CN113548684B - 一种介孔氧化铝基核壳复合材料及其单胶束导向界面组装方法和应用 - Google Patents
一种介孔氧化铝基核壳复合材料及其单胶束导向界面组装方法和应用 Download PDFInfo
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- CN113548684B CN113548684B CN202110870357.5A CN202110870357A CN113548684B CN 113548684 B CN113548684 B CN 113548684B CN 202110870357 A CN202110870357 A CN 202110870357A CN 113548684 B CN113548684 B CN 113548684B
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- alumina
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 239000000693 micelle Substances 0.000 title claims abstract description 36
- 239000011258 core-shell material Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000004094 surface-active agent Substances 0.000 claims abstract description 33
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002253 acid Substances 0.000 claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 19
- 239000005011 phenolic resin Substances 0.000 claims description 19
- 229920001568 phenolic resin Polymers 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- -1 polyethylene Polymers 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 8
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 8
- 229910021389 graphene Inorganic materials 0.000 claims description 8
- 229920000573 polyethylene Polymers 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 239000002736 nonionic surfactant Substances 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229920000428 triblock copolymer Polymers 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 2
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 claims description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 239000001263 FEMA 3042 Substances 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 239000005083 Zinc sulfide Substances 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 claims description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 2
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- LRBQNJMCXXYXIU-QWKBTXIPSA-N gallotannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@H]2[C@@H]([C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-QWKBTXIPSA-N 0.000 claims description 2
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 229940071870 hydroiodic acid Drugs 0.000 claims description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 2
- 239000012621 metal-organic framework Substances 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 2
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- 235000015523 tannic acid Nutrition 0.000 claims description 2
- 229920002258 tannic acid Polymers 0.000 claims description 2
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 2
- LVYZJEPLMYTTGH-UHFFFAOYSA-H dialuminum chloride pentahydroxide dihydrate Chemical compound [Cl-].[Al+3].[OH-].[OH-].[Al+3].[OH-].[OH-].[OH-].O.O LVYZJEPLMYTTGH-UHFFFAOYSA-H 0.000 claims 1
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 claims 1
- 239000008188 pellet Substances 0.000 claims 1
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- 239000000203 mixture Substances 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 6
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
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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
- 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
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Abstract
本发明涉及一种介孔氧化铝基核壳复合材料及其单胶束导向界面组装方法和应用,该制备方法具体为:将铝源、表面活性剂、酸溶解在有机溶剂中,得到混合液;将混合液干燥,得到单胶束凝胶;将单胶束凝胶、功能内核与有机醇水溶液混合,进行水热反应,单胶束凝胶在功能内核表面包裹;最后高温焙烧去除表面活性剂,得到所述具有介孔氧化铝壳层的核壳复合材料。本发明制得的核壳复合材料壳层厚度为5‑500nm,介孔孔径为2‑50nm,比表面积为50‑1200m2/g。本制备方法普适性强,适用于一系列尺寸、形状及组成不同的功能内核等。
Description
技术领域
本发明属于功能材料制备技术领域,涉及一种介孔氧化铝基核壳复合材料及其单胶束导向界面组装方法和应用。
背景技术
在先进纳米复合材料领域,由于核壳结构可以在纳米尺度上将不同的组分有效地结合在一起实现多组分间的协同效应,核壳结构的复合材料越来越多地受到人们的青睐。进一步地,通过合理的设计,在壳层中引入介孔结构,可以提高复合材料的比表面积和功能内核的可及性。在过去的十年中,科研工作者们发展了一系列的方法在不同的功能内核构筑介孔壳层,并探索了核-介孔壳结构复合材料在能源存储和催化等领域的应用。目前,人们已经可以在各种各样的功能内核上可控的构筑介孔二氧化硅、介孔高分子、介孔碳和介孔二氧化钛等壳层。
氧化铝具有热稳定性优异,价格低廉和表面性质可调等优点,被广泛地应用于各个领域(如抛光材料,耐火材料等),尤其是催化领域。以氧化铝作为载体构筑的异相催化剂在小分子的催化转化(如一氧化碳氧化,二氧化碳加氢和低链烷烃脱氢等)和大分子的催化裂化(如渣油加氢,重油裂解等)等领域都展现出了巨大的潜力。鉴于上述优点,近年来,人们开始尝试在各种功能内核上构筑介孔氧化铝壳层。但在已经成功的案例中,由于铝源水解交联和结晶过程比较复杂、随机性强,导致所包裹的氧化铝壳层厚度不均匀或不存在介孔结构,限制了其在应用中性能的发挥。本发明正是基于此而提出的。
发明内容
本发明的目的就是为了提供一种介孔氧化铝基核壳复合材料及其单胶束导向界面组装方法和应用,所制备的具有核壳结构的介孔氧化铝基复合材料壳层厚度、孔径和比表面积均可调等。
本发明的目的可以通过以下技术方案来实现:
本发明的技术方案之一提供了一种介孔氧化铝基核壳复合材料的单胶束导向界面组装方法,首先将表面活性剂、铝源和酸溶解在有机溶剂中,随着溶剂的挥发,表面活性剂和铝源之间发生氢键相互作用,得到单胶束基元;然后在水热条件下,单胶束基元在功能内核表面有序组装;最后高温焙烧去除表面活性剂,得到本发明所述介孔氧化铝基核壳复合材料。
具体的,本发明的单胶束导向界面组装方法包括以下步骤:
(1):取表面活性剂、铝源、酸和有机溶剂混合,得到澄清透明的混合液;
(2):将步骤(1)所得混合液干燥,得到氧化铝单胶束凝胶;
(3):取氧化铝单胶束凝胶与功能内核、有机醇、水混合,水热反应,所得反应产物洗涤、干燥、高温焙烧,即得到目标产物介孔氧化铝基核壳复合材料。
进一步的,本发明的表面活性剂是结构导向剂,在氧化铝壳层上构筑介孔,其可以为阴离子型表面活性剂、阳离子型表面活性剂或非离子型表面活性剂中的一种或几种。
更进一步的,所用的阴离子型表面活性剂为谷氨酸系阴离子表面活性剂、丙氨酸系阴离子表面活性剂、甘氨酸系阴离子表面活性剂、羧酸类阴离子表面活性剂中的一种或几种;
所用阳离子型表面活性剂为烷基季铵盐表面活性剂、双子座表面活性剂、流星锤表面活性剂或三头阳离子表面活性剂中的一种或几种;
所用非离子型表面活性剂为聚环氧乙烷-聚环氧丙烷、聚环氧乙烷-聚环氧丁烷、聚环氧乙烷-聚苯乙烯或聚环氧乙烷-聚甲基丙烯酸甲酯二嵌段共聚物、聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物、聚环氧丙烷-聚环氧乙烷-聚环氧丙烷三嵌段共聚物中的一种或几种。
进一步的,所述的铝源为氧化铝的前驱体,有机铝源或无机铝源中的一种或几种;更进一步的,所述的铝源为硝酸铝、硫酸铝、氯化铝、水合硫酸铝、水合氯化铝、乙酰丙酮铝、异丙醇铝、铝酸钠、三乙基铝、二氯乙基铝、乙氧基铝或仲丁醇铝中的一种或几种。更优选的,为异丙醇铝。
进一步的,所述的酸的作用是调控铝源的水解交联速率,确保其与表面活性剂协同组装,其可以为有机酸或无机酸中的一种或几种。具体的,所述的酸可以为甲酸、乙酸、柠檬酸、丹宁酸、盐酸、硫酸、硝酸、氢溴酸、氢碘酸或磷酸中的一种或几种。
进一步的,所述的有机溶剂为甲醇、乙醇、正丙醇、异丙醇、正丁醇、苯、甲苯、乙醚、四氢呋喃、氯仿或二氯甲烷中的一种或几种。
进一步的,步骤(1)中,表面活性剂、铝源、酸的摩尔比为(0.01-1):1:(12-200)。优选为0.01:1:20。同时,铝源与有机溶剂的摩尔比可以为1:(50~500),优选为1:100。
进一步的,干燥的温度可以为20~150℃,优选为40℃,时间优选为12~120h,优选为48h。
进一步的,步骤(3)中,氧化铝单胶束凝胶与功能内核、有机醇、水的添加量比为1g:(10-500)mg:(10-200)mL:(50-300)mL。优选为1g:50mg:30mL:100mL。
进一步的,所述的功能内核的作用是为单胶束组装提供界面,其可以为酚醛树脂球、沸石、石墨烯、碳纳米管、磷酸铁锂、四氧化三铁、硫化锌、二氧化硅小球、碳酸钙、硫化镉、硒化镉、金属有机框架膜中的一种或几种。
进一步的,所述的有机醇为乙醇、乙二醇、丙三醇、正丁醇、异丙醇、正丙醇、正戊醇或异戊醇中的一种或几种。
进一步的,步骤(3)中,水热反应的温度为80~220℃,时间为12~96h;
焙烧温度为500-1200℃,焙烧时间为2-24h。
本发明的技术方案之二提供了一种介孔氧化铝基核壳复合材料,其采用如上所述的单胶束导向界面组装方法制备得到,其特征在于,该核壳复合材料的比表面积为50-1200m2/g,壳层厚度为5-500nm,介孔尺寸为2-50nm。最终所得的氧化铝材料的晶相为α相,β相或γ相。
本发明的技术方案之三提供了一种介孔氧化铝基核壳复合材料在催化领域中的应用。
与现有技术相比,本发明具有以下优点:
1)从介孔材料的最小组成单元单胶束出发构筑介孔壳层,所得壳层厚度、孔径、比表面积等均可精确控制,可控性强;
2)本发明提供的制备方法适用于一系列尺寸、成分、形状不同的功能内核,普适性强。除核壳结构外,本方法还可以用于制备空心和蛋黄壳结构的介孔氧化铝基复合材料;
3)本发明制备的介孔氧化铝基核壳复合材料具有高的比表面积、大的孔径和孔容,有望在催化领域实现应用。
附图说明
图1为本发明的实施例介孔氧化铝基核壳复合材料的制备流程图;
图2为本发明实施例1提供的酚醛树脂球@介孔氧化铝壳的扫描电镜图;
图3为本发明实施例1提供的酚醛树脂球@介孔氧化铝壳的透射电镜图;
图4为本发明实施例1提供的酚醛树脂球@介孔氧化铝壳的氮气吸脱附图;
图5为本发明实施例1提供的酚醛树脂球@介孔氧化铝壳的孔径分布图;
图6为本发明实施例1提供的酚醛树脂球@介孔氧化铝壳的X射线衍射图;
图7为本发明实施例2提供的石墨烯@介孔氧化铝壳的扫描电镜图;
图8为本发明实施例2提供的石墨烯@介孔氧化铝壳的透射电镜图;
图9为本发明实施例3提供的空心介孔氧化铝纳米球的透射电镜图;
图10为本发明对比例1提供的样品的扫描电镜图;
图11为本发明对比例2提供的样品的扫描电镜图。
具体实施方式
下面结合附图和具体实施例对本发明进行详细说明。本实施例以本发明技术方案为前提进行实施,给出了详细的实施方式和具体的操作过程,但本发明的保护范围不限于下述的实施例。
以下各实施例中,所用的酚醛树脂球和EO125-b-PS186为实验室自制,具体制备方法参考文献Liu.J.et al.,Angew.Chem.Int.Ed.,2011,50,5947和Deng.Y.et al.,J.Am.Chem.Soc.,2007,129,1690.石墨烯分散液购自先丰纳米(浓度:2mg/ml;溶剂:乙醇;片径大于500nm;货号:7440-44-0)
其余如无特别说明的原料或处理技术,则表明其均为本领域的常规市售原料或常规处理技术。
实施例1
将1.5g F127(表面活性剂)、75mL四氢呋喃和12mL浓盐酸(36-38wt%)混合,在室温下搅拌30分钟得到澄清透明的混合液,然后加入2.0g异丙醇铝,继续搅拌一个小时;将混合溶液转移到恒温干燥箱中,在40℃放置48h,得到白色的单胶束凝胶;
将1.0g单胶束凝胶和100mg酚醛树脂球分散在30mL乙醇和100mL水的混合溶液中,然后转移到水热釜中在160℃水热24h;所得产物用无水乙醇洗涤,再将其在氮气保护氛围下700℃高温焙烧3h除去表面活性剂,得到酚醛树脂微球@介孔氧化铝复合材料。
请参见图1,本实施例中以表面活性剂普朗尼克F127(EO106-PO70-EO106)作为模板剂,异丙醇铝作为铝源,模板剂和铝源反应后干燥,使溶剂挥发,得到单胶束凝胶,然后将单胶束凝胶和功能内核分散在乙醇和丙三醇的混合溶液中,进行水热反应使胶束在酚醛树脂微球表面组装,再高温脱除模板剂,得到所述功能内核@介孔氧化铝复合材料,所得功能内核@介孔氧化铝复合材料的壳层厚度为5-500nm,孔道尺寸为2-50nm,比表面积为50-1200m2/g。
具体的,请参见图2-3,图2扫描电镜图显示实施例1所得酚醛树脂微球@介孔氧化铝复合材料具有规则球形形貌,尺寸均一。图3透射电镜显示氧化铝壳层均匀包裹,厚度约为~5nm。
图4是实施例1得到的酚醛树脂球@介孔氧化铝核壳复合材料的氮气吸脱附等温线。吸附曲线是IV曲线,典型的介孔材料吸附等温线。在相对压力0.5-0.8处明显的吸附对应介孔。材料的比表面积为162m2/g
图5是实施例1得到的酚醛树脂球@介孔氧化铝核壳复合材料的孔径分布曲线。曲线显示材料具有均一孔径,尺寸约8.0nm。
图6是实施例1得到的酚醛树脂球@介孔氧化铝核壳复合材料的X射线衍射图,衍射图中可以观测到衍射峰对应γ-Al2O3,对应晶体库编号为10-0425。
实施例2
将1.5g F127、75mL四氢呋喃和12mL浓盐酸(36-38wt%)混合,在室温下搅拌30分钟得到澄清透明的混合液,然后加入2.0g异丙醇铝,继续搅拌一个小时;将混合溶液转移到恒温干燥箱中,在40℃放置48h,得到白色的单胶束凝胶;
将1.0g单胶束凝胶和100mg石墨烯分散在30mL乙醇和100mL水的混合溶液中,然后转移到水热釜中在160℃水热24h;所得产物用无水乙醇洗涤,再将其在700℃高温焙烧3h除去表面活性剂,得到石墨烯@介孔氧化铝复合材料。
请参见图7-8,图7扫描电镜图和图8透射电镜图显示,介孔氧化铝壳层在石墨烯上均匀致密包裹,孔径~5nm。
实施例3
将1.5g F127、75mL四氢呋喃和12mL浓盐酸(36-38wt%)混合,在室温下搅拌30分钟得到澄清透明的混合液,然后加入2.0g异丙醇铝,继续搅拌一个小时;将混合溶液转移到恒温干燥箱中,在40℃放置48h,得到白色的单胶束凝胶;
将1.0g单胶束凝胶和100mg酚醛树脂球分散在30mL乙醇和100mL水的混合溶液中,然后转移到水热釜中在160℃水热24h;所得产物用无水乙醇洗涤,再将其在空气氛围下700℃高温焙烧3h除去表面活性剂,得到空心介孔氧化铝纳米球。
请参见图9,图9透射电镜图显示,空心介孔氧化铝纳米球尺寸均匀,壳层厚度约为~10nm,孔径~5nm。
实施例4
将4.2g EO125-b-PS186(表面活性剂)、75mL四氢呋喃和12mL(36-38wt%)混合,在室温搅拌30分钟得到澄清透明的混合液,然后加入2.0g异丙醇铝,继续搅拌一个小时;将混合溶液转移到恒温干燥箱中,在40℃放置48h,得到白色的单胶束凝胶;
将1.2g单胶束凝胶和100mg酚醛树脂微球分散在30mL乙醇和10mL丙三醇的混合溶液中,然后转移到水热釜中在160℃水热24h;所得产物用无水乙醇洗涤,再将其在氮气保护下700℃高温焙烧3h除去表面活性剂,得到酚醛树脂球@介孔氧化铝核壳复合材料。所得材料孔径约为~18nm。
对比例1:
与实施例1相比,绝大部分都相同,除了本实施例中,省去了表面活性剂的引入。
如图10所示,在没有表面活性剂的存在的情况下,氧化铝壳层并不能在酚醛树脂球的表面均匀包裹。
对比例2:
与实施例1相比,绝大部分都相同,除了本实施例中,省去了醋酸的引入。
如图11所示,在没有醋酸存在的情况下,氧化铝水解速度不可控,造成最终产物聚集在一起,单分散性较差。
实施例5:
与实施例1相比,绝大部分都相同,除了本实施例中表面活性剂、酸、有机溶剂的添加量调整为满足:表面活性剂、铝源、酸、有机溶剂的摩尔比为0.5:1:12:50。
实施例6:
与实施例1相比,绝大部分都相同,除了本实施例中表面活性剂、酸、有机溶剂的添加量调整为满足:表面活性剂、铝源、酸、有机溶剂的摩尔比为1:1:200:500。
实施例7:
与实施例1相比,绝大部分都相同,除了本实施例中表面活性剂、酸、有机溶剂的添加量调整为满足:表面活性剂、铝源、酸、有机溶剂的摩尔比为0.01:1:20:100。
实施例8:
与实施例1相比,绝大部分都相同,除了本实施例中功能内核与有机醇、水调整至满足:
单胶束凝胶、功能内核与有机醇、水的添加量之比调整为1g:10mg:10mL:50mL。
实施例9:
与实施例1相比,绝大部分都相同,除了本实施例中功能内核与有机醇、水调整至满足:
单胶束凝胶、功能内核与有机醇、水的添加量之比调整为1g:500mg:200mL:300mL。
实施例10:
与实施例1相比,绝大部分都相同,除了本实施例中功能内核与有机醇、水调整至满足:
单胶束凝胶、功能内核与有机醇、水的添加量之比调整为1g:50mg::30mL:100mL。
实施例11:
与实施例1相比,绝大部分都相同,除了本实施例中水热反应温度调整为80℃;高温焙烧温度调整为500℃。
实施例12:
与实施例1相比,绝大部分都相同,除了本实施例中水热反应温度调整为220℃;高温焙烧温度调整为1200℃。
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改,并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此,本发明不限于上述实施例,本领域技术人员根据本发明的揭示,不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。
Claims (5)
1.一种介孔氧化铝基核壳复合材料的单胶束导向界面组装方法,其特征在于,包括以下步骤:
(1):取表面活性剂、铝源、酸和有机溶剂混合,得到澄清透明的混合液;
(2):将步骤(1)所得混合液干燥,得到氧化铝单胶束凝胶;
(3):取氧化铝单胶束凝胶与功能内核、有机醇、水混合,水热反应,所得反应产物洗涤、干燥、高温焙烧,即得到目标产物介孔氧化铝基核壳复合材料;
所述的表面活性剂为非离子型表面活性剂,所用非离子型表面活性剂为聚环氧乙烷-聚苯乙烯EO125-b-PS186或聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物EO106-PO70-EO106;
所述的有机溶剂为四氢呋喃;
步骤(1)中,表面活性剂、铝源、酸的摩尔比为(0.01-1):1:(12-200);
步骤(3)中,氧化铝单胶束凝胶与功能内核、有机醇、水的添加量比为1 g:(10-500)mg:(10-200) mL:(50-300)mL;
所述的功能内核为酚醛树脂球、沸石、石墨烯、碳纳米管、磷酸铁锂、四氧化三铁、硫化锌、二氧化硅小球、碳酸钙、硫化镉、硒化镉、金属有机框架膜中的一种或几种;
所述的有机醇为乙醇;步骤(3)中,水热反应的温度为80~220℃,时间为12~96 h;
焙烧温度为500-1200 ℃,焙烧时间为2-24 h。
2.根据权利要求1所述的一种介孔氧化铝基核壳复合材料的单胶束导向界面组装方法,其特征在于,所述的铝源为有机铝源或无机铝源中的一种或几种;
所述的酸为有机酸或无机酸中的一种或几种。
3.根据权利要求2所述的一种介孔氧化铝基核壳复合材料的单胶束导向界面组装方法,其特征在于,所述的铝源为硝酸铝、硫酸铝、氯化铝、水合硫酸铝、水合氯化铝、乙酰丙酮铝、异丙醇铝、铝酸钠、三乙基铝、二氯乙基铝、乙氧基铝或仲丁醇铝中的一种或几种;
所述的酸为甲酸、乙酸、柠檬酸、丹宁酸、盐酸、硫酸、硝酸、氢溴酸、氢碘酸或磷酸中的一种或几种。
4.一种介孔氧化铝基核壳复合材料,其采用如权利要求1-3任一所述的单胶束导向界面组装方法制备得到,其特征在于,该核壳复合材料的比表面积为50-1200 m2/g,壳层厚度为5-500 nm,介孔尺寸为2-50 nm。
5.如权利要求4所述的一种介孔氧化铝基核壳复合材料在催化领域中的应用。
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