CN106995469B - A kind of visible light photocatalysis production hydrogen system and its application including more carbonyl heteronuclear bimetallic sulphur cluster compounds - Google Patents
A kind of visible light photocatalysis production hydrogen system and its application including more carbonyl heteronuclear bimetallic sulphur cluster compounds Download PDFInfo
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- CN106995469B CN106995469B CN201710323093.5A CN201710323093A CN106995469B CN 106995469 B CN106995469 B CN 106995469B CN 201710323093 A CN201710323093 A CN 201710323093A CN 106995469 B CN106995469 B CN 106995469B
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- carbonyl
- hydrogen
- heteronuclear
- visible light
- cluster compounds
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/226—Sulfur, e.g. thiocarbamates
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
- B01J31/2414—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
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Abstract
The invention discloses a kind of, and the visible light photocatalysis including more carbonyl heteronuclear bimetallic sulphur cluster compounds produces hydrogen system, including quantum dot, more two sulphur cluster compounds of carbonyl heteronuclear bimetallic and solvent.Photocatalyzed Hydrogen Production system of the invention has been introduced into the Photocatalyzed Hydrogen Production system containing more carbonyl heteronuclear bimetallics hydrogenation enzyme mimics using quantum dot as photosensitizer, is improved Photocatalyzed Hydrogen Production system efficiency and stability, is reduced the production cost of system.The invention also discloses a kind of preparation methods of more carbonyl heteronuclear bimetallic sulphur cluster compounds, and in methylene chloride, compound A and compound B react to obtain more bis- sulphur cluster compounds of carbonyl heteronuclear Ni-Mn or more bis- sulphur cluster compounds of carbonyl heteronuclear Ni-Ru；The compound A is The compound B is Mn (CO)5Br or [Ru (CO)2Cl2]n.Solve the problems, such as that more carbonyl heteronuclear bimetallic sulphur cluster compound synthesis are difficult.
Description
Technical field
The present invention relates to Photocatalyzed Hydrogen Production technical fields.It include more carbonyl heteronuclear bimetallic sulphur more particularly, to one kind
The visible light photocatalysis of cluster compound produces hydrogen system and its application.
Background technique
With economic rapid development, demand of the mankind to the energy is continuously increased.Sun energy storage capacity is huge, but dispersibility,
Intermittent and low density limitation requirement must be translated into the energy that can store and utilize.Hydrogen Energy combustion heat height (every thousand
The energy that gram combustion of hydrogen generates is three times of gasoline), it is water that burning, which generates product, has the characteristics that free of contamination, is considered as
Century optimal green energy resource.Converting solar energy into Hydrogen Energy is one of optimal storing mode.
By photosynthesis of plant in nature, it converts chemical energy on a large scale by solar energy highly effective, wherein occurring
The primary reaction of photosynthetic reaction centre is efficiently completed by the photosynthetical system being integrated in photosynthetic membrane.Photosynthetical system II absorbs photon
Water-splitting is released oxygen by the hole of generation, is formed by electronics and proton is passed to photosynthetical system I.Certain photosynthetic bacteria systems
The hydrogenase activity center of system I is hydrogen using obtained electronic catalytic proton reduction.Nevertheless, directly extracting and purifying hydrogenation
Enzyme is difficult, once departing from Bio-ontology environmental exposure in air, catalytic activity is reduced rapidly, therefore to native enzyme activity
Center carries out chemical simulation, and synthesizing new manually hydrogenates enzyme mimics, reproduces the efficient mild catalytic proton of nature hydrogenase also
The process for originating in hydrogen has important practical significance.
Hydrogenase is divided into single iron hydrogenase (Fe hydrogenase) according to enzymatic activity metal center difference, iron iron hydrogenase (FeFe
Hydrogenase) and ferronickel hydrogenase (NiFe hydrogenase).Nineteen twenty-nine Reihlen et al. reports the bis- gold of more carbonyl same core FeFe for the first time
Belong to the synthesis of centered complex, but the research of NiFe hydrogenation enzyme mimics is very slow.Professor's Darensbourg synthesis in 1996
First case NiFe metal center hydrogenates enzyme mimics, and synthesis and structure are reported successively, but until Artero in 2006 is taught
Using more carbonyl heteronuclear NiRu metal centers hydrogenation enzyme mimics realize electro-catalysis reduction proton be hydrogen (referring to
Inorg.Chem.2006,[Ni(xbsms)Ru(CO)2Cl2]:a bioinspired nickel-ruthenium
Functional model of [NiFe] hydrogenase, 45,4334-4336), professor Rauchfuss in 2009 utilizes more
Carbonyl heteronuclear NiFe metal center hydrogenates enzyme mimics and realizes that electro-catalysis produces hydrogen (referring to J.Am.Chem.Soc.2009Nickel-
iron dithiolato hydrides relevant to the[NiFe]-hydrogenase active site,131,
6942-6943).The report of first case Photocatalyzed Hydrogen Production from McMaster professor, George professor andProfessor's
Cooperation.They utilize ReCl (CO) within 20143(bpy) make photosensitizer, more carbonyl heterometallocenes NiFe2Hydrogenation enzyme mimics are to urge
Agent, triethylamine makees proton source as electronics sacrificial body and triethanolamine tetrafluoroborate realizes photocatalysis in acetonitrile solvent
Proton reduction is hydrogen, but in optimal conditions the turn over number of system Photocatalyzed Hydrogen Production be only 55 (TON) (referring to
Inorg.Chem.Photochemical dihydrogen production using an analogue of the
active site of[NiFe]hydrogenase,2014,53,6329-6337).Obviously develop Cheap highly effective heteronuclear bimetallic
It is extremely urgent that center hydrogenates enzyme mimics Photocatalyzed Hydrogen Production system.
Accordingly, it is desirable to provide a kind of Cheap highly effective heteronuclear bimetallic center hydrogenation enzyme mimics preparation method and this cheap
The visible light photocatalysis of efficient heteronuclear bimetallic center hydrogenation enzyme mimics produces hydrogen system and its application.
Summary of the invention
It is an object of the present invention to provide a kind of visible light light including more carbonyl heteronuclear bimetallic sulphur cluster compounds
Catalysis produces hydrogen system.
Second object of the present invention is to provide a kind of visible light including more carbonyl heteronuclear bimetallic sulphur cluster compounds
The application of Photocatalyzed Hydrogen Production system.
Third object of the present invention is to provide a kind of preparation method of more carbonyl heteronuclear bimetallic sulphur cluster compounds.For
Reach above-mentioned first purpose, the present invention adopts the following technical solutions:
A kind of visible light photocatalysis production hydrogen system including more carbonyl heteronuclear bimetallic sulphur cluster compounds, including quantum dot,
More two sulphur cluster compounds of carbonyl heteronuclear bimetallic and solvent.The present invention using quantum dot have it is excellent it is visible light-responded, swash more
The characteristics of son generates, light-generated excitons separate and migration, using quantum dot as photosensitizer, with a variety of more carbonyl heteronuclear bimetallic sulphur clusters
It hydrogenates enzyme mimics and constructs Photocatalyzed Hydrogen Production system, obtain report catalytic efficiency and the highest Photocatalyzed Hydrogen Production of stability at present
System.Wherein the introducing of quantum dot greatly reduces the cost of heteronuclear bimetallic Photocatalyzed Hydrogen Production system, improves photic production hydrogen
The stability and efficiency of system.
Preferably, the heteronuclear bimetallic in more two sulphur cluster compounds of carbonyl heteronuclear bimetallic is selected from Ni, Fe, Mn, Ru
One or both of.
Preferably, the heteronuclear bimetallic in more two sulphur cluster compounds of carbonyl heteronuclear bimetallic be Ni-Fe, Ni-Mn or
Ni-Ru；Further, the heteronuclear bimetallic in more two sulphur cluster compounds of carbonyl heteronuclear bimetallic is Ni-Mn or Ni-Ru.
Preferably, it further includes electronics sacrificial body that the visible light photocatalysis, which produces hydrogen system,；Electronics sacrificial body in the present invention
It gives electron transmission to light activated photosensitizer, endlessly provides electronics for entire catalytic cycle.Electronics sacrifice in the present invention
The addition of body can be improved the hydrogen generation efficiency for producing hydrogen system.
Preferably, it further includes proton source that the visible light photocatalysis, which produces hydrogen system,.The addition of proton source can in the present invention
Improve the hydrogen generation efficiency for producing hydrogen system.
Preferably, the electronics sacrificial body is aminated compounds, alcohol compound or thiol compound；Further,
The electronics sacrificial body is selected from isopropanol, triethylamine, triethanolamine, ascorbic acid, ethylenediamine tetra-acetic acid (EDTA), sulfydryl third
Acid, thioacetic acid,(BNAH) andOne of (BIH) or it is a variety of.It is highly preferred that described
Electronics sacrificial body be selected from isopropanol, triethanolamine, ascorbic acid, ethylenediamine tetra-acetic acid (EDTA), mercaptopropionic acid, thioacetic acid,(BNAH) andOne of (BIH) or it is a variety of.Further, the electronics sacrificial body is
Isopropanol.
Preferably, concentration≤15mol/L of the electronics sacrificial body.It is dense that the electronics sacrificial body reaches saturation in a solvent
After degree, the content of electronics sacrificial body can be continued growing, only theoretically without economic value.
Preferably, the proton source is selected from hydrochloric acid, acetic acid, formic acid, trifluoroacetic acid, triethylamine hydrochloride, triethylamine tetrafluoro
One of borate, triethanolamine tetrafluoroborate, isopropanol, methanol, trifluoroethanol, phenol and benzoic acid are a variety of；More
Preferably, the proton source is selected from hydrochloric acid, acetic acid, formic acid, trifluoroacetic acid, triethylamine hydrochloride, isopropanol, methanol, trifluoro second
One of alcohol, phenol and benzoic acid are a variety of.
Preferably, concentration≤1mol/L of the proton source.It, can be with after the proton source reaches saturated concentration in a solvent
The content for continuing growing proton source, only theoretically without economic value.
Preferably, it further includes Bronsted acid that the visible light photocatalysis, which produces hydrogen system,.The present invention is by the way that matter is added into system
Sub- acid stablizes Photocatalyzed Hydrogen Production system.
Preferably, the Bronsted acid be polymer, preferably carbohydrate, biological polypeptide, polyetherimide PEI, chitosan and
One of hyaluronic acid is a variety of；It is highly preferred that the Bronsted acid is hyaluronic acid, i.e., a kind of vitreous humor for being located away from ox
Polymer.
Preferably, concentration≤1.0mg/L of the Bronsted acid can after the Bronsted acid reaches saturated concentration in a solvent
To continue growing the content of Bronsted acid, only theoretically without economic value.
Preferably, the solvent is organic solvent and/or water.Quantum dot is that a kind of good water solubility is photosensitive in the present invention
Agent can not only be dissolved in water and can be dissolved in organic solvent or the mixed system including water and organic solvent, this ectosome
The electronics sacrificial body being added in system is also miscible with water, and hyaluronic acid macromolecule can also assist these components to dissolve, therefore this hair
Solvent in bright is organic solvent and/or water.In addition, the present invention is by adjusting in solvent the ratio of organic solvent and water come into one
Step improves hydrogen generation efficiency.
Preferably, the volume ratio of organic solvent and water is 0~1:1 in the solvent；Further, in certain of the invention
In a little specific embodiments, for example, the volume ratio of the organic solvent and water is 1:0.5~9,1:0.5~8,1:0.5~7,1:
0.5~6,1:0.5~5,1:0.5~4,1:0.5~3,1:0.5~2,1:0.5~1 etc.；It is highly preferred that the organic solvent and
The volume ratio of water is 1:1~9,1:2~8,1:3~7,1:4~6 etc., it is highly preferred that the volume ratio of the organic solvent and water is
1:0.5,1:1,1:2,1:3,1:9 etc..The ratio of organic reagent and water reagent is influenced on hydrogen system efficiency is produced in the present invention,
It is confirmed by comparative experiments, in organic reagent: the production hydrogen system efficiency is best when the volume ratio of water is 1:3.
Preferably, the organic solvent is selected from acetonitrile, n,N-Dimethylformamide, n,N-dimethylacetamide, tetrahydro furan
It mutters, one of ethyl alcohol, methanol, isopropanol and acetone or a variety of；Organic solvent in the present invention can be with water arbitrary proportion
It dissolves each other, and a small amount of organic solvent can be dissolved with cocatalyst.It is highly preferred that the organic solvent is selected from N, N- dimethyl
One of formamide, n,N-dimethylacetamide, tetrahydrofuran, ethyl alcohol, methanol, isopropanol and acetone are a variety of.Further
Ground, the organic solvent are isopropanol.
Preferably, it is 1-14 that the visible light photocatalysis, which produces the pH value range of hydrogen system,.PH value is not only in system of the present invention
It determines the concentration of Photocatalyzed Hydrogen Production system inner proton, and is the ligand that pH will affect photosensitizer surface to photosensitizer effect,
If surface ligand is easy to fall off at low ph values, keep photosensitizer unstable；In pH value range of the invention, system can be stablized
Produce hydrogen；Further, in certain specific embodiments of the invention, for example, the visible light photocatalysis produces the pH of hydrogen system
Being worth range is 1~13,1~12,1~11,1~10,1~9,1~8,1~7,1~6,1~5,1~4,1~3,1~2 etc..Into
One step, the pH value range that the visible light photocatalysis produces hydrogen system is 2~13,3~12,4~11,5~10,6~9,7~8
Deng.It is highly preferred that the pH value range that the visible light photocatalysis produces hydrogen system is 7~9, more preferable pH value is 8.
Preferably, the quantum dot is the quantum dot containing stabilizer, and the stabilizer is MPA, that is, mercaptopropionic acid, due to
Quantum dot size in the present invention is small, and surface can be high, is easy to reunite.Stabilizer can stablize quantum dot surface, increase its dispersion
Property, make quantum dot stable homogeneous in the solution.
Preferably, the quantum dot is selected from CdSe, CdS, CdTe, ZnSe, ZnS, CdSe/ZnS, CdSe/ZnO, CdSe/
One of CdS, CdTe/CdSe, CdS/ZnSe, CdS/ZnTe quantum dot is a variety of；Further, the quantum dot is selected from
CdS, CdTe, ZnSe, ZnS, CdSe/ZnS, CdSe/ZnO, CdSe/CdS, CdTe/CdSe, CdS/ZnSe, CdS/ZnTe quantum
One of point is a variety of.
Preferably, the size range of the quantum dot is 1.5~10.0nm.Further, of the invention certain specific
In embodiment, for example, the size range of the quantum dot be 1.5~9.0nm, 1.5~8.0nm, 1.5~7.0nm, 1.5~
6.0nm, 1.5~5.0nm, 1.5~4.0nm, 1.5~3.0nm, 1.5~2.0nm etc.；Further, the size of the quantum dot
Range is 2.0~9.0nm, 3.0~8.0nm, 4.0~7.0nm, 5.0~6.0nm etc.；It is highly preferred that the size of the quantum dot
Range is 2.0~4.0nm, more preferably 2.5nm.
Preferably, the concentration of the quantum dot is 1 × 10-7~saturated concentration；The quantum dot reaches saturation in a solvent
After concentration, the content of quantum dot can be continued growing, only theoretically without economic value, therefore it is highly preferred that the amount
The concentration of son point is 1 × 10-7~1 × 10-3mol/L.Further, in certain specific embodiments of the invention, for example,
The concentration of the quantum dot is 1 × 10-7~1 × 10-4mol/L、1×10-7~1 × 10-5mol/L、1×10-7~9 × 10- 6mol/L、1×10-7~8 × 10-6mol/L、1×10-7~7 × 10-6mol/L、1×10-7~6 × 10-6mol/L、1×10-7~
5×10-6mol/L、1×10-7~4 × 10-6mol/L、1×10-7~3 × 10-6mol/L、1×10-7~2 × 10-6mol/L、1×
10-7~1 × 10-6Mol/L etc..Further, the concentration of the quantum dot is 1 × 10-6~9 × 10-6mol/L、2×10-6~8
×10-6mol/L、3×10-6~7 × 10-6mol/L、4×10-6~6 × 10-6Mol/L etc..It is highly preferred that the quantum dot
Concentration is 2.68 × 10-6~10.72 × 10-6Mol/L, more preferably 8 × 10-6mol/L。
Preferably, more two sulphur cluster compounds of carbonyl heteronuclear bimetallic are selected from one of C1~C5 structural formula:
.Further, more two sulphur cluster compounds of carbonyl heteronuclear bimetallic are selected from one of C2~C5 structural formula.This
Compound C1 uses literature method (Barton, B.E. in invention；Rauchfuss,T.B.,Hydride-containing
models for the active site of the nickel-iron
Hydrogenases.J.Am.Chem.Soc.2010,132,14877-14885.) it is made, in order to expand NiFe hydrogenation enzyme simulation
Object light causes to produce the type of hydrogen system, solves the problems, such as that more carbonyl heteronuclear bimetallic sulphur cluster compound synthesis are difficult, the present invention proposes
A variety of more carbonyl heteronuclear bimetallic sulphur cluster compounds, and propose the preparation method of the compound, step is simple, and synthesis obtains
A variety of and quantum dot photosensitizer etc. collectively constitutes more carbonyl heteronuclear bimetallic sulphur cluster compounds of a variety of highly effective hydrogen yield systems.
Preferably, it includes following step that the structural formula, which is the preparation of more two sulphur cluster compounds of carbonyl heteronuclear bimetallic of C2,
Rapid: in methylene chloride, mass ratio is the compound N iN of 1~1.5:12S2Ni-1 and compound Mn (CO)5Br reaction
Close object C2；The compound N iN2S2The structural formula of Ni-1 is
Preferably, it includes following step that the structural formula, which is the preparation of more two sulphur cluster compounds of carbonyl heteronuclear bimetallic of C3,
Rapid: in methylene chloride, mass ratio is the compound N i (dppe) (pdt) and compound Mn (CO) of 0.5~3:15Br reacts
To product C3；The structural formula of the compound N i (dppe) (pdt) is
Preferably, it includes following step that the structural formula, which is the preparation of more two sulphur cluster compounds of carbonyl heteronuclear bimetallic of C4,
Rapid: in methylene chloride, mass ratio is the compound N i (dppe) (pdt) and compound [Ru (CO) of 1~3:12Cl2]nIt reacts
To compound C4；The structural formula of the compound N i (dppe) (pdt) is[the Ru (CO)2Cl2]nMiddle n is
Integer 10~20.
Preferably, it includes following step that the structural formula, which is the preparation of more two sulphur cluster compounds of carbonyl heteronuclear bimetallic of C5,
Rapid: in methylene chloride, mass ratio is the compound N iN of 1~2:12S2Ni-2 and compound [Ru (CO)2Cl2]nReactionization
Close object C5；The compound N iN2S2The structural formula of Ni-2 is[the Ru (CO)2Cl2]nMiddle n is integer 10~20.
Preferably, the structural formula specifically includes as follows for the preparation of more two sulphur cluster compounds of carbonyl heteronuclear bimetallic of C2
Step: to compound N iN2S2Ni-1 isMiddle addition Mn (CO)5System top tank air is replaced into Ar by Br compound；
Methylene chloride is squeezed into as reaction solution, stirs 20~30h；Thin-layer chromatography (TLC) contact plate observation reaction, by product column chromatography side
Method separation, collects first brown band；It is spin-dried for, drains, obtaining the brown solid with metallic luster is product C2；
Preferably, the structural formula specifically includes as follows for the preparation of more two sulphur cluster compounds of carbonyl heteronuclear bimetallic of C3
Step: i.e. to Ni (dppe) (pdt)Middle addition Mn (CO)5System is carried out gas exchanges by Br, after being repeated 3 times,
It is that 20~30h is stirred at room temperature in body that the methylene chloride steamed again, which is added to,；TLC observes system reaction, product is spin-dried for, wet process
It fills column wet process loading and collects second brown band；It is spin-dried for, drains, the dark brown solid for obtaining metallic luster is product C3.
Preferably, the structural formula specifically includes as follows for the preparation of more two sulphur cluster compounds of carbonyl heteronuclear bimetallic of C4
Step: i.e. by compound N i (dppe) (pdt)With [Ru (CO)2Cl2]nTwo kinds of compound mixing, will be in system
Air displacement is Ar, and dry methylene chloride is added, stir 24 hours or more；It is detected and is reacted using TLC, product is spin-dried for, column
Chromatography collects brown band, is spin-dried for draining to obtain dark red-brown solid being compound C4.
Preferably, the structural formula specifically includes as follows for the preparation of more two sulphur cluster compounds of carbonyl heteronuclear bimetallic of C5
Step: to compound N iN2S2Ni-2 isMiddle addition [Ru (CO)2Cl2]n, system top tank air is then replaced into Ar,
Methylene chloride is added as reaction solution, stir 24 hours or more；It is detected and is reacted using TLC, product is separated with column chromatography method,
Collect first brown band；It is spin-dried for draining, obtaining red brown solid is compound C5.
Preferably, concentration≤1 × 10 of more two sulphur cluster compounds of carbonyl heteronuclear bimetallic-3mol/L.More carbonyls
After two sulphur cluster compound of heteronuclear bimetallic reaches saturated concentration in a solvent, more two sulphur of carbonyl heteronuclear bimetallic can be continued growing
The content of cluster compound, only theoretically without economic value.
To reach above-mentioned second purpose, the present invention is adopted the following technical solutions:
It is a kind of to produce hydrogen system preparation using the visible light photocatalysis including more carbonyl heteronuclear bimetallic sulphur cluster compounds
The method of hydrogen includes the following steps: that photocatalysis is irradiated using light source produces hydrogen system, gas spectrum monitoring sample；It is complete in illumination reaction
Cheng Hou, the sample hydrogen output being calculated.
Preferably, the illumination wavelength range of the visible light is 300~800nm.The extinction model of quantum dot in the present invention
It encloses for 300~800nm, therefore required visible light illumination range is 300~800nm.
Preferably, the light source is xenon lamp, high-pressure sodium lamp or LED etc..
Preferably, the light irradiation time of the light source is≤45h.
To reach above-mentioned third purpose, the present invention is adopted the following technical solutions:
A kind of preparation method of more carbonyl heteronuclear bimetallic sulphur cluster compounds, the preparation method include the following steps:
In methylene chloride, compound A and compound B react to obtain more bis- sulphur cluster compounds of carbonyl heteronuclear Ni-Mn or more carbonyl heteronuclear Ni-
Bis- sulphur cluster compound of Ru；
The compound A is
The compound B is Mn (CO)5Br or [Ru (CO)2Cl2]n；[the Ru (CO)2Cl2]nMiddle n is integer 10~20.
Preferably, the structural formula of more bis- sulphur cluster compounds of carbonyl heteronuclear Ni-Mn is as shown in C2 or C3:
Preferably, the structural formula of more bis- sulphur cluster compounds of carbonyl heteronuclear Ni-Ru is as shown in C4 or C5:
In order to expand the photic type for producing hydrogen system of NiFe hydrogenation enzyme mimics, more carbonyl heteronuclear bimetallic sulphur clusters are solved
The difficult problem of object synthesis is closed, the invention proposes a variety of more carbonyl heteronuclear bimetallic sulphur cluster compounds, and propose the chemical combination
The preparation method of object, step is simple, synthesizes more carbonyl heteronuclear bimetallic sulphur cluster compounds.
Preferably, when the structural formula of more bis- sulphur cluster compounds of carbonyl heteronuclear Ni-Mn is C2, the reactant A isThe reactant B is Mn (CO)5Br。
Preferably, when the structural formula of more bis- sulphur cluster compounds of carbonyl heteronuclear Ni-Mn is C3, the reactant A isThe reactant B is Mn (CO)5Br。
Preferably, when the structural formula of more bis- sulphur cluster compounds of carbonyl heteronuclear Ni-Ru is C4, the reactant A isThe reactant B is [Ru (CO)2Cl2]n。
Preferably, when the structural formula of more bis- sulphur cluster compounds of carbonyl heteronuclear Ni-Ru is C5, the reactant A isThe reactant B is [Ru (CO)2Cl2]n。
Difficult, production hydrogen rate is synthesized very to solve more carbonyl heteronuclear bimetallic sulphur cluster compounds as the report of catalytic center
Low problem, the present invention utilizes the good performance of quantum dot extinction property, using quantum dot as photosensitive unit and more carbonyl heteronuclears
Bimetallic forms photic production hydrogen system.In addition, in order to solve previous system because of electronics sacrificial body, catalyst photosensitizer, catalyst
Deng being all organic substance, it is insoluble in water, therefore the problem of solvent is only pure organic reagent, the quantum dot photosensitizer that the present invention uses
It can be dissolved in water, electronics sacrificial body is such as dissolved in water, is then directly added into water phase, if solubility is bad, can add a small amount of organic examination
Agent assists dissolving, therefore the preferred solution of the invention is isopropanol, both water-soluble play the role of electronics sacrificial body.
The present invention realizes catalyst Photocatalyzed Hydrogen Production in the mixed system of water and organic solvent for the first time.Among these organic reagent and
The ratio of water reagent is also influenced on producing hydrogen system efficiency, and comparative experiments is passed through, it has been found that in water/organic reagent is 3/
The production hydrogen system efficiency is best when 1.
How the quantum dot photocatalysis high as photosensitizer and more carbonyl heteronuclear bimetallic centers composition hydrogen generation efficiency to be produced
Hydrogen system, and how to obtain the more carbonyl heteronuclear bimetallic chemical combination of various new that production hydrogen system can be formed with quantum dot photosensitizer
Object is the technical issues of present invention overcomes.In order to overcome the above technical problems, the present invention obtains various new by many experiments
More carbonyl Heteronuclear bimetallic complexes, and the mutual cooperations such as its solvent with quantum dot and containing water are constructed into photic production hydrogen
System achievees the effect that each hydrogen output highest can achieve 478mol in terms of 5mL under the synergistic effect of system each component,
Efficient heteronuclear bimetallic Photocatalyzed Hydrogen Production is finally realized, is the best result reported at present.
In addition, unless otherwise specified, it is raw materials used in the present invention can be by commercially available commercially available, documented by the present invention
Any range includes that any numerical value between end value and end value and any number between end value or end value are constituted
Any subrange.
Beneficial effects of the present invention are as follows:
1) Photocatalyzed Hydrogen Production system of the invention has been introduced into using quantum dot as photosensitizer containing the double gold of more carbonyl heteronuclears
In the Photocatalyzed Hydrogen Production system for belonging to hydrogenation enzyme mimics, Photocatalyzed Hydrogen Production system efficiency and stability are improved, system is reduced
Production cost.
2) it is molten in the mixing of water and organic solvent to realize the NiFe hydrogenation photic production hydrogen system of enzyme mimics for the first time by the present invention
High efficiency photocatalysis in liquid produces hydrogen.
3) the more carbonyl Heteronuclear bimetallic complexes of various new produced by the present invention not only solve the double gold of more carbonyl heteronuclears
Belong to the difficult problem of sulphur cluster compound synthesis, and expanded the photic type for producing hydrogen system of NiFe hydrogenation enzyme mimics, with amount
Son point photosensitizer etc. collectively constitutes a variety of highly effective hydrogen yield systems.
4) Photocatalyzed Hydrogen Production system continuously photocatalytic of the invention shines 34 hours, and each hydrogen output highest can reach in terms of 5mL
To 478mol, 12447 are up to based on the hydrogen conversion number that catalyst calculates.
Detailed description of the invention
Specific embodiments of the present invention will be described in further detail with reference to the accompanying drawing.
Fig. 1 shows the synthetic route chart of compound C1~C5 in the embodiment of the present invention 1~5；
Fig. 2 shows the ESI maps of compound C1 obtained in the embodiment of the present invention 1；
Fig. 3 shows compound C2 obtained in the embodiment of the present invention 21H NMR spectra；
Fig. 4 shows compound C3 obtained in the embodiment of the present invention 31H NMR spectra；
Fig. 5 shows compound C4 obtained in the embodiment of the present invention 41H NMR spectra；
Fig. 6 shows compound C5 obtained in the embodiment of the present invention 51H NMR spectra；
Fig. 7 shows the sample hydrogen output figure of different pH value in the embodiment of the present invention 35~47.
Specific embodiment
In order to illustrate more clearly of the present invention, the present invention is done further below with reference to preferred embodiments and drawings
It is bright.Similar component is indicated in attached drawing with identical appended drawing reference.It will be appreciated by those skilled in the art that institute is specific below
The content of description is illustrative and be not restrictive, and should not be limited the scope of the invention with this.
Light source in the present invention uses one of xenon lamp, high-pressure sodium lamp, LED light source.The hydrogen that illumination generates is composed with gas
It detects (GC-14B Shimadzu), argon gas is used as detector as carrier gas, transcranial Doppler detector (TCD).Sample is mounted in and applies
In Lan Ke (Schlenk) test tube, sample sealing is used nitrogen degasification 30 minutes before illumination, reinjects methane gas 1.0mL as internal standard,
Seal illumination.The amounts of hydrogen generated in monitoring sample is composed with gas, is extracted at regular intervals from test tube upper layer gas phase portion certain
Gas injection gas spectrum detection is measured, H is passed through2And CH4Working curve under the gas spectral condition calculates the hydrogen output of sample；Sample
PH value definite value is adjusted to before illumination by HCl or NaOH.
Embodiment 1
Structural formula be C1 more two sulphur cluster compounds of carbonyl heteronuclear bimetallic synthesis, route as shown in Figure 1, step such as
Under:
Taking structural formula of compound isNi (pdt) (dppe) 1.0g is put into Shi Lanke (Schlenk) bottle,
Take 1.5g compound Fe2(CO)9In the Schlenk bottle of 100mL, the methylene chloride of 30mL is added.It is stirred at room temperature 6 hours.
Above-mentioned solvent is evaporated, the acetonitrile reagent wash residual solid of 40mL is then used, then dissolves residual solid, benefit with methylene chloride
With silica gel column chromatography post separation.Eluant, eluent is methylene chloride.It is recrystallized followed by the n-hexane of 100mL.Obtained solid
Dissolution obtains brown product C1, reference with 0.4mL tetrafluoro boric acid etherate solution is then added in methylene chloride thereto
Document J.Am.Chem.Soc.2010,132, Hydride-containing models for the active site of
the nickel-iron hydrogenases,14877-85.The ESI map of compound C1 is as shown in Figure 2.
Embodiment 2
Structural formula be C2 more two sulphur cluster compounds of carbonyl heteronuclear bimetallic synthesis, route as shown in Figure 1, step such as
Under:
Taking 574mg structural formula isCompound N iN2S2Ni-1 is in Schlenk bottles of 10ml, with thereto
The Mn (CO) of 546mg is added5Br compound.System top tank air is then replaced into Ar.Methylene chloride is squeezed into as reaction solution,
Stirring is for 24 hours.It is observed using thin-layer chromatography (TLC) contact plate, to system fully reacting, is separated using column chromatography method.Solvent makes
With absolute dichloromethane, first brown band is collected.It is spin-dried for sample using Rotary Evaporators, is drained for use followed by oil pump.?
It is product C2 to the brown solid with metallic luster, C2's1H NMR spectra is as shown in Figure 3.
Embodiment 3
Structural formula be C3 more two sulphur cluster compounds of carbonyl heteronuclear bimetallic synthesis, route as shown in Figure 1, step such as
Under:
Taking 200mg structural formula isCompound N i (dppe) (pdt) in Schlenk test tube, then
The Mn (CO) of 100mg is added5Br.System is subjected to gas exchanges using vacuum pipeline, after being repeated 3 times.The dichloromethane that will be steamed again
It is in body that alkane, which is added to,.It is stirred at room temperature 2 hours.TLC observes system response situation.Solvent is methylene chloride.To fully reacting.
System is spin-dried for, wet method dress post wet process loading utilizes methylene chloride: petroleum ether is 1:1 (v:v) as solvent, collects second
A brown band.It is removed system after solvent using Rotary Evaporators in being drained on oil pump.The dark-brown for obtaining metallic luster is solid
Body is product C3, C3's1H NMR spectra is as shown in Figure 4.
Embodiment 4
Structural formula be C4 more two sulphur cluster compounds of carbonyl heteronuclear bimetallic synthesis, route as shown in Figure 1, step such as
Under:
Taking 100mg structural formula isCompound N i (dppe) (pdt) and 40mg [Ru (CO)2Cl2]nTwo kinds
Compound is in Schlenk test tube.Being operated using vacuum line by the air displacement in system is Ar.It is suitable then to being added in system
The methylene chloride of the drying of amount, stirring 24 hours or more.It is detected and is reacted using TLC, to fully reacting, system is steamed using rotation
Hair instrument is spin-dried for, and utilizes the silica gel post separation of 12 × 24cm.Column chromatography for separation is carried out as solvent using absolute dichloromethane.It obtains
First brown band be product.It is spin-dried for draining using oil pump.Obtaining dark red-brown solid is compound C4, C4
's1H NMR spectra is as shown in Figure 5.
Embodiment 5
Structural formula be C5 more two sulphur cluster compounds of carbonyl heteronuclear bimetallic synthesis, route as shown in Figure 1, step such as
Under:
Taking 530mg structural formula isCompound N iN2S2Ni-2 is in Schlenk bottles of 10ml, then to system
Middle [the Ru (CO) that 454mg is added2Cl2]n, system top tank air is then replaced into Ar.Methylene chloride is squeezed into as reaction solution,
Stirring 24 hours or more.It is detected and is reacted using TLC, to system fully reacting, separated using column chromatography method.Solvent uses pure
Methylene chloride collects first brown band.It is spin-dried for sample using Rotary Evaporators, is drained for use followed by oil pump.It obtains
Red brown solid is compound C5, C5's1H NMR spectra is as shown in Figure 6.
Embodiment 6~12
A kind of visible light photocatalysis production hydrogen system, H2-producing capacity of measurement hyaluronic acid (i.e. HA) to Photocatalyzed Hydrogen Production system
Influence, i.e., the concentration of hyaluronic acid in change system, the hydrogen output of counting system, as shown in table 1.
System includes compound C1 made from embodiment 1, and MPA-CdSe quantum dot, volume ratio is the water and isopropanol of 3:1
Mixed solvent, hyaluronic acid (i.e. HA)；
Wherein, the concentration of the compound C1 is 1.00 × 10-5mol/L；
The concentration of the MPA-CdSe quantum dot is (with Cd2+Meter) it is 5.36 × 10-6mol/L；
The size of the MPA-CdSe quantum dot is 2.5nm；
The isopropanol is not only solvent, and as the electronics sacrificial body in system, concentration 4.16mol/L；
The total volume of the Photocatalyzed Hydrogen Production system is 5mL；
The pH value of the Photocatalyzed Hydrogen Production system is 8.
The method for preparing hydrogen using the Photocatalyzed Hydrogen Production system:
Using LED light source radiation of visible light sample, every illumination 2 hours, it is primary that gas spectrum monitors sample；At illumination 10 hours
Afterwards, the sample hydrogen output being calculated is as shown in the table, and sample persistently produced hydrogen in preceding ten hours.
The composition and hydrogen output of the Photocatalyzed Hydrogen Production system of 1 embodiment 6 to 12 of table
Conclusion: the concentration of hyaluronic acid (HA) influences the production hydrogen effect of Photocatalyzed Hydrogen Production system, and experiment shows not add matter
Sub- acid, system still is able to produce hydrogen, but the HA of 0.2mg/mL effect in Photocatalyzed Hydrogen Production system is best.
Embodiment 13-16
A kind of visible light photocatalysis production hydrogen system, shadow of the measurement electronics sacrificial body to the H2-producing capacity of Photocatalyzed Hydrogen Production system
It rings, i.e., method and step the difference is that only the concentration of electronics sacrificial body in change system, the production of counting system with embodiment 8
Hydrogen amount, as shown in table 2.
The composition and hydrogen output of the Photocatalyzed Hydrogen Production system of 2 embodiment 13 to 16 of table
Conclusion: electronics sacrifices bulk concentration (in an experiment, the combined influence that isopropanol is electronics sacrificial body and organic reagent)
The production hydrogen effect of Photocatalyzed Hydrogen Production system is influenced, wherein 4.16mol/L (water/isopropanol is 3/1) effect is best.
Embodiment 17-21 and comparative example 1
A kind of visible light photocatalysis production hydrogen system, measures the concentration of more two sulphur cluster compound C1 of carbonyl heteronuclear bimetallic to light
Catalysis produces the influence of the H2-producing capacity of hydrogen system, i.e. method and step the difference is that only that C1 is urged in change system with embodiment 8
The concentration of agent, the hydrogen output of counting system, as shown in table 3.
The composition and hydrogen output of the Photocatalyzed Hydrogen Production system of 3 embodiment 17 to 21 of table and comparative example 1
Conclusion: C1 catalyst concn influences the production hydrogen effect of Photocatalyzed Hydrogen Production system, wherein efficiency is most in 8 μm of ol/L
It is good.Comparative example 1 the result shows that, when not containing catalyst C1, the effect that system still is able to Photocatalyzed Hydrogen Production but produces hydrogen is big
It is big to reduce.
Embodiment 22-24 and comparative example 2
A kind of visible light photocatalysis production hydrogen system, measures production of the concentration of MPA-CdSe quantum dot to Photocatalyzed Hydrogen Production system
The influence of hydrogen performance, i.e. method and step the difference is that only the dense of MPA-CdSe quantum dot in change system with embodiment 20
Degree, the hydrogen output of counting system, as shown in table 4.
The composition and hydrogen output of the Photocatalyzed Hydrogen Production system of 4 embodiment 22 to 24 of table and comparative example 2
Conclusion: the concentration of MPA-CdSe quantum dot influences the production hydrogen effect of Photocatalyzed Hydrogen Production system, wherein in 8.04 μm of ol/
Efficiency is best when L.Comparative example 2 the result shows that, when in system without quantum dot, Photocatalyzed Hydrogen Production system hydrogen output be 0.
Comparative example 3~5
A kind of visible light photocatalysis produces hydrogen system, measures the type of photosensitizer to the H2-producing capacity of Photocatalyzed Hydrogen Production system
It influences, i.e., method and step the difference is that only the type of photosensitizer in change system, the production hydrogen of counting system with embodiment 23
Amount, as a result as shown in the table:
The composition and hydrogen output of the Photocatalyzed Hydrogen Production system of 5 comparative example 3~5 of table
The result shows that with other photosensitizers, (comparative experiments supplements Ru (bpy)3 2+、Ir(ppy)3With eosin eosin Y tri-
Kind photosensitizer, three kinds are conventional commercial photosensitizer) it compares, quantum dot photosensitizer Photocatalyzed Hydrogen Production effect is best.
Embodiment 25-30 and comparative example 6
A kind of visible light photocatalysis production hydrogen system, measures the production of different light sources and light irradiation time to Photocatalyzed Hydrogen Production system
The influence of hydrogen performance, i.e. method and step the difference is that only light source and light irradiation time in change system with embodiment 23, meter
The hydrogen output of calculation system, as shown in table 5.
The composition and hydrogen output of the Photocatalyzed Hydrogen Production system of 5 embodiment 25 to 30 of table
Conclusion: light source and light irradiation time influence to produce the effect of hydrogen, under identical light irradiation time, when light source led, produce hydrogen effect most
It is good；Under same light source, when light irradiation time is 34h, it is best to produce hydrogen effect.
Comparative example the result shows that under no illumination condition, Photocatalyzed Hydrogen Production system effect is simultaneously bad, illustrates the catalysis
Producing illumination in hydrogen system is essential for system.
Embodiment 31-34 and comparative example 7, comparative example 8
A kind of visible light photocatalysis production hydrogen system, measures different types of catalyst to the production hydrogen of Photocatalyzed Hydrogen Production system
The influence of energy, i.e., the type of catalyst in change system, the hydrogen output of counting system, as shown in table 6.
System includes catalyst, MPA-CdSe quantum dot, and volume ratio is the water of 3:1 and the mixed solvent of isopropanol, transparent
Matter acid (i.e. HA)；
Wherein, the concentration of the catalyst is 1.00 × 10-5mol/L；
The concentration of the MPA-CdSe quantum dot is (with Cd2+Meter) it is 8.0 × 10-6mol/L；
The size of the MPA-CdSe quantum dot is 2.5nm；
The isopropanol is not only solvent, and as the electronics sacrificial body in system, concentration 4.16mol/L；
The concentration of the Bronsted acid is 0.2mg/mL.
The total volume of the Photocatalyzed Hydrogen Production system is 5mL；
The pH value of the Photocatalyzed Hydrogen Production system is 8.
The method for preparing hydrogen using the Photocatalyzed Hydrogen Production system:
Using LED light source radiation of visible light sample, every illumination 2 hours, it is primary that gas spectrum monitors sample；At illumination 10 hours
Afterwards, the sample hydrogen output being calculated is as shown in the table, and sample persistently produced hydrogen in preceding ten hours.
The composition and hydrogen output of the Photocatalyzed Hydrogen Production system of 6 embodiment 31 to 34 of table and comparative example 7~8
Conclusion: different catalysts C2~C5 is tested as catalyst and produces hydrogen system effect, is illustrated a variety of under this condition
More carbonyl heteronuclear bimetallic hydrogenation enzyme mimics can produce hydrogen as catalyst high efficiency photocatalysis.Comparative example the result shows that,
Obviously it is not so good as the effect of more carbonyl heteronuclear bimetallic catalysts using other kinds of catalyst effect.
Embodiment 35-47
A kind of visible light photocatalysis production hydrogen system, shadow of the measurement system pH to the H2-producing capacity of Photocatalyzed Hydrogen Production system
It ringing, i.e. method and step the difference is that only the type of photosensitizer in change system with embodiment 8, the hydrogen output of counting system,
Such as Fig. 7, as a result as shown in the table:
The composition and hydrogen output of the Photocatalyzed Hydrogen Production system of 7 embodiment 35 to 47 of table
Conclusion: under the conditions of testing different pH, the efficiency of Photocatalyzed Hydrogen Production system, the results showed that imitated under the conditions of pH=8
Fruit is best.
Embodiment 48~52
A kind of visible light photocatalysis production hydrogen system, measures production hydrogen of the size to Photocatalyzed Hydrogen Production system of different quantum dots
The influence of energy, i.e., the size of quantum dot in change system, the hydrogen output of counting system, as shown in table 6.
System includes compound C1, MPA-CdSe quantum dot, and volume ratio is the water of 3:1 and the mixed solvent of isopropanol, thoroughly
Bright matter is sour (i.e. HA)；
Wherein, the concentration of the compound C1 is 1.00 × 10-5mol/L；
The concentration of the MPA-CdSe quantum dot is (with Cd2+Meter) it is 8.0 × 10-6mol/L；
The isopropanol is not only solvent, and as the electronics sacrificial body in system, concentration 4.16mol/L；
The concentration of the Bronsted acid is 0.2mg/mL.
The total volume of the Photocatalyzed Hydrogen Production system is 5mL；
The pH value of the Photocatalyzed Hydrogen Production system is 8.
The method for preparing hydrogen using the Photocatalyzed Hydrogen Production system:
Using LED light source radiation of visible light sample, every illumination 2 hours, it is primary that gas spectrum monitors sample；At illumination 10 hours
Afterwards, the sample hydrogen output being calculated is as shown in the table, and sample persistently produced hydrogen in preceding ten hours.
The composition and hydrogen output of the Photocatalyzed Hydrogen Production system of 7 embodiment 48 to 52 of table
Conclusion: efficiency of the various sizes of CdSe quantum dot as photosensitizer Photocatalyzed Hydrogen Production system is tested, is illustrated
Under 2.5nm size, effect is best.
In conjunction with above-mentioned comparative example and embodiment it is found that two sulphur cluster chemical combination of quantum dot and more carbonyl heteronuclear bimetallics in the present invention
The mutual cooperation of object, synergistic effect, enable the production hydrogen effect of system optimal, lack any component, all can cause system that can not produce hydrogen
Or produce the decline of hydrogen effect.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention may be used also on the basis of the above description for those of ordinary skill in the art
To make other variations or changes in different ways, all embodiments can not be exhaustive here, it is all to belong to this hair
The obvious changes or variations that bright technical solution is extended out are still in the scope of protection of the present invention.
Claims (8)
1. a kind of visible light photocatalysis including more carbonyl heteronuclear bimetallic sulphur cluster compounds produces hydrogen system, which is characterized in that packet
Include quantum dot, more two sulphur cluster compounds of carbonyl heteronuclear bimetallic and solvent；
More two sulphur cluster compounds of carbonyl heteronuclear bimetallic are one of C2~C5 structural formula:
2. the visible light photocatalysis according to claim 1 including more carbonyl heteronuclear bimetallic sulphur cluster compounds produces hydrogen body
System, which is characterized in that the solvent is organic solvent and/or water.
3. the visible light photocatalysis according to claim 1 including more carbonyl heteronuclear bimetallic sulphur cluster compounds produces hydrogen body
System, which is characterized in that the quantum dot is the quantum dot containing stabilizer.
4. the visible light photocatalysis according to claim 1 including more carbonyl heteronuclear bimetallic sulphur cluster compounds produces hydrogen body
System, which is characterized in that the quantum dot is selected from CdSe, CdS, CdTe, ZnSe, ZnS, CdSe/ZnS, CdSe/ZnO, CdSe/
One of CdS, CdTe/CdSe, CdS/ZnSe, CdS/ZnTe quantum dot is a variety of.
5. the visible light photocatalysis according to claim 1 including more carbonyl heteronuclear bimetallic sulphur cluster compounds produces hydrogen body
System, which is characterized in that it further includes Bronsted acid that the visible light photocatalysis, which produces hydrogen system,.
6. the visible light photocatalysis according to claim 1 including more carbonyl heteronuclear bimetallic sulphur cluster compounds produces hydrogen body
System, which is characterized in that the pH value range that the visible light photocatalysis produces hydrogen system is 1-14.
7. the visible light photocatalysis including more carbonyl heteronuclear bimetallic sulphur cluster compounds as described in claim 1~6 is any produces
The method that hydrogen system prepares hydrogen, which comprises the steps of: produce hydrogen system, gas spectrum using light source irradiation photocatalysis
Monitor sample；After the completion of illumination reaction, the sample hydrogen output that is calculated.
8. the method according to claim 7 for preparing hydrogen, which is characterized in that the light irradiation time of the light source is≤45h.
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