CN106000391B - A kind of small sized metallic oxidate nano cluster/mesoporous SiO2Nanocomposite and preparation method thereof - Google Patents
A kind of small sized metallic oxidate nano cluster/mesoporous SiO2Nanocomposite and preparation method thereof Download PDFInfo
- Publication number
- CN106000391B CN106000391B CN201610333753.3A CN201610333753A CN106000391B CN 106000391 B CN106000391 B CN 106000391B CN 201610333753 A CN201610333753 A CN 201610333753A CN 106000391 B CN106000391 B CN 106000391B
- Authority
- CN
- China
- Prior art keywords
- preparation
- mesoporous sio
- metal oxide
- cluster
- mesoporous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 49
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 49
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 49
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 49
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 49
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 18
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 18
- 239000002114 nanocomposite Substances 0.000 claims abstract description 17
- 239000002077 nanosphere Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 30
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 25
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 13
- 239000000908 ammonium hydroxide Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 12
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 11
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 10
- 229930195733 hydrocarbon Natural products 0.000 claims description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 7
- 229940010552 ammonium molybdate Drugs 0.000 claims description 7
- 239000011609 ammonium molybdate Substances 0.000 claims description 7
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 6
- 239000004088 foaming agent Substances 0.000 claims description 6
- SLYCYWCVSGPDFR-UHFFFAOYSA-N octadecyltrimethoxysilane Chemical group CCCCCCCCCCCCCCCCCC[Si](OC)(OC)OC SLYCYWCVSGPDFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000004064 cosurfactant Substances 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 3
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 2
- -1 dry after Substances 0.000 claims description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims 4
- 239000003599 detergent Substances 0.000 claims 3
- 238000001035 drying Methods 0.000 claims 3
- 239000012046 mixed solvent Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 29
- 239000002131 composite material Substances 0.000 abstract description 18
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 9
- 239000004530 micro-emulsion Substances 0.000 abstract description 4
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 238000010189 synthetic method Methods 0.000 abstract description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 16
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 15
- 239000003921 oil Substances 0.000 description 12
- 238000004088 simulation Methods 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 7
- 239000003093 cationic surfactant Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- JKGITWJSGDFJKO-UHFFFAOYSA-N ethoxy(trihydroxy)silane Chemical class CCO[Si](O)(O)O JKGITWJSGDFJKO-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 4
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000007210 heterogeneous catalysis Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- FUESFIVIIFEDFI-UHFFFAOYSA-N octadecylsilicon Chemical compound CCCCCCCCCCCCCCCCCC[Si] FUESFIVIIFEDFI-UHFFFAOYSA-N 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- LGXAANYJEHLUEM-UHFFFAOYSA-N 1,2,3-tri(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC(C(C)C)=C1C(C)C LGXAANYJEHLUEM-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000000416 hydrocolloid Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- B01J35/61—
-
- B01J35/63—
-
- B01J35/647—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
Abstract
The invention belongs to field of nano material preparation, and in particular to a kind of small sized metallic oxidate nano cluster/mesoporous SiO2Nanocomposite and its synthetic method.The mesoporous SiO2The grain size of nanosphere carrier is 5~30nm, and aperture is 2~5nm；The metal oxide nano cluster is MoO3Or WO3, grain size is 0.1~2nm.Synthesis is using reverse microemulsion process.Small sized metallic oxidate nano cluster/mesoporous SiO is prepared using the method for the invention2Composite material, simple for process, economical, safety, metal oxide nano cluster is highly dispersed at the mesoporous SiO of carrier2On, and the size of metal oxide nano cluster and carrier mesoporous silicon oxide, morphology controllable, there is excellent catalytic performance.
Description
Technical field
The invention belongs to nano material preparation and heterogeneous catalysis technical fields, are related to a kind of MoO3/ mesoporous SiO2And WO3/
Mesoporous SiO2Nanocomposite and its synthetic method are related specifically to prepare MoO using reverse micro emulsion as reaction system3/ be situated between
Hole SiO2And WO3/ mesoporous SiO2Nanocomposite.
Background technology
Mesoporous silicon oxide is a kind of nontoxic material, since it has higher chemical stability and biocompatibility,
And huge specific surface area and uniform adjustable duct, be a kind of carrier of good properties, catalysis, separation, absorption and
It plays an important role in terms of medicament transport.Therefore, high specific area is prepared, the mesoporous silicon oxide of high pore volume becomes grinding for scholars
Study carefully hot spot, a variety of preparation methods have been developed at present.
The nineties in 19th century, Exxon Mobil companies with liquid crystal templated principle (J.Am.Chem.Soc., 1992,
114,10843；Nature., 1992,359,710), using surfactant as the template for preparing mesoporous silicon oxide, using water
Hot method reacts 48h in 150 DEG C of autoclave, is successfully prepared 2~8nm of aperture, 0.7~1.2cm of pore volume3g-1Orderly Jie
Porous molecular sieve MCM-41.Henceforth, nano material is prepared as template with surfactant and just become one important grind
Study carefully field.
At present, the preparation method that researchers use, often grain size is big, pore volume is smaller for obtained mesoporous silicon oxide,
And time-consuming for preparation process, complex process, and energy consumption is big.For example, 1998, Klaus et al. uses co-hydrolysis, by octadecane
Base trimethoxy silane and alkylamine have obtained grain size in 0.1~2 μm, 2~6nm of aperture, pore volume only exists as pore-foaming agent
0.1~0.8cm3g-1The mesoporous silicon oxide (Supramolecular Science, 1998,5,253) of range.2015,
Kuroda et al. hydrocolloid technics, using methyl orthosilicate as silicon source, tri-isopropyl benzene is reacted as additive at 80 DEG C
The mesoporous silicon oxide that grain size is 20nm has been prepared in 12h, and 5~8nm of aperture, this preparation method reaction time is long, process
Complex (Nanoscale, 2015,7,19557).
It is based on more than research conditions, this patent is intended to relatively simple, economic preparation method, and it is small to prepare grain size, has
Mesoporous presence, and high specific area, the earth silicon material of high pore volume, and by metal oxide (MoO3、WO3) as activity
Component is supported on mesoporous silicon oxide so that MoO3/ mesoporous SiO2、 WO3/ mesoporous SiO2As heterogeneous catalysis and use
During the oxidation sweetening of oil product.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of metal oxide nano cluster/mesoporous SiO2Nano combined material
Material and preparation method thereof, the preparation method is mildly simple, by metal oxide (MoO3、WO3) load on mesoporous silicon oxide,
Obtained composite material can be used in heterogeneous catalysis, it is particularly possible to the sulfur-containing compound in efficient removing fuel oil.
The technical scheme is that：
A kind of metal oxide nano cluster/mesoporous SiO2Nanocomposite, including small-size meso-porous SiO2Nanosphere carrier
With the metal oxide nano cluster being highly dispersed on carrier；The mesoporous SiO2The grain size of nanosphere carrier is 5~30nm,
Aperture is 2~5nm；The metal oxide nano cluster is MoO3Or WO3, grain size is 0.1~2nm.
A kind of above-mentioned metal oxide nano cluster/mesoporous SiO2The preparation method of nanocomposite, includes the following steps：
(1) it is 3~6 in molar ratio by cosurfactant and surfactant：1 adds in the mixing of organic hydrocarbon and ammonium hydroxide
In solvent, wherein the molar ratio of organic hydrocarbon and surfactant is 10~18：1, mole of ammonia spirit and surfactant
Than being 3~6：1；It is stirred under the conditions of 25~45 DEG C to forming transparent clear solution.
The surfactant is cationic surface active agent hexadecyltrimethylammonium chloride (CTAC), hexadecane
One kind in base trimethylammonium bromide (CTAB)；The cosurfactant is the alcohols of carbon chain lengths 4~6, including positive fourth
One kind in alcohol, n-amyl alcohol, n-hexyl alcohol, cyclohexanol；The organic hydrocarbon is alkane of the carbon chain lengths 5~8, including positive penta
One kind in alkane, n-hexane, hexamethylene, normal heptane, normal octane, isooctane；The ammonium hydroxide mass fraction is 25~28%.
(2) molybdenum source or tungsten source are added in into the transparent clear solution obtained by step (1), is stirred evenly, above-mentioned temperature is protected
It holds constant, reaction mixture is obtained after 0.5h；The molybdenum source be ammonium molybdate aqueous solution, a concentration of 0.05mol/L~
0.25mol/L；The tungsten source be ammonium metatungstate aqueous solution, a concentration of 0.05mol/L~0.3mol/L.
(3) by pore-foaming agent and silicon source in molar ratio 1:4~40 add in the reaction mixture obtained by step (2), wherein,
Silicon source mole dosage is 0.01~0.5 times of above-mentioned steps (1) ammonia spirit mole dosage, and above-mentioned temperature remains unchanged, stirring
1~4h of reaction obtains reaction solution.The silicon source is ethyl orthosilicate (TEOS), and pore-foaming agent is octadecyl trimethoxysilane
(C18TMS)。
(4) isopropanol is added in into the reaction solution that step (3) obtains, organic hydrocarbon in the volume and reverse micro emulsion of isopropanol
The volume of class is equal, and ultrasound, centrifugation obtain solid.It is dry at 80~120 DEG C after obtained solid ethyl alcohol or isopropanol wash
Solid is finally placed the roasting of tube furnace high temperature by 8~12h, and it is 15~40mL/min's that flow is passed through in entire roasting process
Air, with the rate of 1~10 DEG C/min from room temperature temperature programming to 30~60min of roasting at 250 DEG C, then with 1~5 DEG C/min's
1~4h is roasted when rate program is warming up to 300~600 DEG C and obtains metal oxide nano cluster/mesoporous SiO2Nanocomposite.
Compared with prior art, beneficial effects of the present invention are:
1) MoO is prepared using the method for the invention3/ mesoporous SiO2And WO3/ mesoporous SiO2Composite material, technique letter
It is single, economical, safety.Using cationic surfactant, organic phase is ammonium hydroxide for organic hydrocarbons, water phases such as hexamethylene, n-hexanes
Solution, cosurfactant are n-butanol, n-amyl alcohol etc., form reverse micro emulsion.By the concentration, the gold that adjust surfactant
Belong to total Water and surface-active in the concentration, dosage and system of oxide precursor (ammonium molybdate solution or ammonium metatungstate solution)
The ratio of agent dosage, the dosage of pore-foaming agent, size, the grain size of carrier that can effectively regulate and control metal oxide nano cluster are big
Small, nanocomposite aperture regulates and controls the property of composite material.
2) MoO is prepared using the method for the invention3/ mesoporous SiO2And WO3/ mesoporous SiO2Composite material, metal oxidation
Object nano-cluster (MoO3、WO3) it is highly dispersed at mesoporous SiO2。
3) MoO is prepared using the method for the invention3/ mesoporous SiO2And WO3/ mesoporous SiO2Composite material, size is small,
Aperture is relatively large, and pore volume is high, large specific surface area.
Description of the drawings
Fig. 1 (a) is the MoO that embodiment 2 is prepared3/ mesoporous SiO2The nitrogen adsorption of composite material-desorption curve figure；
Fig. 1 (b) is the MoO that embodiment 2 is prepared3/ mesoporous SiO2The corresponding graph of pore diameter distribution of composite material；
Fig. 2 (a) is the MoO that embodiment 4 is prepared3/ mesoporous SiO2The TEM image of composite material；
Fig. 2 (b) is the MoO that embodiment 4 is prepared3/ mesoporous SiO2The HRTEM images of composite material；
Fig. 3 (a) is the WO that embodiment 5 is prepared3/ mesoporous SiO2The TEM image of composite material；
Fig. 3 (b) is the WO that embodiment 5 is prepared3/ mesoporous SiO2The HRTEM images of composite material；
Fig. 4 (a) is the MoO that embodiment 4 is prepared3/ mesoporous SiO2The oxidation sweetening of catalysis simulation oil product, dibenzo thiophene
The curve that the conversion ratio of fen changes with catalyst amount；
Fig. 4 (b) is the WO being prepared according to embodiment 53/ mesoporous SiO2The oxidation sweetening of catalysis simulation oil product, dibenzo
The curve that the conversion ratio of thiophene changes with oxidizer.
Specific embodiment
The present invention is explained in detail with reference to embodiment, certain present invention is not limited in these specific implementations
Example.
Embodiment 1
The cationic surfactant hexadecyltrimethylammonium chloride of 0.01mol is taken to be added in flask, then again to
11mL hexamethylenes, 3mL n-butanols, 0.6mL ammonium hydroxide are added in flask, 3min is stirred at 25 DEG C, adds 50 μ L ammonium molybdates
(0.05mol/L ammonium molybdate aqueous solutions) continues to stir 40min.0.08mL ethyl orthosilicates are measured, add in octadecyl trimethoxy
Base silane so that octadecyl trimethoxysilane：Ethyl orthosilicate molar ratio is 1:4, react 2h.After reaction, it adds in
Isopropanol then by ultrasound, centrifuges, and washing, roasting process, natural cooling obtains target product.Roasting process is specially：
The air that flow is 20mL/min is passed through in entire roasting process, with the rate of 5 DEG C/min from room temperature temperature programming to 250 DEG C
When roast 30min, then roasting 4h obtains MoO when being warming up to 300 DEG C with the rate program of 2 DEG C/min3Nano-cluster/mesoporous SiO2It receives
Nano composite material.
Embodiment 2
The cationic surfactant cetyl trimethylammonium bromide of 0.01mol is taken to be added in flask, then again to
17mL hexamethylenes, 5mL n-butanols, 0.8mL ammonium hydroxide are added in flask.3min is stirred at 35 DEG C, adds 50 μ L ammonium molybdates
(0.1mol/L ammonium molybdate aqueous solutions) continues to stir 40min.1.8mL ethyl orthosilicates are measured, add in octadecyl
Silane so that C18TMS is 1 with TEOS molar ratios:4, react 2h.After reaction, isopropanol is added in, then by ultrasonic, from
The heart, washing, roasting process, natural cooling obtain target product.Roasting process is specially：Flow is passed through in entire roasting process
For the air of 30 mL/min, with the rate of 10 DEG C/min from room temperature temperature programming to 250 DEG C when roasts 40min, then with 5 DEG C/
2h is roasted when the rate program of min is warming up to 500 DEG C and obtains MoO3Nano-cluster/mesoporous SiO2Nanocomposite.
Fig. 1 (a) is the MoO that embodiment 2 is prepared3/ mesoporous SiO2The nitrogen adsorption of composite material-desorption curve figure, figure
1 (b) is the MoO that embodiment 2 is prepared3/ mesoporous SiO2The corresponding graph of pore diameter distribution of composite material, according to IUPAC to absorption
The classification of desorption curve, MoO3/ mesoporous SiO2The adsorption/desorption curve of composite material belongs to Section IV class, there is lag loop.In nitrogen
Adsorb starting stage, MoO3/ mesoporous SiO2Mono layer adsorption occurs for composite material surface；Adsorbance is with relative pressure (P/ later
P0) increase and rise, show containing a certain amount of micropore；Then adsorption curve no longer overlaps, and adsorption desorption hysteresis loop occurs,
Illustrate capillary condensation phenomenon, prepare in material containing a large amount of mesoporous；Work as P/P0During close to 1, polymolecular has occurred in hole
Layer absorption.
Embodiment 3
The cationic surfactant hexadecyltrimethylammonium chloride of 0.01mol is taken to be added in flask, then again to
19mL hexamethylenes, 5.5mL n-butanols, 1mL ammonium hydroxide are added in flask, 3min is stirred at 45 DEG C, adds 50 μ L ammonium molybdates
(0.2mol/L ammonium molybdate aqueous solutions) continues to stir 40min.6mL ethyl orthosilicates are measured, add in octadecyl silicon
Alkane so that octadecyl trimethoxysilane：Ethyl orthosilicate molar ratio is 1:40, react 2h.After reaction, isopropyl is added in
Alcohol then by ultrasound, centrifuges, and washing, roasting process, natural cooling obtains target product.Roasting process is specially：Entirely
The air that flow is 40mL/min is passed through in roasting process, with the rate of 2 DEG C/min from room temperature temperature programming to 250 DEG C when roasts
50min, then roasting 2h obtains MoO when being warming up to 380 DEG C with the rate program of 1 DEG C/min3Nano-cluster/mesoporous SiO2It is nano combined
Material.
Embodiment 4
The cationic surfactant cetyl trimethylammonium bromide of 0.01mol is taken to be added in flask, then again to
17mL hexamethylenes, 5mL n-butanols, 0.8mL ammonium hydroxide are added in flask.3min is stirred at 35 DEG C, adds 50 μ L ammonium molybdates
(0.1mol/L ammonium molybdate aqueous solutions) continues to stir 40min.1.8mL ethyl orthosilicates are measured, add in octadecyl
Silane so that C18TMS is 1 with TEOS molar ratios:30, react 2h.After reaction, isopropanol is added in, then by ultrasonic, from
The heart, washing, roasting process, natural cooling obtain target product.Roasting process is specially：Flow is passed through in entire roasting process
For the air of 15 mL/min, with the rate of 8 DEG C/min from room temperature temperature programming to 250 DEG C when roasts 60min, then with 3 DEG C/min
Rate program when being warming up to 550 DEG C roasting 1.5h obtain MoO3Nano-cluster/mesoporous SiO2Nanocomposite.
By target product for the oxidation sweetening of catalysis simulation oil product.
The dibenzothiophenes (DBT) for weighing 50mg is dissolved in the decahydronaphthalene of 100mL, and sulfur-containing compound dibenzo thiophene is configured
The simulation oil product of a concentration of 500ppm of fen；The tert-butyl hydroperoxide (TBHP) for weighing 75.2mg is dissolved in the decahydronaphthalene of 100mL
In so that the molar ratio of DBT and TBHP is 1 in two kinds of solution of unit volume:2.
The simulation oil product of 2mL is taken to be placed in reaction tube, is placed in 50 DEG C of water-bath, weighs the target product of certain mass
MoO3/ mesoporous SiO2It is added in reaction system, after quick stirring 10min, adds in the TBHP of 2mL.Continue to stir, react 2h.
After reaction, with the conversion ratio of gas phase process detection dibenzothiophenes.
Fig. 2 (a) is the TEM image of target product, and Fig. 2 (b) is the HRTEM images of target product.By Fig. 2 (a) and Fig. 2
(b) as it can be seen that MoO3/ mesoporous SiO2Composite material grain size is about 15-20nm, spherical in shape, and pattern is uniform, and MoO3Nano-cluster is very
It is small, and high degree of dispersion is in the carrier.Fig. 4 (a) is the oxidation sweetening of application target product catalysis simulation oil product, dibenzothiophenes
The curve that conversion ratio changes with catalyst amount, by Fig. 4 (a) as it can be seen that the conversion ratio of dibenzothiophenes is with catalyst amount
Increase and increase, when being not added with catalyst, reaction almost without, when adding in a small amount of catalyst, reaction can quickly into
Row, and maximum conversion rate is up to 99%.
Embodiment 5
The cationic surfactant cetyl trimethylammonium bromide of 0.01mol is taken to be added in flask, then again to
17mL hexamethylenes, 5mL n-butanols, 0.8mL ammonium hydroxide are added in flask, 3min is stirred at 35 DEG C, adds 100 μ L ammonium metatungstates
(0.1mol/L ammonium metatungstate aqueous solutions) continues to stir 40min.1.8 mL ethyl orthosilicates are measured, add in octadecyl trimethoxy
Base silane so that octadecyl trimethoxysilane：Ethyl orthosilicate molar ratio is 1:20, react 2h.After reaction, it adds in
Isopropanol then by ultrasound, centrifuges, and washing, roasting process, natural cooling obtains target product.Lead in entire roasting process
Inbound traffics are the air of 35mL/min, and with the rate of 5 DEG C/min from room temperature temperature programming to 250 DEG C when roasts 45min, then with 2
DEG C/rate program of min when being warming up to 600 DEG C roasting 1h obtain WO3Nano-cluster/mesoporous SiO2Nanocomposite.
By target product for the oxidation sweetening of catalysis simulation oil product.
The dibenzothiophenes (DBT) for weighing 50mg is dissolved in the decahydronaphthalene of 100mL, and sulfur-containing compound dibenzo thiophene is configured
The simulation oil product of a concentration of 500ppm of fen；The tert-butyl hydroperoxide (TBHP) for weighing 75.2mg is dissolved in the decahydronaphthalene of 100mL
In so that the molar ratio of DBT and TBHP is 1 in two kinds of solution of unit volume:2.
The simulation oil product of 2mL is taken to be placed in reaction tube, is placed in 50 DEG C of water-bath, weighs the target product of certain mass
WO3/ mesoporous SiO2It is added in reaction system, after quick stirring 10min, adds in the TBHP of 2mL.Continue to stir, react 2h.
After reaction, with the conversion ratio of gas phase process detection dibenzothiophenes.
Fig. 3 (a) is the TEM image of target product, by Fig. 3 (a) as it can be seen that WO3/ mesoporous SiO2Composite material grain size is about 10-
15nm, nanocomposite is smaller, and spherical in shape, and pattern is uniform；Fig. 3 (b) is the HRTEM images of target product, by scheming
3 (b) is as it can be seen that WO3Nanocluster size is dispersed in carrier S iO near 1.5nm2In.Fig. 4 (b) is produced for application target
The oxidation sweetening of product catalysis simulation oil product, the curve that the conversion ratio of dibenzothiophenes changes with oxidizer, by Fig. 4 (b)
As it can be seen that the conversion ratio of dibenzothiophenes increases with the increase of oxidizer, when being not added with catalyst or oxidant, instead
It should be almost without when adding in catalyst and carrying out the oxidation sweetening of simulation oil product, the high conversion rate of dibenzothiophenes is up to 98%.
Embodiment 6
The cationic surfactant hexadecyltrimethylammonium chloride of 0.01mol is taken to be added in flask, then again to
17mL hexamethylenes, 5mL n-butanols, 0.8mL ammonium hydroxide are added in flask, 3min is stirred at 45 DEG C, adds 100 μ L ammonium metatungstates
(0.2mol/L ammonium metatungstate aqueous solutions) continues to stir 40min.1.8 mL ethyl orthosilicates are measured, add in octadecyl trimethoxy
Base silane so that octadecyl trimethoxysilane：Ethyl orthosilicate molar ratio is 1:40, react 2h.After reaction, it adds in
Isopropanol then by ultrasound, centrifuges, and washing, roasting process, natural cooling obtains target product.Lead in entire roasting process
Inbound traffics are the air of 20mL/min, and with the rate of 5 DEG C/min from room temperature temperature programming to 250 DEG C when roasts 50min, then with 5
DEG C/rate program of min when being warming up to 550 DEG C roasting 1h obtain WO3Nano-cluster/mesoporous SiO2Nanocomposite.
Claims (9)
1. a kind of metal oxide nano cluster/mesoporous SiO2The preparation method of nanocomposite, the metal oxide nano cluster/
Mesoporous SiO2Nanocomposite includes small-size meso-porous SiO2Nanosphere carrier and the metal oxide being highly dispersed on carrier
Nano-cluster；The mesoporous SiO2The grain size of nanosphere carrier is 5~30nm, and aperture is 2~5nm；The metal oxide
Nano-cluster is MoO3Or WO3, grain size is 0.1~2nm；
The metal oxide nano cluster/mesoporous SiO2The preparation method of nanocomposite, which is characterized in that including as follows
Step：
(1) it is 3~6 in molar ratio by cosurfactant and surfactant：1 adds in the mixed solvent of organic hydrocarbon and ammonium hydroxide
In, it is stirred under the conditions of 25~45 DEG C to forming transparent clear solution；
The organic hydrocarbon and the molar ratio of surfactant are 10~18：1；Ammonia and surface-active in the ammonium hydroxide
The molar ratio of agent is 3~6：1；The ammonium hydroxide mass fraction is 25~28%；
(2) molybdenum source or tungsten source are added in into the transparent clear solution obtained by step (1), stirs evenly, is reacted after 0.5h
Mixed liquor；The molybdenum source be 0.05mol/L~0.25mol/L ammonium molybdate aqueous solution, the tungsten source for 0.05mol/L~
The ammonium metatungstate aqueous solution of 0.3mol/L；
(3) by pore-foaming agent and silicon source in molar ratio 1:4~40 add in the reaction mixture obtained by step (2), wherein, silicon source
Mole dosage is 0.01~0.5 times of the ammonia mole dosage in step (1) ammonium hydroxide, and above-mentioned temperature remains unchanged, and is stirred to react 1
~4h obtains reaction solution；The silicon source is ethyl orthosilicate TEOS, and pore-foaming agent is octadecyl trimethoxysilane C18TMS；
(4) isopropanol, the volume of isopropanol and the volume of step (1) organic hydrocarbon are added in into the reaction solution that step (3) obtains
Equal, ultrasound, centrifugation obtain solid；Obtained solid washed with detergent, dry after, solid high-temperature is roasted, was entirely roasted
The air that flow is 15~40mL/min is passed through in journey, with the rate of 1~10 DEG C/min from room temperature temperature programming to 250 DEG C when roasts
1~4h of roasting obtains metal oxide when burning 30~60min, then being warming up to 300~600 DEG C with the rate program of 1~5 DEG C/min
Nano-cluster/mesoporous SiO2Nanocomposite.
2. preparation method according to claim 1, which is characterized in that surfactant described in step (1) for sun from
One kind in subtype surfactant hexadecyltrimethylammonium chloride CTAC, cetyl trimethylammonium bromide CTAB.
3. preparation method according to claim 1 or 2, which is characterized in that the cosurfactant described in step (1) is
The alcohols of carbon chain lengths 4~6, including one kind in n-butanol, n-amyl alcohol, n-hexyl alcohol, cyclohexanol.
4. preparation method according to claim 1 or 2, which is characterized in that the organic hydrocarbon described in step (1) is carbon chain length
The alkane 5~8 is spent, including one kind in pentane, n-hexane, hexamethylene, normal heptane, normal octane, isooctane.
5. preparation method according to claim 3, which is characterized in that the organic hydrocarbon described in step (1) is carbon chain lengths
In 5~8 alkane, including one kind in pentane, n-hexane, hexamethylene, normal heptane, normal octane, isooctane.
6. according to the preparation method described in claims 1 or 2 or 5, which is characterized in that the detergent described in step (4) is ethyl alcohol
Or isopropanol.
7. preparation method according to claim 3, which is characterized in that the detergent described in step (4) is ethyl alcohol or isopropyl
Alcohol.
8. according to claims 1 or 2 or 5 or 7 or the preparation method, which is characterized in that the dry temperature described in step (4)
It is 80~120 DEG C to spend, and drying time is 8~12h.
9. according to claim 6 or the preparation method, which is characterized in that drying temperature described in step (4) for 80~
120 DEG C, drying time is 8~12h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610333753.3A CN106000391B (en) | 2016-05-18 | 2016-05-18 | A kind of small sized metallic oxidate nano cluster/mesoporous SiO2Nanocomposite and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610333753.3A CN106000391B (en) | 2016-05-18 | 2016-05-18 | A kind of small sized metallic oxidate nano cluster/mesoporous SiO2Nanocomposite and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106000391A CN106000391A (en) | 2016-10-12 |
| CN106000391B true CN106000391B (en) | 2018-06-08 |
Family
ID=57098166
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610333753.3A Active CN106000391B (en) | 2016-05-18 | 2016-05-18 | A kind of small sized metallic oxidate nano cluster/mesoporous SiO2Nanocomposite and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106000391B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107185516B (en) * | 2017-05-26 | 2019-10-01 | 江苏大学 | A kind of preparation method and application of the dendron shape material of mesoporous silicon sphere containing molybdenum |
| CN108126687B (en) * | 2017-12-28 | 2020-10-16 | 沈阳师范大学 | Molybdenum and molybdenum-vanadium co-doped nano silicon oxide-based catalyst, and preparation method and application thereof |
| CN108160041A (en) * | 2018-01-10 | 2018-06-15 | 中国石油大学(华东) | A kind of sulfide in gas deep absorption desulfurization agent and preparation method |
| CN110252384B (en) * | 2019-06-20 | 2021-09-24 | 大连理工大学 | Sub-nano cluster transition metal oxide/MCM-41 composite material, preparation method and application thereof |
| CN110560073A (en) * | 2019-09-24 | 2019-12-13 | 大连理工大学 | Nickel-based catalyst for preparing formic acid by hydrogenating bicarbonate and preparation method thereof |
| CN110885696B (en) * | 2019-11-07 | 2022-01-28 | 武汉科技大学 | Sulfur-containing fuel oil desulfurization method of supported molybdenum oxide quantum dot catalyst |
| CN110882690A (en) * | 2019-11-07 | 2020-03-17 | 武汉科技大学 | Silicon dioxide nanosphere supported molybdenum oxide quantum dot catalyst and preparation method thereof |
| CN111129475B (en) * | 2020-01-15 | 2022-12-02 | 扬州大学 | Preparation method of molybdenum dioxide/carbon/silicon dioxide nanospheres and negative electrode material of lithium ion battery |
| CN112371107A (en) * | 2020-11-12 | 2021-02-19 | 大连理工大学 | Atomic-level dispersed transition metal oxide/SiO2Composite material, preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050453A (en) * | 2009-11-06 | 2011-05-11 | 中国科学院上海硅酸盐研究所 | Monox hollow sphere material with multi-stage pore structure and preparation method of monox hollow sphere material |
| CN104787768A (en) * | 2015-03-19 | 2015-07-22 | 华南理工大学 | Preparation method for mesoporous silica material |
| CN105084372A (en) * | 2014-05-21 | 2015-11-25 | 中国科学院化学研究所 | Method for loading nano-particles of metal or metallic oxide in mesoporous silica channel |
-
2016
- 2016-05-18 CN CN201610333753.3A patent/CN106000391B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050453A (en) * | 2009-11-06 | 2011-05-11 | 中国科学院上海硅酸盐研究所 | Monox hollow sphere material with multi-stage pore structure and preparation method of monox hollow sphere material |
| CN105084372A (en) * | 2014-05-21 | 2015-11-25 | 中国科学院化学研究所 | Method for loading nano-particles of metal or metallic oxide in mesoporous silica channel |
| CN104787768A (en) * | 2015-03-19 | 2015-07-22 | 华南理工大学 | Preparation method for mesoporous silica material |
Non-Patent Citations (3)
| Title |
|---|
| A remarkable Mo catalyst for olefin metathesis: hexagonal mesoporous silica-supported molybdenum oxide (MoO3/HMS);Tooru Ookoshi et al.;《Chem. Commun.》;19981231;2399-2400 * |
| Nanoparticle Architectures Templated by SiO2/Fe2O3 Nanocomposites;Dong Kee Yi et al.;《Chem. Mater.》;20060114;614-619 * |
| 钼基二氧化硅纳米复合材料的合成与性能研究;王加升;《中国博士学位论文全文数据库 工程科技I辑》;20150715;42-63 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106000391A (en) | 2016-10-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106000391B (en) | A kind of small sized metallic oxidate nano cluster/mesoporous SiO2Nanocomposite and preparation method thereof | |
| Wang et al. | Synthesis of three-dimensional ordered mesoporous W-doped KIT-6 for oxidative desulfurization catalyst of fuels | |
| CN106345489B (en) | A kind of sandwich structure nano catalytic material and preparation method thereof | |
| Meng et al. | Pickering emulsion droplets hosting ionic liquid catalysts for continuous-flow cyanosilylation reaction | |
| Liu et al. | Recycling nanoparticle catalysts without separation based on a pickering emulsion/organic biphasic system | |
| CN109433205A (en) | A kind of copper-based catalysts of Hydrogenation of Dimethyl Oxalate and the preparation method and application thereof | |
| CN110170325A (en) | Hollow structure cobalt/cobalt oxide/carbon nanotube preparation administered for propane and products thereof and application | |
| CN111702186B (en) | Preparation method of gold nanoparticles with adjustable size | |
| Keshipour et al. | Nanocomposite of hydrophobic cellulose aerogel/graphene quantum dot/Pd: Synthesis, characterization, and catalytic application | |
| CN106976866B (en) | A kind of preparation method of the porous Nano carbon balls of small size | |
| CN108014789A (en) | A kind of loaded catalyst for the poly- cyclohexyl. vinyl of polystyrene Hydrogenation and preparation method thereof | |
| CN107262097A (en) | A kind of high heat stability NiCo/SiO2The preparation method of nucleocapsid catalyst | |
| CN106040302A (en) | Hydrogenation catalyst | |
| Moon et al. | Tailoring metal–oxide interfaces of oxide-encapsulated Pt/silica hybrid nanocatalysts with enhanced thermal stability | |
| CN110064399A (en) | The preparation of core-shell structure coated with silica cobaltosic oxide catalyst for propane improvement and product and application | |
| CN107638880A (en) | A kind of synthetic method of the noble metal nano catalyst of transition metal oxide modification | |
| CN103566938A (en) | Preparation method for preparing synthesis gas NiO@SiO2 core-shell type catalyst by employing low-concentration coalbed methane | |
| Wang et al. | Preparation of CeO2 nano-support in a novel rotor–stator reactor and its use in Au-based catalyst for CO oxidation | |
| CN107597106A (en) | A kind of preparation method and applications of hollow nanometer capsule parcel platinum catalyst | |
| CN106745262B (en) | A kind of method for preparing amorphous oxide molybdenum nanometer sheet using the few layer molybdenum sulfide of oxidation | |
| Nafria et al. | Embedding catalytic nanoparticles inside mesoporous structures with controlled porosity: Au@ TiO 2 | |
| CN105797748A (en) | Preparation method of Pd-Fe/SiO2 hydrogenation catalyst | |
| CN105664931A (en) | Ru-based catalyst for preparing cyclohexene through partial hydrogenation of benzene and modification method of Ru-based catalyst | |
| CN107469815A (en) | A kind of preparation method and applications of preparing aldehyde by hydro formylating defin effective catalyst | |
| CN109046329A (en) | A kind of preparation method of atomic level two dimensional oxidation platinum quantum dot |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |