CN106995469A - A kind of visible light photocatalysis production hydrogen system and its application including many carbonyl heteronuclear bimetallic sulphur cluster compounds - Google Patents
A kind of visible light photocatalysis production hydrogen system and its application including many carbonyl heteronuclear bimetallic sulphur cluster compounds Download PDFInfo
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- 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 System
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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
- B01J31/22—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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- 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
- B01J2531/72—Manganese
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- 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
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- 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
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
Abstract
Hydrogen system, including quantum dot, many sulphur cluster compounds of carbonyl heteronuclear bimetallic two and solvent are produced the invention discloses a kind of visible light photocatalysis including many carbonyl heteronuclear bimetallic sulphur cluster compounds.The Photocatalyzed Hydrogen Production system of the present invention has been incorporated into quantum dot as sensitising agent in the Photocatalyzed Hydrogen Production system for hydrogenating enzyme mimics containing many carbonyl heteronuclear bimetallics, is improved Photocatalyzed Hydrogen Production system efficiency and stability, is reduced the production cost of system.The invention also discloses a kind of preparation method of many carbonyl heteronuclear bimetallic sulphur cluster compounds, in dichloromethane, compound A and compound B reactions obtain many sulphur cluster compounds of carbonyl heteronuclear Ni Mn bis- or many sulphur cluster compounds of carbonyl heteronuclear Ni Ru bis-；The compound A is The compound B is Mn (CO)5Br or [Ru (CO)2Cl2]n.Solve the problem of many carbonyl heteronuclear bimetallic sulphur cluster compound synthesis are difficult.
Description
Technical field
The present invention relates to Photocatalyzed Hydrogen Production technical field.Include many carbonyl heteronuclear bimetallic sulphur more particularly, to one kind
The visible light photocatalysis production hydrogen system of cluster compound and its application.
Background technology
As economic develops rapidly, the mankind are continuously increased to the demand of the energy.Sun energy storage capacity is huge, but dispersiveness,
Intermittent and low density limitation requirement must be translated into the energy that can be stored and utilize.Hydrogen Energy combustion heat height (every thousand
The energy that gram combustion of hydrogen is produced is three times of gasoline), burning generation product is water, with free of contamination feature, is considered as this
Century optimal green energy resource.It is one of optimal storing mode to convert solar energy into Hydrogen Energy.
By photosynthesis of plant in nature, solar energy highly effective is converted into chemical energy on a large scale, 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, and the electronics and proton formed is passed to photosynthetical system I.Some photosynthetic bacteria systems
System I hydrogenase activity center is hydrogen using obtained electronic catalytic proton reduction.Nevertheless, directly extracting and purifying hydrogenation
Enzyme difficulty is very big, 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 hydrogenases), iron iron hydrogenase (FeFe according to enzymatic activity metal center difference
Hydrogenase) and ferronickel hydrogenase (NiFe hydrogenases).Nineteen twenty-nine Reihlen et al. reports the double gold of many carbonyl same core FeFe first
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 centers hydrogenate enzyme mimics, and it is synthesized and structure is reported successively, but until Artero professors in 2006
Using many 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 many
Carbonyl heteronuclear NiFe metal centers hydrogenation enzyme mimics realize 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) sensitising agent, many carbonyl heterometallocenes NiFe are made2Hydrogenation 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 Cheap highly effective heteronuclear bimetallic is developed
Center hydrogenation enzyme mimics Photocatalyzed Hydrogen Production system is extremely urgent.
Accordingly, it is desirable to provide a kind of Cheap highly effective heteronuclear bimetallic center hydrogenates enzyme mimics preparation method and this cheap
The visible light photocatalysis production hydrogen system of efficient heteronuclear bimetallic center hydrogenation enzyme mimics and its application.
The content of the invention
Include the visible ray light of many carbonyl heteronuclear bimetallic sulphur cluster compounds it is an object of the present invention to provide a kind of
Catalysis production hydrogen system.
Second object of the present invention, which is that offer is a kind of, includes the visible ray of many 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 many carbonyl heteronuclear bimetallic sulphur cluster compounds.For
Above-mentioned first purpose is reached, the present invention uses following technical proposals：
A kind of visible light photocatalysis production hydrogen system including many carbonyl heteronuclear bimetallic sulphur cluster compounds, including quantum dot,
Many the sulphur cluster compounds of carbonyl heteronuclear bimetallic two and solvent.The present invention using quantum dot have it is excellent it is visible light-responded, swash more
The characteristics of son generation, light-generated excitons separation and migration, using quantum dot as sensitising agent, with a variety of many carbonyl heteronuclear bimetallic sulphur clusters
Hydrogenate enzyme mimics and build Photocatalyzed Hydrogen Production system, obtain report catalytic efficiency and stability highest Photocatalyzed Hydrogen Production at present
System.The introducing of wherein 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 many sulphur cluster compounds of carbonyl heteronuclear bimetallic two is selected from Ni, Fe, Mn, Ru
One or both of.
Preferably, the heteronuclear bimetallic in many sulphur cluster compounds of carbonyl heteronuclear bimetallic two be Ni-Fe, Ni-Mn or
Ni-Ru；Further, the heteronuclear bimetallic in many sulphur cluster compounds of carbonyl heteronuclear bimetallic two is Ni-Mn or Ni-Ru.
Preferably, the visible light photocatalysis production hydrogen system also includes electronics sacrificial body；Electronics sacrificial body in the present invention
Light activated sensitising agent is given by electron transmission, is that whole catalytic cycle endlessly provides electronics.Electronics sacrifice in the present invention
The addition of body can improve the hydrogen generation efficiency of production hydrogen system.
Preferably, the visible light photocatalysis production hydrogen system also includes proton source.The addition of proton source can in the present invention
Improve the hydrogen generation efficiency of production 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, TGA,(BNAH) and(BIH) one or more in.It is highly preferred that described
Electronics sacrificial body be selected from isopropanol, triethanolamine, ascorbic acid, ethylenediamine tetra-acetic acid (EDTA), mercaptopropionic acid, TGA,(BNAH) and(BIH) one or more in.Further, the electronics sacrificial body is
Isopropanol.
Preferably, concentration≤15mol/L of the electronics sacrificial body.The electronics sacrificial body reaches that saturation is dense in a solvent
After degree, it can continue to increase the content of electronics sacrificial body, simply in theory without economic value.
Preferably, the proton source is selected from hydrochloric acid, acetic acid, formic acid, trifluoroacetic acid, triethylamine hydrochloride, triethylamine tetrafluoro
One or more in borate, triethanolamine tetrafluoroborate, isopropanol, methanol, trifluoroethanol, phenol and benzoic acid；More
Preferably, the proton source is selected from hydrochloric acid, acetic acid, formic acid, trifluoroacetic acid, triethylamine hydrochloride, isopropanol, methanol, trifluoro second
One or more in alcohol, phenol and benzoic acid.
Preferably, concentration≤1mol/L of the proton source.The proton source reached after saturated concentration in a solvent, can be with
Continue to increase the content of proton source, simply in theory without economic value.
Preferably, the visible light photocatalysis production hydrogen system also includes Bronsted acid.The present invention is by adding matter into system
Sub- acid stablizes Photocatalyzed Hydrogen Production system.
Preferably, the Bronsted acid be polymer, preferably carbohydrate, biological polypeptide, PEI PEI, chitosan and
One or more in hyaluronic acid；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, the Bronsted acid reached after saturated concentration in a solvent, can
To continue the content for increasing Bronsted acid, simply in theory without economic value.
Preferably, the solvent is organic solvent and/or water.Quantum dot is a kind of good water-soluble 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 added in system is also miscible with water, and hyaluronic acid macromolecule can also aid in these components to dissolve, therefore this hair
Solvent in bright is organic solvent and/or water.In addition, the present invention enters one by adjusting the ratio of organic solvent and water in solvent
Step improves hydrogen generation efficiency.
Preferably, the volume ratio of organic solvent and water is 0~1 in the solvent:1；Further, in certain of the invention
In a little 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 has influenceed on production hydrogen system efficiency in the present invention,
Confirmed by contrast experiment, in organic reagent：The volume ratio of water is 1:The production hydrogen system efficiency is optimal when 3.
Preferably, the organic solvent is selected from acetonitrile, DMF, DMA, tetrahydrochysene furan
Mutter, the one or more in ethanol, methanol, isopropanol and acetone；Organic solvent in the present invention can be with water arbitrary proportion
Dissolve 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 or more in formamide, DMA, tetrahydrofuran, ethanol, methanol, isopropanol and acetone.Further
Ground, the organic solvent is isopropanol.
Preferably, the pH value range of the visible light photocatalysis production hydrogen system is 1-14.PH value is not only in system of the present invention
The concentration of Photocatalyzed Hydrogen Production system inner proton is determined, and is that pH can influence the part on sensitising agent surface on sensitising agent effect,
Such as surface ligand easily comes off at low ph values, makes sensitising agent unstable；In the pH value range of the present invention, system can be stablized
Produce hydrogen；Further, in some embodiments of the present invention, for example, the visible light photocatalysis produces the pH of hydrogen system
It 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. to be worth scope.Enter
One step, the pH value range of the visible light photocatalysis production 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 of the visible light photocatalysis production hydrogen system is 7~9, more preferably pH value is 8.
Preferably, the quantum dot is the quantum dot containing stabilizer, and the stabilizer is that MPA is mercaptopropionic acid, due to
Quantum dot size in the present invention is small, and surface can be high, easily reunites.Stabilizer can stablize quantum dot surface, increase it and disperse
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 or more in CdS, CdTe/CdSe, CdS/ZnSe, CdS/ZnTe quantum dot；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 or more in point.
Preferably, the size range of the quantum dot is 1.5~10.0nm.Further, in some specific of the present invention
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
Scope 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
Scope 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, it can continue to increase the content of quantum dot, simply economic value no in theory, therefore the it is highly preferred that amount
The concentration of son point is 1 × 10-7~1 × 10-3mol/L.Further, in some embodiments of the present 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, the one kind of many sulphur cluster compounds of carbonyl heteronuclear bimetallic two in C1~C5 structural formulas：
.Further, the one kind of many sulphur cluster compounds of carbonyl heteronuclear bimetallic two in C2~C5 structural formulas.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 simulations
Object light causes the species of production hydrogen system, solves the problem of many carbonyl heteronuclear bimetallic sulphur cluster compound synthesis are difficult, the present invention is proposed
A variety of many carbonyl heteronuclear bimetallic sulphur cluster compounds, and the preparation method of the compound is proposed, step is simple, and synthesis is obtained
A variety of and quantum dot sensitising agent etc. collectively constitutes many carbonyl heteronuclear bimetallic sulphur cluster compounds of a variety of highly effective hydrogen yield systems.
Preferably, the structural formula includes following step for the preparation of C2 many sulphur cluster compounds of carbonyl heteronuclear bimetallic two
Suddenly：In dichloromethane, mass ratio is 1~1.5：1 compound N iN2S2Ni-1 and compound Mn (CO)5Br reactionizations
Compound C2；The compound N iN2S2Ni-1 structural formula is
Preferably, the structural formula includes following step for the preparation of C3 many sulphur cluster compounds of carbonyl heteronuclear bimetallic two
Suddenly：In dichloromethane, mass ratio is 0.5~3：1 compound N i (dppe) (pdt) and compound Mn (CO)5Br reacts
To product C3；The structural formula of the compound N i (dppe) (pdt) is
Preferably, the structural formula includes following step for the preparation of C4 many sulphur cluster compounds of carbonyl heteronuclear bimetallic two
Suddenly：In dichloromethane, mass ratio is 1~3：1 compound N i (dppe) (pdt) and compound [Ru (CO)2Cl2]nReact
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, the structural formula includes following step for the preparation of C5 many sulphur cluster compounds of carbonyl heteronuclear bimetallic two
Suddenly：In dichloromethane, mass ratio is 1~2：1 compound N iN2S2Ni-2 and compound [Ru (CO)2Cl2]nReactionization
Compound C5；The compound N iN2S2Ni-2 structural formula is[the Ru (CO)2Cl2]nMiddle n is integer 10~20.
Preferably, the structural formula specifically includes as follows for the preparation of C2 many sulphur cluster compounds of carbonyl heteronuclear bimetallic two
Step：To compound N iN2S2Ni-1 isMiddle addition Mn (CO)5Br compounds, Ar is replaced into by system top tank air；
Dichloromethane is squeezed into as reaction solution, 20~30h is stirred；Thin-layer chromatography (TLC) point plate observation reaction, by product column chromatography side
Method is separated, and collects first brown band；It is spin-dried for, drains, it is product C2 to obtain the brown solid with metallic luster；
Preferably, the structural formula specifically includes as follows for the preparation of C3 many sulphur cluster compounds of carbonyl heteronuclear bimetallic two
Step：It is to Ni (dppe) (pdt)Middle addition Mn (CO)5Br, gas exchanges are carried out by system, after being repeated 3 times,
The dichloromethane steamed again is added in being body, 20~30h is stirred at room temperature；TLC observation system reactions, product are spin-dried for, wet method
Fill post wet method loading and collect 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 C4 many sulphur cluster compounds of carbonyl heteronuclear bimetallic two
Step：It is by compound N i (dppe) (pdt)With [Ru (CO)2Cl2]nTwo kinds of compound mixing, by system
Air is replaced into Ar, adds dry dichloromethane, stirs more than 24 hours；Detected and reacted using TLC, product is spin-dried for, post
Chromatography, collects brown band, is spin-dried for draining that to obtain dark red-brown solid be compound C4.
Preferably, the structural formula specifically includes as follows for the preparation of C5 many sulphur cluster compounds of carbonyl heteronuclear bimetallic two
Step：To compound N iN2S2Ni-2 isMiddle addition [Ru (CO)2Cl2]n, system top tank air is then replaced into Ar,
Dichloromethane is added as reaction solution, is stirred more than 24 hours；Detected and reacted using TLC, product is separated with column chromatography method,
Collect first brown band；It is spin-dried for draining, it is compound C5 to obtain red brown solid.
Preferably, concentration≤1 × 10 of many sulphur cluster compounds of carbonyl heteronuclear bimetallic two-3mol/L.Many carbonyls
The sulphur cluster compound of heteronuclear bimetallic two is reached after saturated concentration in a solvent, can continue to increase many sulphur of carbonyl heteronuclear bimetallic two
The content of cluster compound, simply in theory without economic value.
To reach above-mentioned second purpose, the present invention uses following technical proposals：
It is a kind of to be prepared using the visible light photocatalysis production hydrogen system including many carbonyl heteronuclear bimetallic sulphur cluster compounds
The method of hydrogen, comprises the following steps：Use light source irradiation photocatalysis production hydrogen system, gas spectrum monitoring sample；It is complete in illumination reaction
Cheng Hou, calculates obtained sample hydrogen output.
Preferably, the illumination wavelength scope of the visible ray is 300~800nm.The extinction model of quantum dot in the present invention
Enclose for 300~800nm, therefore required visible ray 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 3rd purpose, the present invention uses following technical proposals：
A kind of preparation method of many carbonyl heteronuclear bimetallic sulphur cluster compounds, the preparation method comprises the following steps：
In dichloromethane, compound A and compound B reactions obtain many sulphur cluster compounds of carbonyl heteronuclear Ni-Mn bis- or many carbonyl heteronuclear Ni-
The sulphur cluster compounds of Ru bis-；
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 many sulphur cluster compounds of carbonyl heteronuclear Ni-Mn bis- is as shown in C2 or C3：
Preferably, the structural formula of many sulphur cluster compounds of carbonyl heteronuclear Ni-Ru bis- is as shown in C4 or C5：
In order to expand the species of the photic production hydrogen system of NiFe hydrogenation enzyme mimics, many carbonyl heteronuclear bimetallic sulphur clusters are solved
The problem of compound synthesis is difficult, the present invention proposes a variety of many carbonyl heteronuclear bimetallic sulphur cluster compounds, and proposes the chemical combination
The preparation method of thing, step is simple, synthesizes many carbonyl heteronuclear bimetallic sulphur cluster compounds.
Preferably, when the structural formula of many sulphur cluster compounds of carbonyl heteronuclear Ni-Mn bis- is C2, the reactant A isThe reactant B is Mn (CO)5Br。
Preferably, when the structural formula of many sulphur cluster compounds of carbonyl heteronuclear Ni-Mn bis- is C3, the reactant A isThe reactant B is Mn (CO)5Br。
Preferably, when the structural formula of many sulphur cluster compounds of carbonyl heteronuclear Ni-Ru bis- is C4, the reactant A isThe reactant B is [Ru (CO)2Cl2]n。
Preferably, when the structural formula of many sulphur cluster compounds of carbonyl heteronuclear Ni-Ru bis- is C5, the reactant A isThe reactant B is [Ru (CO)2Cl2]n。
In order to solve many carbonyl heteronuclear bimetallic sulphur cluster compounds difficult, production hydrogen rate is synthesized as the report of catalytic center very
Low the problem of, the present invention regard quantum dot as photosensitive unit and many carbonyl heteronuclears using the good performance of quantum dot extinction property
Bimetallic constitutes photic production hydrogen system.In addition, in order to solve conventional system because of electronics sacrificial body, catalyst sensitising agent, catalyst
Deng being all organic substance, water is insoluble in, therefore solvent is the problem of be only pure organic reagent, the quantum dot sensitising agent that the present invention is used
Water can be dissolved in, electronics sacrificial body is such as dissolved in water, is then directly added into aqueous phase, if solubility is bad, a small amount of organic examination can be added
Agent come aid in dissolving, therefore preferred scheme of the present invention be isopropanol, its both water-soluble effect that may also function as electronics sacrificial body.
The present invention realizes catalyst Photocatalyzed Hydrogen Production in the mixed system of water and organic solvent first.Among these organic reagent and
The ratio of water reagent has also influenceed on production hydrogen system efficiency, passes through contrast experiment, it has been found that in water/organic reagent be 3/
The production hydrogen system efficiency is optimal when 1.
How quantum dot is constituted into the high photocatalysis of hydrogen generation efficiency as sensitising agent and many carbonyl heteronuclear bimetallic centers to produce
Hydrogen system, and how to obtain can with quantum dot sensitising agent constitute production hydrogen system many carbonyl heteronuclear bimetallic chemical combination of various new
Thing is the technical problem that the present invention overcomes.In order to overcome above-mentioned technical problem, the present invention obtains various new by many experiments
Many carbonyl Heteronuclear bimetallic complexes, and the mutual cooperation such as its solvent with quantum dot and containing water is constructed into photic production hydrogen
System, under the synergy of system each component, reaches that each hydrogen output highest can reach 478mol effect in terms of 5mL,
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, described in the present invention
What any number that any scope includes between any numerical value and end value or end value between end value and end value was constituted
Any subrange.
Beneficial effects of the present invention are as follows：
1) Photocatalyzed Hydrogen Production system of the invention has been incorporated into containing the double gold of many carbonyl heteronuclears using quantum dot as sensitising agent
In the Photocatalyzed Hydrogen Production system of category hydrogenation enzyme mimics, Photocatalyzed Hydrogen Production system efficiency and stability are improved, system is reduced
Production cost.
2) present invention realize first NiFe hydrogenation enzyme mimics it is photic production hydrogen system it is molten in the mixing of water and organic solvent
High efficiency photocatalysis production hydrogen in liquid.
3) many carbonyl Heteronuclear bimetallic complexes of various new produced by the present invention, not only solve the double gold of many carbonyl heteronuclears
Belong to the problem of synthesis of sulphur cluster compound is difficult, and expanded the species of the photic production hydrogen system of NiFe hydrogenation enzyme mimics, with amount
Son point sensitising agent 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 is calculated.
Brief description of the drawings
The embodiment to the present invention is described in further detail below in conjunction with the accompanying drawings.
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 collection of illustrative plates of obtained compound C1 in the embodiment of the present invention 1；
Fig. 3 shows obtained compound C2 in the embodiment of the present invention 21H NMR spectras；
Fig. 4 shows obtained compound C3 in the embodiment of the present invention 31H NMR spectras；
Fig. 5 shows obtained compound C4 in the embodiment of the present invention 41H NMR spectras；
Fig. 6 shows obtained compound C5 in the embodiment of the present invention 51H NMR spectras；
Fig. 7 shows the sample hydrogen output figure of different pH value in the embodiment of the present invention 35~47.
Embodiment
In order to illustrate more clearly of the present invention, the present invention is done further with reference to preferred embodiments and drawings
It is bright.Similar part is indicated with identical reference in accompanying drawing.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 kind in xenon lamp, high-pressure sodium lamp, LED/light source.The hydrogen that illumination is produced is composed with gas
Detect (GC-14B Shimadzu), argon gas is used as detector as carrier gas, transcranial Doppler detector (TCD).Sample is mounted in and applied
In Lan Ke (Schlenk) test tube, sample sealing nitrogen degasification 30 minutes, reinjects methane gas 1.0mL as internal standard before illumination,
Seal illumination.The amounts of hydrogen generated in monitoring sample is composed with gas, is extracted at regular intervals from test tube upper strata gas phase portion certain
Gas injection gas spectrum detection is measured, passes through H2And CH4Working curve under the gas spectral condition calculates the hydrogen output of sample；Sample
PH value adjusted by HCl or NaOH before illumination to definite value.
Embodiment 1
Structural formula for C1 many sulphur cluster compounds of carbonyl heteronuclear bimetallic two 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 compounds Fe2(CO)9In 100mL Schlenk bottles, 30mL dichloromethane is added.It is stirred at room temperature 6 hours.
Above-mentioned solvent is evaporated, then with 40mL acetonitrile reagent wash residual solid, then residual solid, profit is dissolved with dichloromethane
Use silica gel column chromatography post separation.Eluant, eluent is dichloromethane.Recrystallized followed by 100mL n-hexane.Obtained solid
Dissolving obtains brown product C1, reference with then adding 0.4mL tetrafluoro boric acid etherate solution in dichloromethane thereto
Document J.Am.Chem.Soc.2010,132, Hydride-containing models for the active site of
the nickel-iron hydrogenases,14877-85.Compound C1 ESI collection of illustrative plates is as shown in Figure 2.
Embodiment 2
Structural formula for C2 many sulphur cluster compounds of carbonyl heteronuclear bimetallic two synthesis, route as shown in figure 1, step such as
Under：
Taking 574mg structural formulas isCompound N iN2S2Ni-1 is in Schlenk bottles of 10ml, with thereto
Add 546mg Mn (CO)5Br compounds.System top tank air is then replaced into Ar.Dichloromethane is squeezed into as reaction solution,
Stir 24h.Observed using thin-layer chromatography (TLC) point plate, treat that system reaction is complete, separated using column chromatography method.Solvent makes
With absolute dichloromethane, first brown band is collected.Sample is spin-dried for using Rotary Evaporators, is drained followed by oil pump stand-by.
It is product C2 to the brown solid with metallic luster, C2's1H NMR spectras are as shown in Figure 3.
Embodiment 3
Structural formula for C3 many sulphur cluster compounds of carbonyl heteronuclear bimetallic two synthesis, route as shown in figure 1, step such as
Under：
Taking 200mg structural formulas isCompound N i (dppe) (pdt) in Schlenk test tubes, then
Add 100mg Mn (CO)5Br.System is subjected to gas exchanges using vacuum pipeline, after being repeated 3 times.By the dichloromethane steamed again
Alkane, which is added to, is body.It is stirred at room temperature 2 hours.TLC observes system response situation.Solvent is dichloromethane.Question response is complete.
System is spin-dried for, wet method dress post wet method loading utilizes dichloromethane：Petroleum ether is 1：1(v:V) as solvent, second is collected
Individual brown band.Removed system using Rotary Evaporators after solvent in being drained on oil pump.The dark-brown for obtaining metallic luster is consolidated
Body is product C3, C3's1H NMR spectras are as shown in Figure 4.
Embodiment 4
Structural formula for C4 many sulphur cluster compounds of carbonyl heteronuclear bimetallic two synthesis, route as shown in figure 1, step such as
Under：
Taking 100mg structural formulas isCompound N i (dppe) (pdt) and 40mg [Ru (CO)2Cl2]nTwo kinds
Compound is in Schlenk test tubes.The air in system is replaced into Ar using vacuum line operation.It is suitable then to being added in system
The dichloromethane of the drying of amount, is stirred more than 24 hours.Detected and reacted using TLC, completely, system is steamed using rotation for question response
Hair instrument is spin-dried for, and utilizes 12 × 24cm silica gel post separation.Using absolute dichloromethane column chromatography for separation is carried out as solvent.Obtain
The band of first brown be product.It is spin-dried for draining using oil pump.Dark red-brown solid is obtained for compound C4, C4
's1H NMR spectras are as shown in Figure 5.
Embodiment 5
Structural formula for C5 many sulphur cluster compounds of carbonyl heteronuclear bimetallic two synthesis, route as shown in figure 1, step such as
Under：
Taking 530mg structural formulas isCompound N iN2S2Ni-2 is in Schlenk bottles of 10ml, then to system
Middle addition 454mg [Ru (CO)2Cl2]n, system top tank air is then replaced into Ar.Dichloromethane is squeezed into as reaction solution,
Stirring more than 24 hours.Detected and reacted using TLC, treated that system reaction is complete, separated using column chromatography method.Solvent uses pure
Dichloromethane, collects first brown band.Sample is spin-dried for using Rotary Evaporators, is drained followed by oil pump stand-by.Obtain
Red brown solid is compound C5, C5's1H NMR spectras are as shown in Figure 6.
Embodiment 6~12
A kind of visible light photocatalysis produces hydrogen system, determines hyaluronic acid (i.e. HA) to the H2-producing capacity of 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 dots, volume ratio is 3：1 water and isopropanol
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 dots is (with Cd2+Gauge) it is 5.36 × 10-6mol/L；
The size of the MPA-CdSe quantum dots is 2.5nm；
The isopropanol is not only solvent, and as the electronics sacrificial body in system, its concentration is 4.16mol/L；
The cumulative 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, per illumination 2 hours, gas spectrum monitoring sample was once；In illumination 10 hours
Afterwards, the sample hydrogen output that calculating is obtained 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 the embodiment 6 to 12 of table 1
Conclusion：The concentration of hyaluronic acid (HA) influences the production hydrogen effect of Photocatalyzed Hydrogen Production system, and experiment shows without matter
Sub- acid, system remains able to produce hydrogen, but 0.2mg/mL HA effects in Photocatalyzed Hydrogen Production system are best.
Embodiment 13-16
A kind of visible light photocatalysis produces hydrogen system, determines shadow of the electronics sacrificial body to the H2-producing capacity of Photocatalyzed Hydrogen Production system
Ring, i.e. method and step be the same as Example 8, the difference is that only the concentration of electronics sacrificial body in change system, the production of counting system
Hydrogen amount, as shown in table 2.
The composition and hydrogen output of the Photocatalyzed Hydrogen Production system of the embodiment 13 to 16 of table 2
Conclusion：Electronics sacrifice bulk concentration (in an experiment, isopropanol be electronics sacrificial body and organic reagent combined influence)
The production hydrogen effect of Photocatalyzed Hydrogen Production system is influenceed, 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 produces hydrogen system, determines many sulphur cluster compound C1 of carbonyl heteronuclear bimetallic two concentration to light
The influence of the H2-producing capacity of catalysis production hydrogen system, i.e. method and step be the same as Example 8, the difference is that only that C1 is urged in change system
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 the embodiment 17 to 21 of table 3 and comparative example 1
Conclusion：C1 catalyst concns influence the production hydrogen effect of Photocatalyzed Hydrogen Production system, wherein efficiency is most in 8 μm of ol/L
It is good.The result of comparative example 1 shows, when not containing catalyst C1, and the effect that system remains able to Photocatalyzed Hydrogen Production but produces hydrogen is big
Big reduction.
Embodiment 22-24 and comparative example 2
A kind of visible light photocatalysis produces hydrogen system, determines production of the concentration of MPA-CdSe quantum dots to Photocatalyzed Hydrogen Production system
The influence of hydrogen performance, i.e. method and step be the same as Example 20, the difference is that only the dense of MPA-CdSe quantum dots in change system
Degree, the hydrogen output of counting system, as shown in table 4.
The composition and hydrogen output of the Photocatalyzed Hydrogen Production system of the embodiment 22 to 24 of table 4 and comparative example 2
Conclusion：The concentration of MPA-CdSe quantum dots influences the production hydrogen effect of Photocatalyzed Hydrogen Production system, wherein in 8.04 μm of ol/
Efficiency is best during L.The result of comparative example 2 shows, when in system without quantum dot, and Photocatalyzed Hydrogen Production system hydrogen output is 0.
Comparative example 3~5
A kind of visible light photocatalysis produces hydrogen system, determines the species of sensitising agent to the H2-producing capacity of Photocatalyzed Hydrogen Production system
Influence, i.e. method and step be the same as Example 23, the difference is that only the species of sensitising agent in change system, the production hydrogen of counting system
Amount, it is as a result as shown in the table：
The composition and hydrogen output of the Photocatalyzed Hydrogen Production system of the comparative example 3~5 of table 5
As a result show, (contrast experiment supplements Ru (bpy) with other sensitising agents3 2+、Ir(ppy)3With eosin eosin Y tri-
Sensitising agent is planted, three kinds are conventional commercial sensitising agent) to compare, quantum dot sensitising agent Photocatalyzed Hydrogen Production effect is best.
Embodiment 25-30 and comparative example 6
A kind of visible light photocatalysis produces hydrogen system, determines 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 be the same as Example 23, the difference is that only light source and light irradiation time in change system, meter
The hydrogen output of calculation system, as shown in table 5.
The composition and hydrogen output of the Photocatalyzed Hydrogen Production system of the embodiment 25 to 30 of table 5
Conclusion：Under the effect of light source and light irradiation time influence production hydrogen, identical light irradiation time, during light source led, production hydrogen effect is most
It is good；Under same light source, when light irradiation time is 34h, production hydrogen effect is best.
The result of comparative example shows that under no illumination condition Photocatalyzed Hydrogen Production system effect is simultaneously bad, illustrates the catalysis
It is essential for system to produce illumination in hydrogen system.
Embodiment 31-34 and comparative example 7, comparative example 8
A kind of visible light photocatalysis produces hydrogen system, determines production hydrogen of different types of catalyst to Photocatalyzed Hydrogen Production system
The influence of energy, i.e., the species of catalyst in change system, the hydrogen output of counting system, as shown in table 6.
System includes catalyst, and MPA-CdSe quantum dots, volume ratio is 3：1 water and the mixed solvent of isopropanol are 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 dots is (with Cd2+Gauge) it is 8.0 × 10-6mol/L；
The size of the MPA-CdSe quantum dots is 2.5nm；
The isopropanol is not only solvent, and as the electronics sacrificial body in system, its concentration is 4.16mol/L；
The concentration of the Bronsted acid is 0.2mg/mL.
The cumulative 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, per illumination 2 hours, gas spectrum monitoring sample was once；In illumination 10 hours
Afterwards, the sample hydrogen output that calculating is obtained 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 the embodiment 31 to 34 of table 6 and comparative example 7~8
Conclusion：Different catalysts C2~C5 is tested as catalyst and produces hydrogen system effect, illustrates a variety of under this condition
Many carbonyl heteronuclear bimetallic hydrogenation enzyme mimics can produce hydrogen as catalyst high efficiency photocatalysis.The result of comparative example shows,
Substantially it is not so good as the effect of many carbonyl heteronuclear bimetallic catalysts using other kinds of catalyst effect.
Embodiment 35-47
A kind of visible light photocatalysis produces hydrogen system, determines shadow of the system pH to the H2-producing capacity of Photocatalyzed Hydrogen Production system
Ring, i.e. method and step be the same as Example 8, the difference is that only the species of sensitising agent in change system, 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 the embodiment 35 to 47 of table 7
Conclusion：Test under the conditions of different pH, as a result the efficiency of Photocatalyzed Hydrogen Production system show effect under the conditions of pH=8
It is really best.
Embodiment 48~52
A kind of visible light photocatalysis produces hydrogen system, determines 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 3：1 water 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 dots is (with Cd2+Gauge) it is 8.0 × 10-6mol/L；
The isopropanol is not only solvent, and as the electronics sacrificial body in system, its concentration is 4.16mol/L；
The concentration of the Bronsted acid is 0.2mg/mL.
The cumulative 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, per illumination 2 hours, gas spectrum monitoring sample was once；In illumination 10 hours
Afterwards, the sample hydrogen output that calculating is obtained 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 the embodiment 48 to 52 of table 7
Conclusion：Various sizes of CdSe quantum dot is tested as the efficiency of sensitising agent Photocatalyzed Hydrogen Production system, is illustrated
Under 2.5nm sizes, effect is best.
Understood with reference to above-mentioned comparative example and embodiment, quantum dot and the sulphur cluster chemical combination of many carbonyl heteronuclear bimetallics two in the present invention
The mutual cooperation of thing, synergy, make the production hydrogen effect of system optimal, lack any component, all system can be caused can not to produce hydrogen
Or production hydrogen effect declines.
Obviously, the above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not pair
The restriction of embodiments of the present invention, for those of ordinary skill in the field, may be used also on the basis of the above description
To make other changes in different forms, all embodiments can not be exhaustive here, it is every to belong to this hair
Row of the obvious changes or variations that bright technical scheme is extended out still in protection scope of the present invention.
Claims (14)
1. a kind of visible light photocatalysis production hydrogen system including many carbonyl heteronuclear bimetallic sulphur cluster compounds, it is characterised in that bag
Include quantum dot, many sulphur cluster compounds of carbonyl heteronuclear bimetallic two and solvent.
2. the visible light photocatalysis production hydrogen body according to claim 1 including many carbonyl heteronuclear bimetallic sulphur cluster compounds
System, it is characterised in that the heteronuclear bimetallic in many sulphur cluster compounds of carbonyl heteronuclear bimetallic two is in Ni, Fe, Mn, Ru
One or two.
3. the visible light photocatalysis production hydrogen body according to claim 1 including many carbonyl heteronuclear bimetallic sulphur cluster compounds
System, it is characterised in that heteronuclear bimetallic in many sulphur cluster compounds of carbonyl heteronuclear bimetallic two for Ni-Fe, Ni-Mn or
Ni-Ru。
4. the visible light photocatalysis production hydrogen body according to claim 1 including many carbonyl heteronuclear bimetallic sulphur cluster compounds
System, it is characterised in that the solvent is organic solvent and/or water.
5. the visible light photocatalysis production hydrogen body according to claim 1 including many carbonyl heteronuclear bimetallic sulphur cluster compounds
System, it is characterised in that the quantum dot is the quantum dot containing stabilizer.
6. the visible light photocatalysis production hydrogen body according to claim 1 including many carbonyl heteronuclear bimetallic sulphur cluster compounds
System, it is characterised in that the quantum dot is selected from CdSe, CdS, CdTe, ZnSe, ZnS, CdSe/ZnS, CdSe/ZnO, CdSe/
One or more in CdS, CdTe/CdSe, CdS/ZnSe, CdS/ZnTe quantum dot.
7. the visible light photocatalysis production hydrogen body according to claim 1 including many carbonyl heteronuclear bimetallic sulphur cluster compounds
System, it is characterised in that the visible light photocatalysis production hydrogen system also includes Bronsted acid.
8. the visible light photocatalysis production hydrogen body according to claim 1 including many carbonyl heteronuclear bimetallic sulphur cluster compounds
System, it is characterised in that many sulphur cluster compounds of carbonyl heteronuclear bimetallic two are one kind in C1~C5 structural formulas：
9. the visible light photocatalysis production hydrogen body according to claim 8 including many carbonyl heteronuclear bimetallic sulphur cluster compounds
System, it is characterised in that the structural formula includes as follows for the preparation of C2~C5 many sulphur cluster compounds of carbonyl heteronuclear bimetallic two
Step：
The structural formula comprises the following steps for the preparation of C2 many sulphur cluster compounds of carbonyl heteronuclear bimetallic two：In dichloromethane
In, mass ratio is 1~1.5：1 compound N iN2S2Ni-1 and compound Mn (CO)5Br reactions obtain compound C2；Describedization
Compound NiN2S2Ni-1 structural formula is
The structural formula comprises the following steps for the preparation of C3 many sulphur cluster compounds of carbonyl heteronuclear bimetallic two：In dichloromethane
In, mass ratio is 0.5~3：1 compound N i (dppe) (pdt) and compound Mn (CO)5Br reactions obtain product C3；It is described
Compound N i (dppe) (pdt) structural formula is
The structural formula comprises the following steps for the preparation of C4 many sulphur cluster compounds of carbonyl heteronuclear bimetallic two：In dichloromethane
In, mass ratio is 1~3：1 compound N i (dppe) (pdt) and compound [Ru (CO)2Cl2]nReaction obtains compound C4；Institute
The structural formula for stating compound N i (dppe) (pdt) is[the Ru (CO)2Cl2]nMiddle n is integer 10~20；
The structural formula comprises the following steps for the preparation of C5 many sulphur cluster compounds of carbonyl heteronuclear bimetallic two：In dichloromethane
In, mass ratio is 1~2：1 compound N iN2S2Ni-2 and compound [Ru (CO)2Cl2]nReaction obtains compound C5；Describedization
Compound NiN2S2Ni-2 structural formula is[the Ru (CO)2Cl2]nMiddle n is integer 10~20.
10. the visible light photocatalysis production hydrogen body according to claim 1 including many carbonyl heteronuclear bimetallic sulphur cluster compounds
System, it is characterised in that the pH value range of the visible light photocatalysis production hydrogen system is 1-14.
11. include the visible light photocatalysis of many carbonyl heteronuclear bimetallic sulphur cluster compounds as described in claim 1~10 is any
The method that production hydrogen system prepares hydrogen, it is characterised in that comprise the following steps：Use light source irradiation photocatalysis production hydrogen system, gas
Spectrum monitoring sample；After the completion of illumination reaction, obtained sample hydrogen output is calculated.
12. the method according to claim 11 for preparing hydrogen, it is characterised in that the light irradiation time of the light source for≤
45h。
13. a kind of preparation method of many carbonyl heteronuclear bimetallic sulphur cluster compounds, it is characterised in that the preparation method is included such as
Lower step：
In dichloromethane, compound A and compound B reactions obtain many sulphur cluster compounds of carbonyl heteronuclear Ni-Mn bis- or many carbonyls
The sulphur cluster compounds of heteronuclear Ni-Ru bis-；
The compound A is
The compound B is Mn (CO)5Br or [Ru (CO)2Cl2]n。
14. the preparation method of many carbonyl heteronuclear bimetallic sulphur cluster compounds as claimed in claim 13, it is characterised in that described
Obtained many sulphur cluster compounds of carbonyl heteronuclear Ni-Mn bis- or many sulphur cluster compounds of carbonyl heteronuclear Ni-Ru bis- have following structural formula：
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