CN105749976A - Preparation method of chiral organometallic ruthenium functionalized hydrophobic meso-porous silicon spheres - Google Patents
Preparation method of chiral organometallic ruthenium functionalized hydrophobic meso-porous silicon spheres Download PDFInfo
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- CN105749976A CN105749976A CN201610143522.6A CN201610143522A CN105749976A CN 105749976 A CN105749976 A CN 105749976A CN 201610143522 A CN201610143522 A CN 201610143522A CN 105749976 A CN105749976 A CN 105749976A
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- meso
- porous silicon
- organometallic ruthenium
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- ruthenium
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 17
- 125000002524 organometallic group Chemical group 0.000 title claims abstract description 15
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229910021426 porous silicon Inorganic materials 0.000 title abstract 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 12
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 claims abstract description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 5
- 238000001556 precipitation Methods 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 23
- 229910052710 silicon Inorganic materials 0.000 claims description 23
- 239000010703 silicon Substances 0.000 claims description 23
- 238000007306 functionalization reaction Methods 0.000 claims description 12
- -1 ethylphenyl Chemical group 0.000 claims description 8
- 239000004305 biphenyl Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000013335 mesoporous material Substances 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- DLCNNPYHAKSPDG-UHFFFAOYSA-N 1,2-diphenyl-2-(sulfonylamino)ethanamine Chemical compound C=1C=CC=CC=1C(N)C(N=S(=O)=O)C1=CC=CC=C1 DLCNNPYHAKSPDG-UHFFFAOYSA-N 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000009396 hybridization Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- 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
-
- 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
- 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
- B01J31/2208—Oxygen, e.g. acetylacetonates
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of chiral organometallic ruthenium functionalized hydrophobic meso-porous silicon spheres.The preparation method includes subjecting tetraethoxysilane, hexadecyl trimethyl ammonium bromide, diphenyl dichlorosilane and (R,R)-4-(methyltrimethoxysilane)ethylphenylamino sulfonyl-1,2-diphenylethylenediamine to copolymerization in an alkaline aqueous solution at 70 DEG C and to precipitation at 100 DEG C, and subjecting metallic ruthenium and a hydrophobic meso-porous silicon sphere carrier to coordination in anhydrous dichloromethane so as to synthesize the chiral organometallic ruthenium functionalized hydrophobic meso-porous silicon spheres.The chiral organometallic ruthenium functionalized hydrophobic meso-porous silicon spheres can be well dispersed in organic solvents and adsorb oily substrates quickly to accelerate reaction rate.Compared with common meso-porous materials, the phenyl-modified chiral organometallic ruthenium functionalized hydrophobic meso-porous silicon spheres are capable of increasing catalytic reaction rate as a heterogeneous catalyst.
Description
Technical field
The present invention relates to mesoporous material, refer specifically to Jie of a kind of hydrophobicity chirality Organometallic ruthenium functionalization
The preparation method of hole silicon ball.
Background technology
Since the order mesoporous silica-base materials of C.T.Kresge reported first in 1992, organic mesoporous silicon base material
Expect one of the performance focus being always scientific research because of its excellence, the most in recent years since, various
Organic mesoporous silicon sill of form is constantly in the news, and its application is also constantly being expanded.
Compare SBA-15 Yu MCM-41 series inorganic silicon mesoporous material, the mesoporous silicon base material of organic inorganic hybridization
Material not only has a feature such as stability of inorganic silicon material, but also have the oleophylic of organosilicon material
Characteristic, is therefore widely used in the fields such as absorption, catalysis and medicine transmission.(C.T.Kresge.et al.,
Nature,1992,359,710-712.M.Jaroniec.et al.,J.Am.Chem.S℃.2005,
127,60-61.S.Minakata.et al.,Chem.Rev.2009,109,711–724.H.X.Li.et al.J.
Am.Chem.S℃.2010,132,1492–1493.M.Kuroki.et al.J.Am.Chem.S℃.
2002,124,13886-13895.Xiaobo Li et al.J.Mater.Chem.A,2013,1,1525–
1535)
In organic inorganic hybridization mesoporous silicon sill, there is the material of relatively strong-hydrophobicity and super-hydrophobicity
Good achievement is achieved at some catalytic field, because its good lipophile, can be with fast enriching
Oiliness substrate so that it is be combined with catalytic active center, can play quickening reaction rate and improve productivity
Effect.Hydrophobic Mesoporous silicon materials generally use the method for copolymerization or the method for rear grafting to synthesize,
The kind of silane used is the most each variant, and the present invention uses tetraethoxysilane and diphenyl dichloro
Silane method of copolymerization in the alkaline aqueous solution of cetyl trimethylammonium bromide is prepared hydrophobicity and is situated between
Porous materials.(Juan Peng,et al.Chem.Commun.,2014,50,10830--10833.Shi
Song,et al.Chem.Commun.,2013,49,9591--9593)
Summary of the invention
It is an object of the invention to prepare a kind of loaded catalyst that can be well dispersed in reaction system,
Compared with traditional mesoporous silicon sphere loaded catalyst, owing to introducing phenyl at material, have good
Lipophile, this catalyst can accelerate reaction rate.
Solve the problems referred to above and have a following approach:
The present invention takes the method for silicon source copolymerization to synthesize a kind of hydrophobicity chirality Organometallic ruthenium functionalization
Mesoporous silicon sphere, specially tetraethoxysilane, cetyl trimethylammonium bromide, diphenyl dichloro
Silane and (R, R)-4-(trimethoxymethylsila,e) ethylphenyl sulfonyl-1,2-diphenyl diamine are at 70 DEG C
Alkaline aqueous solution carries out copolymerization, under the conditions of 100 DEG C, then carries out precipitation, finally at anhydrous dichloro
In methane, metal Ru is coordinated with Hydrophobic Mesoporous silicon ball carrier, thus synthesizing hydrophobic chirality organic metal
The mesoporous silicon sphere of ruthenium functionalization.
Present invention optimizes the preparation technology of Hydrophobic Mesoporous silicon ball, compared with disclosed patent, this
The mesoporous silicon sphere of the hydrophobicity chirality Organometallic ruthenium functionalization of bright preparation, due in this mesoporous silicon sphere
Be mixed with phenyl, therefore its can dispersed in organic solvent, and can be rich in reaction system
Collection oiliness substrate, quickly transports it catalytic active center to, thus plays the effect accelerating reaction rate.
So comparing with common mesoporous material, the hydrophobicity chirality Organometallic ruthenium functionalization of the present invention mesoporous
Silicon ball is as heterogeneous catalyst, it is possible to increase the reaction rate of catalytic reaction.Therefore, prepared by the present invention
The mesoporous silicon sphere of hydrophobicity chirality Organometallic ruthenium functionalization have huge potential at catalytic field.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) of loaded catalyst of the present invention.
Fig. 2 is the transmission electron microscope (TEM) of loaded catalyst of the present invention.
Fig. 3 is the contact angle (C/A) of loaded catalyst of the present invention.
Detailed description of the invention
Provide present pre-ferred embodiments below in conjunction with the accompanying drawings, to describe technical scheme in detail.
Embodiment:
Take 0.4g cetyl trimethylammonium bromide, 180mL deionized water, 1.4mL 2mol/L hydrogen-oxygen
Changing sodium solution, be sequentially added in the there-necked flask of 250mL, 70 DEG C of mechanical agitation 1 hour, rotating speed is
800r/min。
It is subsequently adding the sym-trimethylbenzene. of 1.136mL, ultrasonic 1 hour so that it is form homogeneous emulsion.
It is added dropwise over 1.8mL tetraethoxysilane and 1.6ml ethyl acetate the most simultaneously, stirs 10min,
It is added dropwise over 0.45g (R, R)-4-(trimethoxymethylsila,e) ethylphenyl sulfonyl-1,2-diphenyl two again
Amine, stirs 5min, is added dropwise over 2.84ml diphenyl dichlorosilane the most again, stirs 2h.Wherein four
Ethoxysilane, diphenyl dichlorosilane, (R, R)-4-(trimethoxymethylsila,e) ethylphenyl sulphonyl
Base-1, the mol ratio of 2-diphenyl diamine is 9:10:1, and (R, R)-4-(trimethoxymethylsila,e) ethyl
Phenyl sulfonyl-1, the dchloromethane of 2-diphenyl diamine 0.5mL, rate of addition is per minute
90-95 drips.
Precipitation 24h at last 100 DEG C, precipitation terminates to carry out afterwards sucking filtration, and obtain after sucking filtration is white
Color solid is put in vacuum drying oven 60-65 DEG C and is dried overnight, the white powdery solids finally given
It is catalyst carrier material.
Take 500mg said catalyst carrier with 40mg sym-trimethylbenzene. ruthenium dimer in round-bottomed flask,
Being subsequently adding 40mL anhydrous methylene chloride, 24h is stirred at room temperature, reaction terminates to be spin-dried for afterwards solvent,
With dichloromethane surname extraction 4h.The faint yellow solid finally given is put in vacuum drying oven,
60-65 DEG C is dried overnight and obtains loaded catalyst: hydrophobicity chirality Organometallic ruthenium functionalization mesoporous
Silicon ball.Its scanning electron microscope (SEM) and transmission electron microscope (TEM) are distinguished the most as depicted in figs. 1 and 2, its contact angle
(C/A) Fig. 3 is seen.(R, R)-4-(trimethoxymethylsila,e) ethylphenyl sulfonyl-1,2-prepared by the present invention
The Hydrophobic Mesoporous silicon ball of about the 60nm of diphenyl diamine functionalization, has Jie of about 3.5nm
Hole, contact angle reaches 131 degree.
Claims (2)
1. a preparation method for the mesoporous silicon sphere of hydrophobicity chirality Organometallic ruthenium functionalization, its feature
It is, tetraethoxysilane, cetyl trimethylammonium bromide, diphenyl dichlorosilane and (R, R)-4-(three
Methoxy methyl base silane) ethylphenyl sulfonyl-1,2-diphenyl diamine carries out in 70 DEG C of alkaline aqueous solutions
Copolymerization, then carries out precipitation under the conditions of 100 DEG C, finally in anhydrous methylene chloride metal Ru with dredge
Aqueous mesoporous silicon sphere carrier is coordinated, thus the mesoporous silicon of synthesizing hydrophobic chirality Organometallic ruthenium functionalization
Ball.
The mesoporous silicon sphere of hydrophobicity chirality Organometallic ruthenium functionalization the most according to claim 1
Preparation method, it is characterised in that tetraethoxysilane, diphenyl dichlorosilane, (R, R)-4-(trimethoxy
Butyldimethylsilyl) mol ratio of ethylphenyl sulfonyl-1,2-diphenyl diamine is 9:10:1.
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| CN201610143522.6A CN105749976A (en) | 2016-03-14 | 2016-03-14 | Preparation method of chiral organometallic ruthenium functionalized hydrophobic meso-porous silicon spheres |
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| CN201610143522.6A CN105749976A (en) | 2016-03-14 | 2016-03-14 | Preparation method of chiral organometallic ruthenium functionalized hydrophobic meso-porous silicon spheres |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020083386A1 (en) * | 2018-10-26 | 2020-04-30 | 中国石油化工股份有限公司 | Polyolefin catalyst component containing mesoporous material, preparation method therefor and use thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103387238A (en) * | 2013-06-25 | 2013-11-13 | 上海师范大学 | Preparation technology of Ethyl-bridged functionalized ordered mesoporous PMO |
| CN103962152A (en) * | 2014-04-28 | 2014-08-06 | 上海师范大学 | Ru-Pd bi-metal loading chiral catalyst and preparation technology thereof |
| CN104307566A (en) * | 2014-09-29 | 2015-01-28 | 上海师范大学 | TsDPEN functional ordered mesoporous silicon ball material and synthetic method thereof |
-
2016
- 2016-03-14 CN CN201610143522.6A patent/CN105749976A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103387238A (en) * | 2013-06-25 | 2013-11-13 | 上海师范大学 | Preparation technology of Ethyl-bridged functionalized ordered mesoporous PMO |
| CN103962152A (en) * | 2014-04-28 | 2014-08-06 | 上海师范大学 | Ru-Pd bi-metal loading chiral catalyst and preparation technology thereof |
| CN104307566A (en) * | 2014-09-29 | 2015-01-28 | 上海师范大学 | TsDPEN functional ordered mesoporous silicon ball material and synthetic method thereof |
Non-Patent Citations (2)
| Title |
|---|
| JUAN PENG等: "Superhydrophobic mesoporous silica nanospheres achieved via a high level of organo-functionalization", 《CHEM.COMMUN.》 * |
| 刘锐: "有机无机骨架介孔硅基材料负载型手性金属催化剂的制备及其活性的研究", 《上海师范大学硕士学位论文》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020083386A1 (en) * | 2018-10-26 | 2020-04-30 | 中国石油化工股份有限公司 | Polyolefin catalyst component containing mesoporous material, preparation method therefor and use thereof |
| CN113166302A (en) * | 2018-10-26 | 2021-07-23 | 中国石油化工股份有限公司 | Polyolefin catalyst component containing mesoporous material and preparation method and application thereof |
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Application publication date: 20160713 |