum monitoring sample is once; After 8 hours, the sample hydrogen output that calculates is about 108.19 μ mol (TON=27) in illumination; Sample continued to produce hydrogen in the first six hour, and the explanation system is basicly stable in the illumination process of the first six hour.
Many carbonyls two iron two sulphur cluster compounds among said many carbonyls two iron, two sulphur cluster compounds and the embodiment 1 are same substances.
Embodiment 9
Hydrogen system is produced in a kind of photocatalysis that contains many carbonyl two iron two sulphur cluster compounds: wherein, the concentration of water-soluble many carbonyl two iron two sulphur cluster compounds is 2.00 * 10
-4M; The concentration of MPA-CdSe QDs is 8.04 * 10
-2G/L; Ascorbic acid (H
2A) concentration is 1.00 * 10
-2M; The size of MPA-CdSe QDs is about 1.73nm; Solvent is a water; Population of samples is long-pending to be 10ml; PH=4.0 before the sample illumination.
The method of utilizing above-mentioned photocatalysis product hydrogen system to prepare hydrogen is: use the radiation of visible light sample of λ＞400nm, and every illumination 2 hours, gas spectrum monitoring sample is once; After 8 hours, the sample hydrogen output that calculates is about 111.37 μ mol (TON=56) in illumination; Sample continued to produce hydrogen in the first six hour, and the explanation system is basicly stable in the illumination process of the first six hour.
Many carbonyls two iron two sulphur cluster compounds among said many carbonyls two iron, two sulphur cluster compounds and the embodiment 1 are same substances.
Embodiment 10
Hydrogen system is produced in a kind of photocatalysis that contains many carbonyl two iron two sulphur cluster compounds: wherein, the concentration of water-soluble many carbonyl two iron two sulphur cluster compounds is 2.00 * 10
-5M; The concentration of MPA-CdSe QDs is 8.04 * 10
-2G/L; Ascorbic acid (H
2A) concentration is 1.00 * 10
-2M; The size of MPA-CdSe QDs is about 1.73nm; Solvent is a water; Population of samples is long-pending to be 10ml; PH=4.0 before the sample illumination.
The method of utilizing above-mentioned photocatalysis product hydrogen system to prepare hydrogen is: use the radiation of visible light sample of λ＞400nm, and every illumination 2 hours, gas spectrum monitoring sample is once; After 8 hours, the sample hydrogen output that calculates is about 67.11 μ mol (TON=336) in illumination; Sample continued to produce hydrogen in the first six hour, and the explanation system is basicly stable in the illumination process of the first six hour.
Many carbonyls two iron two sulphur cluster compounds among said many carbonyls two iron, two sulphur cluster compounds and the embodiment 1 are same substances.
Embodiment 11
Hydrogen system is produced in a kind of photocatalysis that contains many carbonyl two iron two sulphur cluster compounds: wherein, the concentration of water-soluble many carbonyl two iron two sulphur cluster compounds is 1.00 * 10
-5M; The concentration of MPA-CdSe QDs is 8.04 * 10
-2G/L; Ascorbic acid (H
2A) concentration is 1.00 * 10
-2M; The size of MPA-CdSe QDs is about 1.73nm; Solvent is a water; Population of samples is long-pending to be 10ml; PH=4.0 before the sample illumination.
The method of utilizing above-mentioned photocatalysis product hydrogen system to prepare hydrogen is: use the radiation of visible light sample of λ＞400nm, and every illumination 2 hours, gas spectrum monitoring sample is once; After 8 hours, the sample hydrogen output that calculates is about 60.19 μ mol (TON=602) in illumination; Sample continued to produce hydrogen in the first six hour, and the explanation system is basicly stable in the illumination process of the first six hour.
Many carbonyls two iron two sulphur cluster compounds among said many carbonyls two iron, two sulphur cluster compounds and the embodiment 1 are same substances.
Hydrogen system is produced in a kind of photocatalysis that contains many carbonyl two iron two sulphur cluster compounds: wherein, the concentration of water-soluble many carbonyl two iron two sulphur cluster compounds is 1.00 * 10
-4M; The concentration of MPA-CdSe QDs is 2.01 * 10
-2G/L; Ascorbic acid (H
2A) concentration is 1.00 * 10
-2M; The size of MPA-CdSe QDs is about 1.73nm; Solvent is a water; Population of samples is long-pending to be 10ml; PH=4.0 before the sample illumination.
The method of utilizing above-mentioned photocatalysis product hydrogen system to prepare hydrogen is: use the radiation of visible light sample of λ＞400nm, and every illumination 2 hours, gas spectrum monitoring sample is once; After 8 hours, the sample hydrogen output that calculates is about 89.77 μ mol (TON=90) in illumination; Sample continued to produce hydrogen in the first six hour, and the explanation system is basicly stable in the illumination process of the first six hour.
Many carbonyls two iron two sulphur cluster compounds among said many carbonyls two iron, two sulphur cluster compounds and the embodiment 1 are same substances.
Embodiment 13
Hydrogen system is produced in a kind of photocatalysis that contains many carbonyl two iron two sulphur cluster compounds: wherein, the concentration of water-soluble many carbonyl two iron two sulphur cluster compounds is 1.00 * 10
-4M; The concentration of MPA-CdSe QDs is 4.02 * 10
-2G/L; Ascorbic acid (H
2A) concentration is 1.00 * 10
-2M; The size of MPA-CdSe QDs is about 1.73nm; Solvent is a water; Population of samples is long-pending to be 10ml; PH=4.0 before the sample illumination.
The method of utilizing above-mentioned photocatalysis product hydrogen system to prepare hydrogen is: use the radiation of visible light sample of λ＞400nm, and every illumination 2 hours, gas spectrum monitoring sample is once; After 8 hours, the sample hydrogen output that calculates is about 105.76 μ mol (TON=106) in illumination; Sample continued to produce hydrogen in the first six hour, and the explanation system is basicly stable in the illumination process of the first six hour.
Many carbonyls two iron two sulphur cluster compounds among said many carbonyls two iron, two sulphur cluster compounds and the embodiment 1 are same substances.
Embodiment 14
Hydrogen system is produced in a kind of photocatalysis that contains many carbonyl two iron two sulphur cluster compounds: wherein, the concentration of water-soluble many carbonyl two iron two sulphur cluster compounds is 1.00 * 10
-4M; The concentration of MPA-CdSe QDs is 4.02 * 10
-1G/L; Ascorbic acid (H
2A) concentration is 1.00 * 10
-2M; The size of MPA-CdSe QDs is about 1.73nm; Solvent is a water; Population of samples is long-pending to be 10ml; PH=4.0 before the sample illumination.
The method of utilizing above-mentioned photocatalysis product hydrogen system to prepare hydrogen is: use the radiation of visible light sample of λ＞400nm, and every illumination 2 hours, gas spectrum monitoring sample is once; After 8 hours, the sample hydrogen output that calculates is about 91.32 μ mol (TON=91) in illumination; Sample continued to produce hydrogen in the first six hour, and the explanation system is basicly stable in the illumination process of the first six hour.
Many carbonyls two iron two sulphur cluster compounds among said many carbonyls two iron, two sulphur cluster compounds and the embodiment 1 are same substances.
Embodiment 15
Hydrogen system is produced in a kind of photocatalysis that contains many carbonyl two iron two sulphur cluster compounds: wherein, the concentration of water-soluble many carbonyl two iron two sulphur cluster compounds is 1.00 * 10
-4M; The concentration of MPA-CdSe QDs is 8.04 * 10
-2G/L; Ascorbic acid (H
2A) concentration is 2.00 * 10
-3M; The size of MPA-CdSe QDs is about 1.73nm; Solvent is a water; Population of samples is long-pending to be 10ml; PH=4.0 before the sample illumination.
The method of utilizing above-mentioned photocatalysis product hydrogen system to prepare hydrogen is: use the radiation of visible light sample of λ＞400nm, and every illumination 2 hours, gas spectrum monitoring sample is once; After 8 hours, the sample hydrogen output that calculates is about 19.32 μ mol (TON=19) in illumination; Sample continued to produce hydrogen in the first six hour, and the explanation system is basicly stable in the illumination process of the first six hour.
Many carbonyls two iron two sulphur cluster compounds among said many carbonyls two iron, two sulphur cluster compounds and the embodiment 1 are same substances.
Hydrogen system is produced in a kind of photocatalysis that contains many carbonyl two iron two sulphur cluster compounds: wherein, the concentration of water-soluble many carbonyl two iron two sulphur cluster compounds is 1.00 * 10
-4M; The concentration of MPA-CdSe QDs is 8.04 * 10
-2G/L; Ascorbic acid (H
2A) concentration is 2.00 * 10
-3M; The size of MPA-CdSe QDs is about 1.73nm; Solvent is a water; Population of samples is long-pending to be 10ml; PH=4.0 before the sample illumination.
The method of utilizing above-mentioned photocatalysis product hydrogen system to prepare hydrogen is: use the radiation of visible light sample of λ＞400nm, and every illumination 2 hours, gas spectrum monitoring sample is once; After 8 hours, the sample hydrogen output that calculates is about 355.90 μ mol (TON=356) in illumination; Sample continued to produce hydrogen in the first six hour, and the explanation system is basicly stable in the illumination process of the first six hour.
Many carbonyls two iron two sulphur cluster compounds among said many carbonyls two iron, two sulphur cluster compounds and the embodiment 1 are same substances.
Embodiment 17
Hydrogen system is produced in a kind of photocatalysis that contains many carbonyl two iron two sulphur cluster compounds: wherein, the concentration of water-soluble many carbonyl two iron two sulphur cluster compounds is 1.00 * 10
-4M; The concentration of MPA-CdSe QDs is 8.04 * 10
-2G/L; Ascorbic acid (H
2A) concentration is 1.00 * 10
-1M; The size of MPA-CdSe QDs is about 1.73nm; Solvent is a water; Population of samples is long-pending to be 10ml; PH=4.0 before the sample illumination.
The method of utilizing above-mentioned photocatalysis product hydrogen system to prepare hydrogen is: use the radiation of visible light sample of λ＞400nm, and every illumination 2 hours, gas spectrum monitoring sample is once; After 8 hours, the sample hydrogen output that calculates is about 403.23 μ mol (TON=403) in illumination; Sample continued to produce hydrogen in the first six hour, and the explanation system is basicly stable in the illumination process of the first six hour.
Many carbonyls two iron two sulphur cluster compounds among said many carbonyls two iron, two sulphur cluster compounds and the embodiment 1 are same substances.
Embodiment 18
Hydrogen system is produced in a kind of photocatalysis that contains many carbonyl two iron two sulphur cluster compounds: wherein, the concentration of water-soluble many carbonyl two iron two sulphur cluster compounds is 1.00 * 10
-5M; The concentration of MPA-CdSe QDs is 4.02 * 10
-2G/L; Ascorbic acid (H
2A) concentration is 1.00 * 10
-1M; The size of MPA-CdSe QDs is about 1.73nm; Solvent is a water; Population of samples is long-pending to be 10ml; PH=7.0 before the sample illumination.
The method of utilizing above-mentioned photocatalysis product hydrogen system to prepare hydrogen is: use the radiation of visible light sample of λ＞400nm, and every illumination 2 hours, gas spectrum monitoring sample is once; After 18 hours, the sample hydrogen output that calculates is about 90.65 μ mol (TON=907) in illumination; Sample continues to produce hydrogen in the illumination process, and the explanation system is basicly stable in preceding illumination process.
Many carbonyls two iron two sulphur cluster compounds among said many carbonyls two iron, two sulphur cluster compounds and the embodiment 1 are same substances.
Embodiment 19
Hydrogen system is produced in a kind of photocatalysis that contains many carbonyl two iron two sulphur cluster compounds: wherein, the concentration of water-soluble many carbonyl two iron two sulphur cluster compounds is 1.00 * 10
-4M; The concentration of MPA-CdSe QDs is 4.02 * 10
-2G/L; Ascorbic acid (H
2A) concentration is 1.00 * 10
-1M; The size of MPA-CdSe QDs is about 1.73nm; Solvent is a water; Population of samples is long-pending to be 10ml; PH=4.0 before the sample illumination.
The method of utilizing above-mentioned photocatalysis product hydrogen system to prepare hydrogen is: use the radiation of visible light sample of λ＞400nm, and every illumination 2 hours, gas spectrum monitoring sample is once; After 18 hours, the sample hydrogen output that calculates is about 405.75 μ mol (TON=406) in illumination; Sample continues to produce hydrogen in the illumination process, and the explanation system is basicly stable in preceding illumination process.
Many carbonyls two iron two sulphur cluster compounds among said many carbonyls two iron, two sulphur cluster compounds and the embodiment 1 are same substances.
Embodiment 20
Hydrogen system is produced in a kind of photocatalysis that contains many carbonyl two iron two sulphur cluster compounds: wherein, the concentration of water-soluble many carbonyl two iron two sulphur cluster compounds is 1.00 * 10
-4M; The concentration of MPA-CdSe QDs is 4.02 * 10
-2G/L; Ascorbic acid (H
2A) concentration is 1.00 * 10
-1M; The size of MPA-CdSe QDs is about 1.73nm; Solvent is a water; Population of samples is long-pending to be 10ml; PH=6.6 before the sample illumination.
The method of utilizing above-mentioned photocatalysis product hydrogen system to prepare hydrogen is: use the radiation of visible light sample of λ＞400nm, and every illumination 2 hours, gas spectrum monitoring sample is once; After 18 hours, the sample hydrogen output that calculates is about 276.19 μ mol (TON=276) in illumination; Sample continues to produce hydrogen in the illumination process, and the explanation system is basicly stable in preceding illumination process.
Many carbonyls two iron two sulphur cluster compounds among said many carbonyls two iron, two sulphur cluster compounds and the embodiment 1 are same substances.
The preparation method of the water-soluble many carbonyls two iron two sulphur cluster compounds among the embodiment 1-20 comprises the steps:
1) 0.08～0.12g S1 and 0.45～0.50g 4-acetylenylbenzene formic acid are dissolved in 20～30ml oxolane, add 7～9ml anhydrous triethylamine again, the argon gas degasification added 0.015～0.020g Pd (PPh more than 25 minutes after degasification finishes
3)
2Cl
2With 0.008～0.010g CuI, refluxed 5～7 hours, after monitoring reaction finishes, separate with silicagel column, dash pouring with the mixed solution of ethanol/methylene=1/10 (v/v) and obtain product S 2;
2) in 45～55ml DMF, add 7.50～7.70g S3,2.55～2.65g, one end is by the propane diamine of Boc protection, 7.75～7.80g PyBOP and 18～22ml triethylamine; The stirring at room mixed liquor is poured mixed liquor in 140～160ml water into more than 1 hour then, with dichloromethane extraction 2～4 times; Keep organic layer, again with saturated aqueous common salt extraction 7～9 times, to remove the DMF in the mixed system; Keep organic layer, add Na
2SO
4Dry; Concentrate the mixed solution contain product, silicagel column separates, and dashes pouring with the mixed solution of ethanol/methylene=1/100 (v/v) and obtains product S 4;
3) get 0.35～0.40g S4 and dissolve in 25～35ml carrene, add 8～12ml trifluoroacetic acid stirring at room simultaneously more than 1 hour, then reaction system is moved in the ice bath, in system, drip triethylamine and transfer alkalescence to up to system; In reaction system, add 12～18ml DMF, 0.28～0.32gS2 and 0.29～0.33g PyBOP, stirring at room more than 1 hour after; Reaction mixture is changed in 140～160ml water,, keep organic layer with dichloromethane extraction 2～4 times; Again with saturated common salt washing 7～9 times; To remove the DMF in the mixed system, keep organic layer, add Na
2SO
4Dry; Concentrate the mixed solution contain product, silicagel column separates, and dashes pouring with the mixed solution of ethanol/methylene=1/20 (v/v) and obtains product.
Embodiment 22
Hydrogen system is produced in a kind of photocatalysis that contains many carbonyl two iron two sulphur cluster compound catalyst: wherein, many carbonyl two iron two sulphur cluster compounds are [(μ-CH
2)
3Fe
2S
2(CO)
6], its concentration is 4.87 * 10
-4M; The concentration of MPA-CdSe QDs is 1.24 * 10
-1M; Ascorbic acid (H
2A) concentration is 1.00 * 10
-2M; The size of MPA-CdSe QDs is about 1.73nm; Solvent is water and acetonitrile (volume ratio=7: 3); Population of samples is long-pending to be 10ml.
The method of utilizing above-mentioned photocatalysis product hydrogen system to prepare hydrogen is: use the radiation of visible light sample of λ＞400nm, gas spectrum monitoring sample.After 3 hours, the sample hydrogen output that calculates is about 30.25 μ mol (TON=6.2) in illumination.
Said many carbonyls two iron two sulphur cluster compound [(μ-CH
2)
3Fe
2S
2(CO)
6] molecular structure following:
Embodiment 23
Hydrogen system is produced in a kind of photocatalysis that contains many carbonyl two iron two sulphur cluster compound catalyst: wherein, many carbonyl two iron two sulphur cluster compounds are [(μ-CH
2)
3Fe
2(CO)
5(CNph)], its concentration is 4.36 * 10
-4M; The concentration of MPA-CdSe QDs is 1.24 * 10
-1M; Ascorbic acid (H
2A) concentration is 1.00 * 10
-2M; The size of MPA-CdSe QDs is about 1.73nm; Solvent is water and acetonitrile (volume ratio=7: 3); Population of samples is long-pending to be 10ml.
The method of utilizing above-mentioned photocatalysis product hydrogen system to prepare hydrogen is: use the radiation of visible light sample of λ＞400nm, gas spectrum monitoring sample; After 3 hours, the sample hydrogen output that calculates is about 11.67 μ mol (TON=2.7) in illumination.
Said many carbonyls two iron two sulphur cluster compound [(μ-CH
2)
3Fe
2(CO)
5(CNph)] molecular structure is following:
Embodiment 24
Hydrogen system is produced in a kind of photocatalysis that contains many carbonyl two iron two sulphur cluster compound catalyst: wherein, many carbonyl two iron two sulphur cluster compounds are [(μ-CH
2)
3Fe
2(CO)
5(CNphCCph)], its concentration is 2.55 * 10
-4M; The concentration of MPA-CdSe QDs is 1.24 * 10
-1M; Ascorbic acid (H
2A) concentration is 1.00 * 10
-2M; The size of MPA-CdSe QDs is about 1.73nm; Solvent is water and acetonitrile (volume ratio=7: 3); Population of samples is long-pending to be 10ml.
The method of utilizing above-mentioned photocatalysis product hydrogen system to prepare hydrogen is: use the radiation of visible light sample of λ＞400nm, gas spectrum monitoring sample; After 3 hours, the sample hydrogen output that calculates is about 2.04 μ mol (TON=0.8) in illumination.
Said many carbonyls two iron two sulphur cluster compound [(μ-CH
2)
3Fe
2(CO)
5(CNphCCph)] molecular structure is following:
Embodiment 25
Hydrogen system is produced in a kind of photocatalysis that contains many carbonyl two iron two sulphur cluster compound catalyst: wherein, many carbonyl two iron two sulphur cluster compounds are [(μ-CH
2)
3Fe
2(CO)
5(CNphCCphF)], its concentration is 3.64 * 10
-4M; The concentration of MPA-CdSe QDs is 1.24 * 10
-1M; Ascorbic acid (H
2A) concentration is 1.00 * 10
-2M; The size of MPA-CdSe QDs is about 1.73nm; Solvent is water and acetonitrile (volume ratio=7: 3); Population of samples is long-pending to be 10ml.
The method of utilizing above-mentioned photocatalysis product hydrogen system to prepare hydrogen is: use the radiation of visible light sample of λ＞400nm, gas spectrum monitoring sample; After 3 hours, the sample hydrogen output that calculates is about 45.77 μ mol (TON=13) in illumination.
Said many carbonyls two iron two sulphur cluster compound [(μ-CH
2)
3Fe
2(CO)
5(CNphCCphF)] molecular structure is following:
Embodiment 26
Hydrogen system is produced in a kind of photocatalysis that contains many carbonyl two iron two sulphur cluster compound catalyst: wherein, many carbonyl two iron two sulphur cluster compounds are [(μ-CH
2)
3Fe
2(CO)
5(CNphCCphOMe)], its concentration is 4.01 * 10
-4M; The concentration of MPA-CdSe QDs is 1.24 * 10
-1M; Ascorbic acid (H
2A) concentration is 1.00 * 10
-2M; The size of MPA-CdSe QDs is about 1.73nm; Solvent is water and acetonitrile (volume ratio=7: 3); Population of samples is long-pending to be 10ml.
The method of utilizing above-mentioned photocatalysis product hydrogen system to prepare hydrogen is: use the radiation of visible light sample of λ＞400nm, gas spectrum monitoring sample; After 3 hours, the sample hydrogen output that calculates is about 53.53 μ mol (TON=13) in illumination.
Said many carbonyls two iron two sulphur cluster compound [(μ-CH
2)
3Fe
2(CO)
5(CNphCCphOMe)] molecular structure is following:
Embodiment 27
Hydrogen system is produced in a kind of photocatalysis that contains many carbonyl two iron two sulphur cluster compound catalyst: wherein, many carbonyl two iron two sulphur cluster compounds are [(μ-CH
2)
3Fe
2(CO)
5(CNphCCphNO
2)], its concentration is 4.43 * 10
-4M; The concentration of MPA-CdSe QDs is 1.24 * 10
-1M; Ascorbic acid (H
2A) concentration is 1.00 * 10
-2M; The size of MPA-CdSe QDs is about 1.73nm; Solvent is water and acetonitrile (volume ratio=7: 3); Population of samples is long-pending to be 10ml.
The method of utilizing above-mentioned photocatalysis product hydrogen system to prepare hydrogen is: use the radiation of visible light sample of λ＞400nm, gas spectrum monitoring sample; After 3 hours, the sample hydrogen output that calculates is about 13.30 μ mol (TON=3) in illumination.
Said many carbonyls two iron two sulphur cluster compound [(μ-CH
2)
3Fe
2(CO)
5(CNphCCphNO
2)] molecular structure following:
Embodiment 28
Hydrogen system is produced in a kind of photocatalysis that contains many carbonyl two iron two sulphur cluster compound catalyst: wherein, many carbonyl two iron two sulphur cluster compounds are [(μ-CH
2)
3Fe
2(CO)
5(CNphCCphCOOEt)], its concentration is 4.04 * 10
-4M; The concentration of MPA-CdSe QDs is 1.24 * 10
-1M; Ascorbic acid (H
2A) concentration is 1.00 * 10
-2M; The size of MPA-CdSe QDs is about 1.73nm; Solvent is water and acetonitrile (volume ratio=7: 3); Population of samples is long-pending to be 10ml.
The method of utilizing above-mentioned photocatalysis product hydrogen system to prepare hydrogen is: use the radiation of visible light sample of λ＞400nm, gas spectrum monitoring sample; After 3 hours, the sample hydrogen output that calculates is about 59.96 μ mol (TON=15) in illumination.
Said many carbonyls two iron two sulphur cluster compound [(μ-CH
2)
3Fe
2(CO)
5(CNphCCphCOOEt)] molecular structure is following:
Obviously, the above embodiment of the present invention only be for clearly the present invention is described and is done for example, and be not to be qualification to embodiment of the present invention.For the those of ordinary skill in affiliated field, on the basis of above-mentioned explanation, can also make other multi-form variation or change.Here can't give exhaustive to all embodiments.Everyly belong to the row that conspicuous variation that technical scheme of the present invention extends out or change still are in protection scope of the present invention.
Claims (10)
1. contain many carbonyl two iron, two sulphur cluster compounds and the catalysis of CdSe quantum dot light and produce hydrogen system, it is characterized in that: it comprises:
Many carbonyl two iron two sulphur cluster compounds,
The CdSe quantum dot,
Ascorbic acid and
Aqueous solvent.
2. hydrogen system is produced in photocatalysis according to claim 1, and it is characterized in that: said CdSe quantum dot is to be stabilizing agent with the mercaptopropionic acid; And the size of said CdSe quantum dot is about 1.70～1.80nm; In the quality of CdSe quantum dot in system, the concentration of said CdSe quantum dot is 1.00 * 10
2Can dissolve the Cmax of CdSe quantum dot in g/L～system.
3. hydrogen system is produced in photocatalysis according to claim 1, it is characterized in that: said ascorbic acid produces concentration>=1 * 10 in the hydrogen system in photocatalysis
-3Mol/L.
4. hydrogen system is produced in photocatalysis according to claim 1, and it is characterized in that: said many carbonyl two iron two sulphur cluster compounds are water-soluble many carbonyls two iron, two sulphur cluster compounds or water-insoluble many carbonyls two iron two sulphur cluster compounds.
5. hydrogen system is produced in photocatalysis according to claim 4, and it is characterized in that: said water-soluble many carbonyl two iron two sulphur cluster compounds are the compounds with following formula (I) molecular structure:
6. hydrogen system is produced in photocatalysis according to claim 5, and it is characterized in that: said aqueous solvent is a water.
7. hydrogen system is produced in photocatalysis according to claim 4, and it is characterized in that: said water-insoluble many carbonyl two iron two sulphur cluster compounds are the compounds with following molecular structure:
Wherein, L is carbonyl or isocyano group benzene, and X is hydrogen atom or fluorine atom or methoxyl group or nitro or carbethoxyl group.
8. hydrogen system is produced in photocatalysis according to claim 7, and it is characterized in that: said aqueous solvent is acetonitrile and water, and said acetonitrile and water volume ratio are 3: 7.
9. the preparation method of the water-soluble many carbonyl two iron two sulphur cluster compounds of the formula described in claim 5 (I); It is characterized in that: this method is to utilize carboxyl and amino condensation reaction will contain the contract hydrophilic radical of triethylene glycol monomethyl ether chain of four of many branching to be incorporated on many carbonyl two iron two sulphur bunch, generates to have the proton active water-soluble many carbonyl two iron two sulphur cluster compounds of catalytic reduction.
10. according to the preparation method of water-soluble many carbonyls two iron two sulphur cluster compounds of formula described in the claim 9 (I), it is characterized in that: comprise following concrete steps:
1) with 0.08～0.12g C
15H
10Fe
2INO
5S
2(being called for short S1 later on) is dissolved in 20～30ml oxolane with 0.45～0.50g 4-acetylenylbenzene formic acid, adds 7～9ml anhydrous triethylamine again, and the argon gas degasification added 0.015～0.020g Pd (PPh more than 25 minutes after degasification finishes
3)
2Cl
2With 0.008～0.010g CuI, refluxed 5～7 hours, after monitoring reaction finishes, separate with silicagel column, dash pouring with the mixed solution of ethanol/methylene=1/10 (v/v) and obtain product S 2;
2) in 45～55ml DMF, add 7.50～7.70g C
28H
48O
14(being called for short S3 later on), 2.55～2.65g, one end by tertbutyloxycarbonyl (abbreviate as later on: Boc) protection propane diamine, 7.75～7.80g hexafluorophosphoric acid BTA-1-base-oxygen base tripyrrole alkyl phosphorus (abbreviate as later on: PyBOP) with 18～22ml triethylamine; The stirring at room mixed liquor is more than 1 hour; Then mixed liquor is poured in 140～160ml water,, kept organic layer with dichloromethane extraction 2～4 times; Again with saturated aqueous common salt extraction 7～9 times; To remove the DMF in the mixed system, keep organic layer, add Na
2SO
4Dry; Concentrate the mixed solution contain product, silicagel column separates, and dashes pouring with the mixed solution of ethanol/methylene=1/100 (v/v) and obtains product S 4;
3) get 0.35～0.40g S4 and dissolve in 25～35ml carrene, add 8～12ml trifluoroacetic acid stirring at room simultaneously more than 1 hour, then reaction system is moved in the ice bath, in system, drip triethylamine and transfer alkalescence to up to system; In reaction system, add 12～18ml DMF, 0.28～0.32gS2 and 0.29～0.33g PyBOP, stirring at room more than 1 hour after; Reaction mixture is changed in 140～160ml water,, keep organic layer with dichloromethane extraction 2～4 times; Again with saturated common salt washing 7～9 times; To remove the DMF in the mixed system, keep organic layer, add Na
2SO
4Dry; Concentrate the mixed solution contain product, silicagel column separates, and dashes pouring with the mixed solution of ethanol/methylene=1/20 (v/v) and obtains product.
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