CN106799217A - A kind of Al2O3‑Ce2O3Mesoporous silica-base materials of/SBA 15 and preparation method thereof - Google Patents
A kind of Al2O3‑Ce2O3Mesoporous silica-base materials of/SBA 15 and preparation method thereof Download PDFInfo
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- CN106799217A CN106799217A CN201710040562.2A CN201710040562A CN106799217A CN 106799217 A CN106799217 A CN 106799217A CN 201710040562 A CN201710040562 A CN 201710040562A CN 106799217 A CN106799217 A CN 106799217A
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- 239000000463 material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 229910000421 cerium(III) oxide Inorganic materials 0.000 claims abstract description 55
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 28
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 27
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 20
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000004411 aluminium Substances 0.000 claims abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 18
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 claims description 17
- 238000002425 crystallisation Methods 0.000 claims description 16
- 230000008025 crystallization Effects 0.000 claims description 16
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- QTCPNSFIUHILTD-UHFFFAOYSA-N [C].CCCCCCCCO Chemical compound [C].CCCCCCCCO QTCPNSFIUHILTD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003093 cationic surfactant Substances 0.000 claims description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium nitrate Inorganic materials [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical class CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- XICHKUZHYIMXSQ-UHFFFAOYSA-N C(CCCCCCCCCCC)[Mg]C(C1=CC=CC=C1)(C)C Chemical compound C(CCCCCCCCCCC)[Mg]C(C1=CC=CC=C1)(C)C XICHKUZHYIMXSQ-UHFFFAOYSA-N 0.000 claims 1
- 229920000642 polymer Polymers 0.000 claims 1
- 238000005054 agglomeration Methods 0.000 abstract description 12
- 230000002776 aggregation Effects 0.000 abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000010703 silicon Substances 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 4
- 238000005034 decoration Methods 0.000 abstract 1
- 238000007747 plating Methods 0.000 abstract 1
- 239000002585 base Substances 0.000 description 31
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 238000001354 calcination Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 230000006378 damage Effects 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 229910000420 cerium oxide Inorganic materials 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- -1 rare earth metal cerium oxide Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical group [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 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
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/42—Materials comprising a mixture of inorganic materials
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a kind of mesoporous silicon substrate Al2O3‑Ce2O3Materials of/SBA 15 and preparation method thereof, the oxide direct plating decorations of metallic cerium and aluminium are arrived the surface of SBA 15 using bimodulus version method, the meso-hole structure of prepared material preserves more intact, and the agglomeration of metallic cerium is eliminated, it is easily prepared, operation is simple, and hydrothermal stability is good with heat endurance.
Description
Technical field
The invention belongs to Material Field, it is related to a kind of double-template method to prepare Al2O3-Ce2O3/ SBA-15 mesoporous solid silicon substrates
Material.
Background technology
The mesoporous silica-base material specific surfaces of SBA-15 are big, meso-hole structure is homogeneous, heat endurance and hydrothermal stability are high, but lack
Few avtive spot, alkali resistance are poor, therefore a definite limitation is subject in terms of adsorbing separation and catalytic applications.There is research in recent years by metal
It is oxide carried on SBA-15 surfaces or to be doped to SBA-15 skeletons, it is with the avtive spot for improving SBA-15 steady with its hydro-thermal
It is qualitative.Al2O3, MgO and rare-earth oxide be usually used in SBA-15 material modifications.Patent 201410318627.1 uses a step
Hydro-thermal method is by Al2O3It is entrained in SBA-15 skeletons, is slabbing Al2O3- SBA-15 materials, improve SBA-15 meso-hole structures special
Property, increase acidic site.Wang Ning (International Journal of Hydrogen Energy, 2012,37：19-30),
Haruhiko Ono (Applied Physics Letters, 2001,78：1832-1834) report rare earth metal cerium oxide not
Only coating can be formed on SBA-15 surfaces, and the thermally-stabilised of mesoporous silica-base material, hydrothermally stable and alkali resistance can be improved.Sun Lin
Soldier (Current Organic Chemistry, 2014,18：1296-1304) report metallic cerium oxide by rear grafting
It is immobilized to SBA-15 surfaces, it has been found that cause that it is irregular in SBA-15 surface distributeds due to its own agglomeration, in addition gold
The basic site for belonging to cerium oxide also results in certain destruction to the original meso-hole structures of SBA-15.
The content of the invention
Regarding to the issue above, the present invention proposes that a kind of double-template prepares Al2O3-Ce2O3/ SBA-15 mesoporous solid silicon substrates
The method of material, using the addition of double-template method and metal aluminum oxide, had both eliminated metallic cerium oxide on SBA-15 surfaces
Agglomeration and cause its be evenly distributed, destruction of the metallic cerium oxide basic site to the original meso-hole structures of SBA-15 is avoided again
Effect.
Technical scheme
1. a kind of Al2O3-Ce2O3The mesoporous silica-base materials of/SBA-15 and preparation method thereof are as follows：
(1) Al2O3-Ce2O3The quality mol ratio of Al, Ce, Si element is 0.04 in the mesoporous silica-base materials of/SBA-15
~0.18: 0.30~0.48: 1；
(2) Al2O3-Ce2O3The mesoporous silica-base materials of/SBA-15 are that aluminium and cerium are modified to SBA- by double-template method
15 surfaces are prepared from：By Al (NO3)3·9H2O、Ce(NO3)3·6H2The crystallization state mixture I that O and template 1 are formed,
It is added slowly under stirring in the mixtures II formed by tetraethyl orthosilicate and template 2, after 4~8h of stirring mixing, is turned
Enter in the stainless steel water heating kettle of polytetrafluoroethyllining lining, 40~60h of crystallization at 100~120 DEG C, through filtering, washing, do
It is dry, 400~600 DEG C are risen to 1~5 DEG C/min heating rates, 4~6h is calcined, cooling obtains the Al2O3-Ce2O3/
The mesoporous silica-base materials of SBA-15；
It is described form crystallization state mixture I method be：By Al (NO3)3·9H2O and Ce (NO3)3·6H2O is dissolved in together
In alcohols solvent, 0.5~4h is stirred at 25~60 DEG C, obtain mixed liquor A, while template 1 is dissolved in alcohols solvent, 25
~60 DEG C of 0.5~4h of stirring, obtain mixed liquid B, and mixed liquor A is slowly added into mixed liquid B under stirring, 25~
60 DEG C continue stir 0.5~4h after, be transferred in the stainless steel water heating kettle of polytetrafluoroethyllining lining, 80~130 DEG C of crystallization 3~
6h, forms crystallization state mixture I；
Al (the NO for forming crystallization state mixture I3)3·9H2O、Ce(NO3)3·6H2O, the mass ratio of template 1 are
0.1~0.45: 0.9~1.4: 1；
The template 1 is cationic surfactant cetyl trimethylammonium bromide, dodecyl dimethyl benzyl
At least one in ammonium chloride etc.；
The alcohols solvent is at least one in methyl alcohol, ethanol, normal propyl alcohol；
It is described formed mixtures II method be：In 25~60 DEG C of hydrochloric acid that template 2 is dissolved in into 1.6mol/L, quickly
After 0.5~4h of stirring, tetraethyl orthosilicate is added, continue to stir 6~12h, form mixtures II；
The tetraethyl orthosilicate for forming mixtures II is 2~2.5: 1 with the mass ratio of template 2；
The template 2 is that nonionic surface active agent type PEO-PPOX-PEO three is embedding
At least one in section copolymer (P123), ethoxylated dodecyl alcohol, the carbon octanol APEO of straight chain eight；
Prepare the Al2O3-Ce2O3Each raw material components Al (NO of the mesoporous silica-base materials of/SBA-153)3·9H2O、Ce
(NO3)3·6H2O, tetraethyl orthosilicate, template 1, the mass ratio of template 2 are 0.1~0.9: 0.9~2.8: 2~2.5: 1~2
∶1。
2. according to described in 1, it is preferable that prepare mesoporous silica-base material Al2O3-Ce2O3Each raw material components Al (NO of/SBA-153)3·
9H2O、Ce(NO3)3·6H2O、Si(OC2H5)4, template 1, the mass ratio of template 2 for 0.3~0.7: 1.2~2.5: 2~
2.5: 1.3~1.7: 1.
3. according to described in 1, it is preferable that the mesoporous silica-base material Al2O3-Ce2O3The matter of Al, Ce, Si element in/SBA-15
Amount mol ratio is 0.06~0.16: 0.33~0.45: 1.
Technical advantage of the invention and feature
(1) by double-template method by Al2O3、Ce2O3To pre-formed SBA-15 surfaces, SEM scans electric for coating modification together
Mirror and TEM transmission electron microscopes show with photo, prepared Al2O3-Ce2O3The metallic cerium oxide group of the mesoporous silica-base materials of/SBA-15
Poly- phenomenon is eliminated and meso-hole structure is remained intact；(2) material preparation method is simple, it is easy to operate, and show compared with
Well thermally-stabilised, hydrothermally stable and alkali resistance.
Brief description of the drawings
Fig. 1 is (A) SBA-15, (B) Ce2O3/SBA-15、(C)Al2O3-Ce2O3The small angle of the mesoporous silica-base materials of/SBA-15
There is SBA-15 meso-hole structure characteristic peaks in (100), (110) and (200) in degree XRD, three samples.
Fig. 2 is (A) Ce2O3/SBA-15、(B)Al2O3-Ce2O3The SEM spectrograms of/SBA-15, by contrast, Fig. 2 (B) sample
Arrangement is more regular, and sample surfaces agglomeration is also little.
Fig. 3 is (A) Ce2O3/SBA-15、(B)Al2O3-Ce2O3The TEM spectrograms of/SBA-15, by contrast, Fig. 3 (A) has
Ce2O3Reunion spot occurs, and Fig. 3 (B) is then little.
Fig. 4 is (A) SBA-15, (B) Ce2O3/SBA-15、(C)Al2O3-Ce2O3The N of/SBA-152Adsorption isotherm line chart, three
The H1 hysteresis loops of individual sample are appeared under relative pressure higher, it was demonstrated that prepared material has regular mesopore orbit.
Fig. 5 is (A) SBA-15, (B) Ce2O3/SBA-15、(C)Al2O3-Ce2O3/ SBA-15 graph of pore diameter distribution, it is known that SBA-
15 introduce Al2O3、Ce2O3After, its mesoporous pore size decreases, and this also demonstrates Al2O3、Ce2O3By effective coating in SBA-15
Mesopore surfaces.
Fig. 6 is (A) SBA-15, (B) Ce2O3/SBA-15、(C)Al2O3-Ce2O3The FT-IR spectrograms of/SBA-15, by
967cm-1Knowable to the characteristic peak at place, the Al of introducing2O3、Ce2O3It is attached to SBA-15 mesopore surfaces.
In Fig. 1-6, Ce2O3The mol ratio of Ce and Si is 0.44: 1, Al in/SBA-152O3-Ce2O3Al, Ce in/SBA-15
It is 0.06: 0.44: 1 with the mol ratio of Si.
Specific embodiment
Embodiment of the present invention is explained below by embodiment.
Embodiment 1 is by 2.14gAl (NO3)3·9H2O and 19.78g Ce (NO3)3·6H2O is dissolved in the anhydrous second of 119mL together
In alcohol, 3h is stirred at 40 DEG C, obtain mixed liquor A；14.94g cetyl trimethylammonium bromides are dissolved in 100mL absolute ethyl alcohols,
3h is stirred at 40 DEG C, mixed liquid B is obtained；Mixed liquor A is slowly dropped in mixed liquid B, after stirring 3h at 40 DEG C, then is transferred to poly-
In the stainless steel water heating kettle of tetrafluoroethene liner, the crystallization 5h in 110 DEG C forms crystallization state mixture I.At 40 DEG C by 10.35g
PEO-PPOX-PEO triblock copolymer is dissolved in the hydrochloric acid of 384.5g 1.6mol/L, acute
After strong stirring 3h, 21.97g tetraethyl orthosilicate reagents are added, continue to stir 12h, form mixtures II.By crystallization state mixture
I is added slowly in mixtures II under agitation, after stirring mixing 6h, is transferred in polytetrafluoroethyllining lining stainless steel water heating kettle,
In 100 DEG C of crystallization 48h；The mixed system that will be obtained is filtered, washs, dried, and the white powder for obtaining is in box Muffle furnace with 2
DEG C/after min heating rates rise to 550 DEG C and keep 6h from room temperature, cooling, that is, it is 0.056 that Al, Ce, Si elemental mole ratios are obtained:
0.44: 1 Al2O3-Ce2O3The mesoporous silica-base material 13.81g of/SBA-15, account for Al, Ce, Si oxide mass percentage in charging
99.28%, illustrate prepared Al2O3-Ce2O3The mesoporous silica-base materials of/SBA-15 are very few by hydro-thermal and calcination process loss,
Good stability, through BET, FT-IR, XRD, SEM, tem analysis test and sign, shows the intact presence of its meso-hole structure, and SBA-
15 mesopore surfaces do not have agglomeration.
With embodiment 1, its difference is the experimental procedure of embodiment 2：Al (NO are added in mixed liquor A3)3·9H2O、Ce
(NO3)3·6H2O is respectively 6.425g, 14.43g, and other holdings are constant, and obtained is that Al, Ce, Si element quality mol ratio are
0.167: 0.333: 1 Al2O3-Ce2O3The mesoporous silica-base material 12.56g of/SBA-15, account for Al, Ce, Si oxide mass in charging
The 99.52% of percentage, illustrates prepared Al2O3-Ce2O3The mesoporous silica-base materials of/SBA-15 are lost in by hydro-thermal and calcination process
Very few, good stability, through BET, FT-IR, XRD, SEM, tem analysis test and sign, shows that its meso-hole structure is subject to certain journey
Degree destruction, and SBA-15 mesopore surfaces have many agglomerations.
With embodiment 1, its difference is the experimental procedure of embodiment 3：Al (the NO added in mixed liquor A3)3·9H2O、
Ce(NO3)3·6H2O mass is respectively 4.8g, 16.7g, and other holdings are constant, and obtained is Al, Ce, Si element quality mol ratio
It is 0.125: 0.375: 1 Al2O3-Ce2O3The mesoporous silica-base material 13.03g of/SBA-15, account for Al, Ce, Si oxidation material in charging
The 99.39% of amount percentage, illustrates prepared Al2O3-Ce2O3The mesoporous silica-base materials of/SBA-15 are by hydro-thermal and calcination process stream
Very few, good stability is lost, through BET, FT-IR, XRD, SEM, tem analysis test and sign, shows that its meso-hole structure is subject to
Destruction, and SBA-15 mesopore surfaces some agglomerations, but slowed down than embodiment 2.
With embodiment 1, its difference is the experimental procedure of embodiment 4：Al (the NO added in mixed liquor A3)3·9H2O、
Ce(NO3)3·6H2O mass is respectively 3.75g, 17.51g, and other holdings are constant, and obtained is Al, Ce, Si element quality mole
Than the Al for 0.1: 0.4: 12O3-Ce2O3The mesoporous silica-base material 13.34g of/SBA-15, account for Al, Ce, Si oxide mass in charging
The 99.55% of percentage, illustrates prepared Al2O3-Ce2O3The mesoporous silica-base materials of/SBA-15 are lost in by hydro-thermal and calcination process
Very few, good stability, through BET, FT-IR, XRD, SEM, tem analysis test and sign, shows that its meso-hole structure is broken on a small quantity
It is bad, and SBA-15 mesopore surfaces have a small amount of agglomeration, but slowed down than embodiment 3.
With embodiment 1, its difference is the experimental procedure of embodiment 5：Al (the NO added in mixed liquor A3)3·9H2O、
Ce(NO3)3·6H2O mass is respectively 3.05g, 18.55g, and other holdings are constant, and obtained is Al, Ce, Si element quality mole
Than the Al for 0.083: 0.416: 12O3-Ce2O3The mesoporous silica-base material 13.51g of/SBA-15, account for Al, Ce, Si oxide in charging
The 99.41% of mass percent, illustrates prepared Al2O3-Ce2O3The mesoporous silica-base materials of/SBA-15 are by hydro-thermal and calcination process
Very few, good stability is lost in, through BET, FT-IR, XRD, SEM, tem analysis test and sign, shows that its meso-hole structure is only limited by
Slow down again than embodiment 4 to slight damage, and SBA-15 mesopore surfaces agglomeration.
With embodiment 1, its difference is the experimental procedure of embodiment 6：Preparing mesoporous silicon substrate Al2O3-Ce2O3/SBA-15
Material, the Al (NO added in mixed liquor A3)3·9H2O、Ce(NO3)3·6H2O mass is respectively 2.74g, 19.31g, other
Keep constant, obtained is the Al that Al, Ce, Si element quality mol ratio are 0.071: 0.429: 12O3-Ce2O3/ SBA-15 is mesoporous
Silica-base material 13.65g, accounts for 99.42% of Al, Ce, Si oxide mass percentage in charging, illustrates prepared Al2O3-
Ce2O3The mesoporous silica-base materials of/SBA-15 are lost in very few, good stability by hydro-thermal and calcination process, through BET, FT-IR, XRD,
SEM, tem analysis test and sign, show that its meso-hole structure is subject to slight damage, and SBA-15 mesopore surfaces are have very few group
Poly- phenomenon, but and slowed down than embodiment 5.
With embodiment 1, its difference is the experimental procedure of embodiment 7：Al (the NO added in mixed liquor A3)3·9H2O、
Ce(NO3)3·6H2O mass is respectively 1.905g, 20.05g, and other holdings are constant, and obtained is that Al, Ce, Si element quality are rubbed
You are than the Al for 0.05: 0.45: 12O3-Ce2O3The mesoporous silica-base material 13.89g of/SBA-15, account for Al, Ce, Si oxide in charging
The 99.36% of mass percent, illustrates prepared Al2O3-Ce2O3The mesoporous silica-base materials of/SBA-15 are by hydro-thermal and calcination process
Be lost in very few, good stability, through BET, FT-IR, XRD, SEM, tem analysis test with characterize, show its meso-hole structure destruction with
SBA-15 mesopore surfaces agglomeration is very few.
With embodiment 1, its difference is the experimental procedure of embodiment 8：Al (the NO added in mixed liquor A3)3·9H2O、
Ce(NO3)3·6H2O mass is respectively 1.62g, 20.75g, and other holdings are constant, and obtained is Al, Ce, Si element quality mole
Than the Al for 0.045: 0.45: 12O3-Ce2O3The mesoporous silica-base material 16.09g of/SBA-15, account for Al, Ce, Si oxide in charging
The 99.51% of mass percent, illustrates prepared Al2O3-Ce2O3The mesoporous silica-base materials of/SBA-15 are by hydro-thermal and calcination process
Very few, good stability is lost in, through BET, FT-IR, XRD, SEM, tem analysis test and sign, shows that its meso-hole structure is subject to few
Amount destruction, SBA-15 mesopore surfaces also have a small amount of agglomeration.
With embodiment 1, its difference is the experimental procedure of embodiment 9：Without addition Al (NO in mixed liquor A3)3·
9H2O, adds Ce (NO3)3·6H2O mass is 22.25g, and other holdings are constant, and obtained is Al, Ce, Si element quality mole
Than the Ce for 0: 0.5: 12O3The mesoporous silica-base material 14.50g of/SBA-15, account for Al, Ce, Si oxide mass percentage in charging
99.59%, illustrate prepared Al2O3-Ce2O3The mesoporous silica-base materials of/SBA-15 are very few by hydro-thermal and calcination process loss, surely
It is qualitative good, but through BET, FT-IR, XRD, SEM, tem analysis test and characterize, show that its meso-hole structure is destroyed and SBA-15
Mesopore surfaces agglomeration is serious.
Above example 1-9 is listed in table 1 using mesoporous silica-base material parameter obtained in different Al, Ce mol ratios.
The embodiment 1-9 results of table 1
Claims (3)
1. a kind of Al2O3-Ce2O3Mesoporous silica-base materials of/SBA-15 and preparation method thereof, it is characterized in that：
(1) Al2O3-Ce2O3The quality mol ratio of Al, Ce, Si element is 0.04~0.18 in the mesoporous silica-base materials of/SBA-15
: 0.30~0.48: 1；
(2) Al2O3-Ce2O3The mesoporous silica-base materials of/SBA-15 are that aluminium and cerium are modified to SBA-15 surfaces by double-template method
It is prepared from：By Al (NO3)3·9H2O、Ce(NO3)3·6H2The crystallization state mixture I that O and template 1 are formed, in stirring shape
It is added slowly under state in the mixtures II formed by tetraethyl orthosilicate and template 2, after 4~8h of stirring mixing, is transferred to poly-
In the stainless steel water heating kettle of tetrafluoroethene liner, 40~60h of crystallization at 100~120 DEG C through filtering, washing, is dried, with 1~
5 DEG C/min heating rates rise to 400~600 DEG C, are calcined 4~6h, and cooling obtains the Al2O3-Ce2O3/ SBA-15 is mesoporous
Silica-base material；
It is described form crystallization state mixture I method be：By Al (NO3)3·9H2O and Ce (NO3)3·6H2O is dissolved in alcohols together
In solvent, 0.5~4h is stirred at 25~60 DEG C, obtain mixed liquor A, while template 1 is dissolved in alcohols solvent, 25~60
DEG C stirring 0.5~4h, obtain mixed liquid B, mixed liquor A is slowly added into mixed liquid B under stirring, at 25~60 DEG C
After continuing to stir 0.5~4h, it is transferred in the stainless steel water heating kettle of polytetrafluoroethyllining lining, in 80~130 DEG C of 3~6h of crystallization,
Form crystallization state mixture I；
Al (the NO for forming crystallization state mixture I3)3·9H2O、Ce(NO3)3·6H2O, the mass ratio of template 1 for 0.1~
0.45: 0.9~1.4: 1；
The template 1 is cationic surfactant cetyl trimethylammonium bromide, dodecyl dimethyl Benzylmagnesium chloride
At least one in ammonium etc.；
The alcohols solvent is at least one in methyl alcohol, ethanol, normal propyl alcohol；
It is described formed mixtures II method be：In 25~60 DEG C of hydrochloric acid that template 2 is dissolved in into 1.6mol/L and stir 0.5
After~4h, tetraethyl orthosilicate is added, continue to stir 6~12h, form mixtures II；
The tetraethyl orthosilicate for forming mixtures II is 2~2.5: 1 with the mass ratio of template 2；
The template 2 is common for nonionic surface active agent type PEO-PPOX-PEO three block
At least one in polymers (P123), ethoxylated dodecyl alcohol, the carbon octanol APEO of straight chain eight；
Prepare the Al2O3-Ce2O3Each raw material components Al (NO of the mesoporous silica-base materials of/SBA-153)3·9H2O、Ce(NO3)3·
6H2O, tetraethyl orthosilicate, template 1, the mass ratio of template 2 are 0.1~0.9: 0.9~2.8: 2~2.5: 1~2: 1.
2. according to described in claim 1, it is characterised in that：Prepare mesoporous silica-base material Al2O3-Ce2O3Each raw material components Al of/SBA-15
(NO3)3·9H2O、Ce(NO3)3·6H2O、Si(OC2H5)4, template 1, the mass ratio of template 2 for 0.3~0.7: 1.2~
2.5: 2~2.5: 1.3~1.7: 1.
3. according to described in claim 1, it is characterised in that：The mesoporous silica-base material Al2O3-Ce2O3Al, Ce, Si unit in/SBA-15
The quality mol ratio of element is 0.06~0.16: 0.33~0.45: 1.
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