CN105772085B - (S) the thiourea modified Cr Anderson types heteropolyacid catalyst of 1 (1 ethoxy, 1 isopropyl), preparation method and applications - Google Patents
(S) the thiourea modified Cr Anderson types heteropolyacid catalyst of 1 (1 ethoxy, 1 isopropyl), preparation method and applications Download PDFInfo
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- CN105772085B CN105772085B CN201610211227.XA CN201610211227A CN105772085B CN 105772085 B CN105772085 B CN 105772085B CN 201610211227 A CN201610211227 A CN 201610211227A CN 105772085 B CN105772085 B CN 105772085B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
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Abstract
The invention discloses a kind of (S) 1 (1 ethoxy, 1 isopropyl) thiourea modified Cr Anderson types heteropolyacid catalyst, preparation method and applications.The present invention is first by ammonium molybdate and chromic nitrate reaction generation Cr Anderson type heteropoly acids (NH4)3[Cr(OH)6Mo6O18], then itself and trihydroxy aminomethane hydro-thermal reaction are obtained into the amido modified polyoxometallate in organic one side；Then using L valerian ammonia alcohols as Material synthesis (S) 1 (1 ethoxy, 1 isopropyl) isothiocyanic acid；(S) 1 (1 ethoxy, 1 isopropyl) isothiocyanic acid and the amido modified polyoxometallic acid reactant salt in organic one side are finally obtained into final catalyst.Preparation process condition of the present invention is gentle, environmental-friendly；Obtained catalyst activity is high, and enantioselectivity is high, recoverable.
Description
Technical field
The invention belongs to technical field of catalytic chemistry, more particularly to asymmetric selective catalysis, specifically (S) -1- (1-
Ethoxy -1- isopropyls) thiourea modified Cr-Anderson types heteropolyacid catalyst, preparation method and applications.
Background technology
Nobel laureate professor Noyori points out within 2001：" following synthesis chemistry must be economic, safety
, chemistry environmental-friendly and that save resource and the energy, chemist needed to realize ' perfect reactive chemistry ' and effort,
The product that needs are only generated with 100% selectivity and 100% yield is produced without waste ".Chiral catalysis synthesis is made
To realize one of the important channel of " perfection synthesis chemistry ", wherein, chiral catalyst is the most crucial section in chiral catalysis research
Knowledge is inscribed.From reaction principle, chiral organic micromolecule catalysis is by reversible with unstable covalent bond with reaction substrate
If the Viability intermediate of landform or by interaction, such as oxygen key, Van der Waals force or ion equity priming reaction substrate.Homogeneous hand
Property catalysis have the characteristics that efficient, high enantioselectivity and reaction condition are gentle.
Catalysis is most promising and most practical value research direction in polyoxometallate application.Polyoxometallate
Integrate the good characteristic of acid base catalysator, oxidation reduction catalyst, metal oxide nanocatalyst etc. at the same time, be considered
It is a kind of widely used green multifunction catalyst.Early in early 20th century, people begin to the catalytic performance of polyacid into
Research is gone.To being at present, existing 8 polyacid catalysis industry projects are successfully developed.It is catalyzed into in Chemistry of Polyacids one
The eternal research topic of item.After chiral polyoxometallate is successfully synthesized, people have just started chiral polyacid not
The exploration in asymmetric catalytic field.Chiral polyoxometallate integrates the various excellent properties of polyacid and chiral material.Its is only
Special soluble class mineral metal-oxide structure, for chiral transmission in chiral non-origin of life theory and inoganic solids
Exploration provides preferable model；Its high elecrtonegativity, adjustable acid-base property, redox active and nano-scale are more more
Design, the synthesis of the new materials such as function nonlinear optics, nano material, stereoselectivity catalysis and medicine bring new wish
Hope.
At present, chiral organic micromolecule catalyst is difficult to realize for industrialized production, mainly due to catalyst activity compared with
It is low, dosage is high and is not easily recycled utilization.Realize the application of these catalytic reactions industrially, it is necessary to solve expensive catalyst
The problem of recycling is a serious.
Since Zubieta in 1993 et al. exists《Nature》Upper report is successfully prepared similar DNA using hydrothermal technique
Chiral double-stranded compound (Me2NH2)K4[V10O10(H2O)4(OH)4(PO4)7]·H2After O, people have just started chirality
Exploration of the polyacid in asymmetric catalysis field.The Chinese Academy of Sciences chemistry institute Luo Sanzhong teach et al. urged with organic amine small molecules
Agent is made that outstanding work (Organic as the field of catalyst-supporting carriers as counter cation, polyacid
letters,2007,9(18):3675-3678.).They have synthesized a series of secondary amine-tertiary amine-type proline derivative, use
Polyanionic [the PW of highly acid12O40]3-The mineral acid in traditional Acid-Base concerted catalysis is substituted, it is organic to have synthesized a series of chiralitys
Amine-polyacid hybrid material.These materials all show the direct asymmetric Aldol reaction of aldehyde ketone, asymmetric Michael addition reaction etc.
Very high catalytic activity and chiral selectivity.Organic amine small molecules are assembled as counter cation with polyacid by electrostatic interaction,
But these materials do not have clear and definite molecular structure, it is impossible to further probe into catalytic mechanism, it is impossible to explain the association of Chiral Amine and polyacid
Same-action.Dalian materialization institute Duan Chun meet seminar meet using the composition of polyoxometallate (POMs), the diversity of structure and
A series of adjustable denaturation of electric charge, porous POMOFs with catalysis of design and assembly, realizes them and is urged in multiphase
Application (Journal of the American Chemical Society, 2013,135 (28) in change:10186-
10189.), but these materials are also without clear and definite molecular structure, it is impossible to further probe into catalytic mechanism, it is impossible to explain MOFs
With the synergistic effect of POMs.
The content of the invention
For deficiency of the prior art, it is an object of the invention to provide one kind (S) -1- (1- ethoxy -1- isopropyls
Base) thiourea modified Cr-Anderson types heteropolyacid catalyst, preparation method and applications.The present invention solves existing chirality
Organic micromolecule catalyst activity is relatively low, dosage is high and is not easily recycled the technical problem utilized.The present invention is urged from organic molecule
The mentality of designing of agent is set out, and innovatively proposes to utilize " Acid-Base " concerted catalysis strategy, with the hand with potential catalytic activity
Property organic molecule as precursor, the methods of passing through organic decoration, dexterously make organic molecule acid with high Bronsted
Vacant polyanionic combine, construct chiral polyacid material, the polyacid material of organic decoration of the invention not only remains polyacid
Original structure, and the research field of polyacid has been expanded, make it that there is potential application in terms of catalysis, medicine and functional material
Value.In addition, polyacid has hydrophily, available green, cheap water as solvent carry out catalytic reaction, and reaction terminates can be to system
After middle addition organic solvent (ethanol, methanol etc.), polyacid easily separates out, and may be recovered utilization.
The present invention provides the thiourea modified Cr-Anderson types of one kind (S) -1- (1- ethoxy -1- isopropyls) are miscellaneous more
The preparation method of acid catalyst (structure is shown in Fig. 1), comprises the following steps that：
1) it is starting material by ammonium molybdate and chromic nitrate, it is anti-under conditions of pH value is 4~5, temperature is 80 DEG C~100 DEG C
Cr-Anderson type heteropoly acid parents (NH should be generated4)3[Cr(OH)6Mo6O18]；
2) by Cr-Anderson types heteropoly acid parent (NH obtained above4)3[Cr(OH)6Mo6O18] and trihydroxy amino
Methane is placed in water heating kettle, and hydro-thermal reaction is carried out at a temperature of 135 DEG C~145 DEG C, obtains the amido modified Cr- in organic one side
Anderson type polyoxometallates；
3) using L- valerian ammonia alcohols as Material synthesis (S) -1- (1- ethoxy -1- isopropyls) isothiocyanates；
4) it is (S) -1- (1- ethoxy -1- isopropyls) isothiocyanates and organic one side that step 2) obtains is amido modified
Cr-Anderson type polyoxometallates be dissolved in organic solvent, at a temperature of 45-55 DEG C reaction obtain (S) -1- (1- hydroxyls
Ethyl -1- isopropyls) thiourea modified Cr-Anderson type heteropolyacid catalysts.
In the present invention, in step 1), the molar ratio of ammonium molybdate and chromic nitrate is 1:1~1：2.
In the present invention, in step 1), the pH of system is transferred to 4~5 with concentrated nitric acid.
In the present invention, in step 2), Cr-Anderson type heteropoly acid parents (NH4)3[Cr(OH)6Mo6O18] and trihydroxy
The molar ratio of aminomethane is 1:2~1：5, the hydro-thermal reaction time is 20h~30h.
In the present invention, in step 2), the amido modified Cr-Anderson type polyoxometallates in organic one side are [TBA]3
{[NH2C(CH2O)3]CrMo6O18(OH)3, it is by adding 80 DEG C~90 DEG C of tetrabutylammonium bromide in the product after hydro-thermal reaction
At a temperature of react obtain, (NH4)3[Cr(OH)6Mo6O18] and tetrabutylammonium bromide molar ratio 1:3~1：5.
In the present invention, in step 3), by L- valerian ammonia alcohols, CS2With triethylamine with molar ratio 1:(2~4):1 ratio mixing,
Reaction 1h~2h is stirred at room temperature, then Boc is added under condition of ice bath2O and DMAP, after adding, continues to react under condition of ice bath
3h~5h, is prepared (S) -1- (1- ethoxy -1- isopropyls) isothiocyanates；Wherein：L- valerian ammonia alcohols, Boc2O and DMAP
Molar ratio 1:1:(0.02~0.05).
In the present invention, in step 4), (S) -1- (1- ethoxy -1- isopropyls) isothiocyanates has with what step 2) obtained
The molar ratio of the unilateral amido modified Cr-Anderson type polyoxometallates of machine is 1:3~1：5.
In the present invention, in step 4), organic solvent is DMF or DMSO.
(S) -1- (1- ethoxy -1- isopropyls) thiocarbamide being prepared the present invention also provides a kind of above-mentioned preparation method
The Cr-Anderson type heteropolyacid catalysts of modification.
Further, the present invention also provides a kind of thiourea modified Cr- of above-mentioned (S) -1- (1- ethoxy -1- isopropyls)
Application of the Anderson types heteropolyacid catalyst in the asymmetric dihydroxylation field of alkene.
Preferably, application process is as follows：Suitable alkene is taken, at 30 DEG C~50 DEG C, using water and acetonitrile as mixed solvent
Under the conditions of, add hydrogen peroxide and (S) -1- (1- ethoxy -1- isopropyls) thiourea modified Cr-Anderson type heteropoly acids are urged
Agent, reacts 24h, obtains vicinal diol compound.It is further preferred that the molar ratio of water and acetonitrile is 1:1~3:1, peroxidating
Hydrogen is oxygen source, its usage amount is 1-3 equivalents (using alkene as reference), and (S) -1- (1- ethoxy -1- isopropyls) is thiourea modified
Cr-Anderson type heteropolyacid catalysts are that the amount of alkene is 0.5mol%~5mol%.
The beneficial effects of the present invention are：The present invention can not only utilize the covalent modification of chiral organic micromolecule to beat
The high symmetry of broken polyacid, introduces chirality, improves its stereoselectivity in catalytic reaction, and can be small by organic chiral
The functional characteristic such as the asymmetry catalysis of molecule or biological medicine activity introduces polyacid, and makes organic moiety and inorganic polyanionic
Organically it is integrated into a whole, so that producing synergistic effect obtains more novel properties.The preparation method reaction of the present invention
It is mild condition, environmental-friendly；Obtained catalyst activity height, enantioselectivity is high, and recoverable, is applicable to industry
Metaplasia is produced.
Brief description of the drawings
Fig. 1 is the structural formula of final catalyst of the present invention.
Fig. 2 is the synthetic route chart of the present invention.
Fig. 3 is parent (NH4)3[Cr(OH)6Mo6O18] infrared spectrum.
Fig. 4 is the nuclear magnetic spectrogram of (S) -1- (1- ethoxy -1- isopropyls) isothiocyanates.
Fig. 5 is the infrared spectrum of unilateral amido modified Cr-Anderson type polyoxometallates.
Embodiment
Below using embodiment come the embodiment that the present invention will be described in detail, whereby to the present invention how application technology means
To solve technical problem, and that reaches technique effect realizes that process can fully understand and implement according to this.
Synthetic route such as Fig. 2 of the present invention.
Embodiment 1
Cr-Anderson type heteropoly acid parents (NH4)3[Cr(OH)6Mo6O18] preparation
Take 7.41g (6mmol) ammonium molybdate to be added in 20mL deionized waters, be sufficiently stirred to obtain clarified solution, be added dropwise afterwards
Concentrated nitric acid, is transferred to 4~5. by the pH of system and is heated to seethe with excitement, and maintains strong stirring, starts to be slowly added to 1.66g (7mmol) nitre
Sour chromium solid, stirring stop stirring, stand 15~30 minutes to there is a large amount of pink solids to produce.Filter, obtain 5.26g powder
Red crystalline solid raw material, yield 82%.
Parent (NH4)3[Cr(OH)6Mo6O18] infrared spectrum it is as shown in Figure 3.
Embodiment 2
(S) preparation of -1- (1- ethoxy -1- isopropyls) isothiocyanates
(R)-(+) -1- (2- naphthyls) ethamine (0.8562g, 5mmol) is added in dry reaction vessel, with 20mL second
Alcohol dissolves, and is then respectively added slowly to add CS2(0.1142g, 15mmol) and triethylamine (0.506mg, 5mmol), is stirred in room temperature
After mixing reaction 1h, di-tert-butyl dicarbonate (Boc is then added under the conditions of 0 DEG C2O) (1.091mg, 5mmol) and 4- diformazan ammonia
Yl pyridines (DMAP) (18mg, 0.15mmol), be stirred at room temperature reaction 2h after (have gas generation in the process of stirring, it should be noted that
Deflate and depressurize), 0.8448g (R) -1- (2- (naphthyl) ethyl) isothiocyanates can be obtained.Yield is 79.6%.
(S) nuclear magnetic spectrogram of -1- (1- ethoxy -1- isopropyls) isothiocyanates is as shown in figure 4, specific data are as follows：
1H NMR(501MHz,CDCl3) δ 8.17 (s, 1H), 4.62 (t, J=9.1Hz, 1H), 4.32 (t, J=7.8Hz,
1H), 3.78 (d, J=7.4Hz, 1H), 1.86-1.71 (m, 1H), 0.89 (dd, J=24.8,6.7Hz, 6H)
Embodiment 3
The preparation of unilateral amido modified Cr-Anderson type polyoxometallates
By Anderson parents (NH obtained above4)3[Cr(OH)6Mo6O18] 1.071g (1mmol) 10mL deionizations
Dissolved in water, after obtaining light red clear liquid, be slowly added to trihydroxy aminomethane 0.402g (3mmol).Afterwards by above-mentioned system
Add in water heating kettle, be heated to 140 DEG C, after reaction carries out 24h, add 4.83g tetrabutylammonium bromide under the conditions of 85 DEG C
In the solution stated, a large amount of pink precipitates i.e. crude product is produced, filters and can obtain red liquid, placement is crystallized, and is
The Cr-Anderson types polyacid [TBA] that organic one side amino decorations are repaiied3{[NH2C(CH2O)3]CrMo6O18(OH)3}。
Infrared spectrum such as Fig. 5 of unilateral amido modified Cr-Anderson type polyoxometallates.
Embodiment 4
(S) preparation of Cr-Anderson type heteropolyacid catalysts thiourea modified -1- (1- ethoxy -1- isopropyls)
Organic one side is amido modified [TBA]3{[NH2C(CH2O)3]CrMo6O18(OH)30.5g (0.275mmol) uses 5mL
DMF dissolve under the conditions of 50 DEG C after, add (S) -1- (1- ethoxy -1- isopropyls) isothiocyanates 0.145g (1mmol),
Maintain under 50 DEG C of stirring conditions, 2~3 days reaction time, bright pink clarified solution is placed in ether atmosphere crystallize after reaction, if
It can obtain red crystals behind dry day, that is, it is miscellaneous to obtain the thiourea modified Cr-Anderson types of (S) -1- (1- ethoxy -1- isopropyls)
More acid catalysts.
Embodiment 5
(S) asymmetry of Cr-Anderson type polyacid catalyzed alkenes thiourea modified -1- (1- ethoxy -1- isopropyls)
Dihydroxylation
1.0415g (0.01mol) styrene is added in clean reaction bulb, adds 10ml mixed solvents (water and second
The molar ratio of nitrile is 1:1~3:1), being eventually adding 30% hydrogen peroxide of 1.7g and 0.0210g (S) -1-, (1- ethoxys -1- is different
Propyl group) thiourea modified more acid catalysts of Cr-Anderson types, react 24h, take 5ml ethanol to add reaction system, centrifugation makes to urge
Agent settles, and adds 3ml ethanol separating catalyst again, filters, obtains catalyst, is dried in vacuo.Will be anti-with ethyl acetate
System is answered to extract 3 times, solvent is removed under reduced pressure in obtained product, and column chromatography for separation obtains vicinal diol compound, obtains product
1.3599g yield 99%.The enantiomeric excess of product is measured by chiral high performance liquid chromatography, and ee values are up to 99%.The catalyst
The progress of catalytic reaction that can be different degrees of, and there is preferable stereoselectivity.Use different olefin catalytics
Reaction equation is as follows, and obtained experimental result is shown in Table 1.
The asymmetric dihydroxylation experimental result of 1 polyacid catalyzed alkene of table
Recycle obtained catalyst and be directly used in next reaction (dihydroxylation of styrene), resulting product
Enantiomeric excess value measures (chiral AS-H columns, isopropanol by HPLC：N-hexane=3:7,254nm,20℃,0.5mL/min).Urge
Agent recycling is obtained to the results are shown in Table 2.
The experimental result that 2 catalyst of table recycles
All above-mentioned primary embodiments, the not this new product of implementation of other forms and/or new method setting
Limitation.Those skilled in the art will utilize this important information, the above modification, to realize similar implementation status.But
All modifications or transformation based on the present invention belong to the right of reservation.
The above described is only a preferred embodiment of the present invention, being not the limitation for making other forms to the present invention, appoint
What those skilled in the art changed or be modified as possibly also with the technology contents of the disclosure above equivalent variations etc.
Imitate embodiment.But it is every without departing from technical solution of the present invention content, the technical spirit according to the present invention is to above example institute
Any simple modification, equivalent variations and the remodeling made, still fall within the protection domain of technical solution of the present invention.
Claims (9)
1. the preparation of Cr-Anderson type heteropolyacid catalysts thiourea modified one kind (S) -1- (1- ethoxy -1- isopropyls)
Method, it is characterised in that comprise the following steps that：
1) it is starting material by ammonium molybdate and chromic nitrate, life is reacted under conditions of pH value is 4~5, temperature is 80 DEG C~100 DEG C
Into Cr-Anderson type heteropoly acid parents (NH4)3[Cr(OH)6Mo6O18]；
2) by Cr-Anderson types heteropoly acid parent (NH obtained above4)3[Cr(OH)6Mo6O18] and trihydroxy aminomethane
It is placed in water heating kettle, carries out hydro-thermal reaction at a temperature of 135 DEG C~145 DEG C, add tetrabutylammonium bromide, at a temperature of 80 DEG C~90 DEG C
Reaction obtains, (NH4)3[Cr(OH)6Mo6O18] and tetrabutylammonium bromide molar ratio 1:3~1：5, obtain organic unilateral amino and repair
The Cr-Anderson type polyoxometallates of decorations, the amido modified Cr-Anderson type polyoxometallates in organic one side are
[TBA]3{[NH2C(CH2O)3]CrMo6O18(OH)3}；
3) using L- valerian ammonia alcohols as Material synthesis (S) -1- (1- ethoxy -1- isopropyls) isothiocyanates；
4) the organic one side obtained (S) -1- (1- ethoxy -1- isopropyls) isothiocyanates and step 2) is amido modified
Cr-Anderson type polyoxometallates are dissolved in organic solvent, are reacted at a temperature of 45-55 DEG C and are obtained (S) -1- (1- hydroxyl second
Base -1- isopropyls) thiourea modified Cr-Anderson type heteropolyacid catalysts.
2. preparation method as claimed in claim 1, it is characterised in that in step 1), the molar ratio of ammonium molybdate and chromic nitrate is
1:1~1：2.
3. preparation method as claimed in claim 1, it is characterised in that in step 1), the pH of system is transferred to 4 with concentrated nitric acid~
5。
4. preparation method as claimed in claim 1, it is characterised in that in step 2), Cr-Anderson type heteropoly acid parents
(NH4)3[Cr(OH)6Mo6O18] with the molar ratio of trihydroxy aminomethane it is 1:2~1：5, the hydro-thermal reaction time is 20h~30h.
5. preparation method as claimed in claim 1, it is characterised in that in step 3), by L- valerian ammonia alcohols, CS2 and triethylamine with
Molar ratio 1:(2~4):1 ratio mixing, is stirred at room temperature reaction 1h~2h, then two dimethyl dicarbonates are added under condition of ice bath
Butyl ester and 4-dimethylaminopyridine, after adding, continue to react 3h~5h under condition of ice bath, (S) -1- (1- hydroxyl second are prepared
Base -1- isopropyls) isothiocyanates；Wherein：The molar ratio of L- valerian ammonia alcohols, two dimethyl dicarbonate butyl esters and 4-dimethylaminopyridine
1:1:(0.02~0.05).
6. preparation method as claimed in claim 1, it is characterised in that in step 4), (S) -1- (1- ethoxy -1- isopropyls)
The molar ratio of the isothiocyanates Cr-Anderson type polyoxometallate amido modified with organic one side that step 2) obtains is
1:3~1：5.
7. preparation method as claimed in claim 1, it is characterised in that in step 4), organic solvent is DMF or DMSO.
A kind of 8. (S) -1- (1- ethoxy -1- isopropyls) thiocarbamide that preparation method as described in one of claim 1-7 obtains
The Cr-Anderson type heteropolyacid catalysts of modification.
9. a kind of Cr-Anderson types thiourea modified (S) -1- (1- ethoxy -1- isopropyls) as claimed in claim 8 are miscellaneous
Application of more acid catalysts in the asymmetric dihydroxylation field of alkene.
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| CN106475140A (en) * | 2016-10-12 | 2017-03-08 | 上海应用技术大学 | (S) the unilateral Fe Anderson type heteropolyacid catalyst modified of 1 (1 ethoxy 1 isopropyl) thiourea, preparation method and applications |
| CN106513040A (en) * | 2016-10-12 | 2017-03-22 | 上海应用技术大学 | (S)-1-(1-hydroxyethyl-1-isopropyl)thiourea-modified Al-Anderson type heteropoly acid catalyst, preparation method and application thereof |
| CN109847775A (en) * | 2017-11-30 | 2019-06-07 | 中国科学院大连化学物理研究所 | A kind of method of Aqueous phase preparation protonation Type B Anderson type heteropoly acid |
| CN110483246A (en) * | 2018-05-15 | 2019-11-22 | 中国石油天然气股份有限公司 | A kind of β-Anderson type heteropolymolybdate organic derivative of unilateral modification |
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