CN110545917A - 含有TiO2的多孔整料及其生产方法 - Google Patents
含有TiO2的多孔整料及其生产方法 Download PDFInfo
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- CN110545917A CN110545917A CN201880027993.8A CN201880027993A CN110545917A CN 110545917 A CN110545917 A CN 110545917A CN 201880027993 A CN201880027993 A CN 201880027993A CN 110545917 A CN110545917 A CN 110545917A
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- monolith
- porous monolith
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 30
- 239000011148 porous material Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 24
- 239000002243 precursor Substances 0.000 claims description 21
- 238000001354 calcination Methods 0.000 claims description 18
- 239000000839 emulsion Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 239000010936 titanium Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 239000004094 surface-active agent Substances 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- 230000002378 acidificating effect Effects 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 11
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 230000006641 stabilisation Effects 0.000 claims description 7
- 238000011105 stabilization Methods 0.000 claims description 7
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 150000002894 organic compounds Chemical class 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 239000007787 solid Substances 0.000 description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 238000002485 combustion reaction Methods 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical group CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000011941 photocatalyst Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000035800 maturation Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000012686 silicon precursor Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- -1 titanium alkoxides Chemical class 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 238000001429 visible spectrum Methods 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000012687 aluminium precursor Substances 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- MDDPTCUZZASZIQ-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]alumane Chemical compound [Al+3].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] MDDPTCUZZASZIQ-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/87—Ceramics
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
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- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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Abstract
本发明涉及一种多孔整料，其包含相对于整料的总重量计20重量%至70重量%的TiO2和相对于整料的总重量计30重量%至80重量%的选自二氧化硅、氧化铝或二氧化硅‑氧化铝的耐火氧化物，其特征在于所述多孔整料具有小于0.19 g/ml的堆密度。
Description
技术领域
本发明的领域在于具有分级结构的材料。更特别地，本发明涉及含有TiO2的多孔整料及其制备方法。
现有技术
制备具有多重孔隙率的基于无机氧化物，特别基于二氧化硅的整料是已知做法，借助通过直接乳液成型的方法获得大孔率。
A. Araya等人（US 4 888 309）和A. Imhof等人（Nature, vol. 389, 1997年10月30日，第948-952页）描述了使用溶解在醇中并通过加入少量水水解的醇盐实施溶胶-凝胶法，要强调的是，大多数醇盐与水的反应性高并且没有产生稳定乳液。这一文献也描述了由油在甲酰胺中的单分散乳液制备孔径为50 nm至几微米的氧化钛、氧化锆或二氧化硅的单分散微孔材料。
B. P. Binks（Adv. Mater., 2002, 14, No. 24, 第1824-1827页，12月17日）描述了在不存在表面活性剂的情况下由仅用二氧化硅粒子稳定化的乳液制备多孔二氧化硅。
J. S. Beck等人（J. Am. Chem. Soc., 1992, 114, 10834-10843）描述了由硅酸盐或铝硅酸盐构成的介孔固体的制备。
专利申请WO 2015/110772描述了多孔整料形式的基于N-TiO2的材料作为用于空气或水中的污染物在可见光谱辐射下降解或用于水在可见光谱辐射下裂解成H2的光催化剂的用途。
另一专利申请FR 2975309描述了含TiO2的多孔整料的制备模式及其作为用于空气或水中的污染物在辐照下降解的光催化剂的用途。所要求保护的整料具有大约1 g/ml的堆密度。
从M. Tahir和N. S. Amin（Appl. Catal. A: General 467 (2013), 483-496和Chem. Eng. J., 230 (2013), 314-327）中也已知使用含有被半导体化合物涂布的毫米级通道的“蜂窝”型整料。这种类型的物体也具有高的每单位体积密度（大约0.8至0.9 g/ml）。
但是，现有技术文献无一描述了含有至少20重量% TiO2并具有小于0.19 g/ml的堆密度的多孔整料类型的材料。根据本发明的主题，高TiO2含量和低堆密度的组合使得有可能提供与现有技术相比具有增加的暴露TiO2表面的整料。这些性质允许根据本发明的整料有利地用于催化或光催化用途。
更特别地，本发明描述了一种多孔整料，其含有相对于整料的总重量计20重量%至70重量%的TiO2、相对于整料的总重量计30重量%至80重量%的选自二氧化硅、氧化铝或二氧化硅-氧化铝的耐火氧化物并具有小于0.19 g/ml的堆密度。通过取多孔整料的重量与其几何体积的比率计算堆密度。
根据一个变体，所述多孔整料具有对于0.2至50 nm的孔径而言0.01至1 ml/g，优选0.05至0.5 ml/g的介孔体积。
根据一个变体，所述多孔整料具有0.1至3 ml/g，优选0.2至2.5 ml/g的I型大孔体积，即其孔径大于50 nm和小于或等于1000 nm。
根据一个变体，所述多孔整料具有0.1至8 ml/g，优选0.5至8 ml/g的II型大孔体积，即其孔径大于1 µm和小于或等于10 µm。
根据一个优选变体，多孔整料形式的所述光催化剂具有如上所述的介孔率和/或I型大孔率和/或II型大孔率。
根据一个变体，所述多孔整料也具有对于大于10 µm的孔径而言小于0.5 ml/g的大孔体积。
大孔和介孔体积通过根据标准ASTM D4284-83在4000巴（400 MPa）的最大压力下、使用484达因/厘米的表面张力和140º的接触角的压汞法测量。
根据一个变体，多孔整料形式的所述光催化剂具有150至700 m2/g，优选200至600m2/g的比表面积（根据由如S. Brunauer, P.H. Emmett, E. Teller, J. Am. Chem.Soc., 1938, 60 (2), 第309-319页中规定的Brunauer, Emmett, Teller方法，即BET方法建立的标准ASTM D 3663-78测量）。
优选地，TiO2为其锐钛矿和金红石形式，锐钛矿:金红石比优选在95:5至50:50之间。
本发明还涉及一种制备所述多孔整料的方法，其中在与硅和/或铝氧化物前体不同的步骤中引入Ti前体。该方法包括下列步骤：
a) 将含表面活性剂的溶液与酸性水溶液混合以获得含表面活性剂的酸性水溶液；
b) 将至少一种硅和/或铝前体添加到在步骤a)中获得的溶液中；
c) 将至少一种与在步骤b)中获得的溶液不混溶的液体有机化合物添加到在步骤b)中获得的溶液中以形成乳液；
d) 在步骤c)中获得的乳液在湿状态下熟化以获得凝胶；
e) 用有机溶液洗涤在步骤d)中获得的凝胶；
f) 将在步骤e)中获得的凝胶干燥和煅烧以获得多孔整料；
g) 将包含至少一种可溶性钛前体的溶液浸渍在步骤f)中获得的多孔整料的孔隙中；
h) 任选地，在步骤g)中获得的多孔整料在湿状态下熟化；
i) 将在步骤g)或h)中获得的多孔整料干燥和煅烧以获得含TiO2的多孔整料。
发明详述
定义
在下文中，化学元素的族根据CAS分类给出（CRC Handbook of Chemistry andPhysics，CRC Press出版，主编D. R. Lide，第81版，2000-2001）。例如，根据CAS分类的第VIII族对应于根据新IUPAC分类的第8、9和10列的金属。
在本说明书中，根据IUPAC公约，术语“微孔”意在表示直径小于2 nm的孔隙；术语“介孔”意在表示直径大于2 nm和小于或等于50 nm的孔隙，且术语“大孔”意在表示直径大于50 nm的孔隙，更特别地，术语“I型大孔”意在表示直径大于50 nm和小于或等于1000 nm（1 µm）的孔隙，且术语“II型大孔”意在表示直径大于1 µm和小于或等于10 µm的孔隙。
描述
根据本发明，该多孔整料包含相对于整料的总重量计20重量%至70重量%的TiO2，优选20重量%至60重量%的TiO2。根据本发明的多孔整料还包含相对于整料的总重量计30重量%至80重量%的选自二氧化硅、氧化铝或二氧化硅-氧化铝的耐火氧化物，优选40重量%至80重量%。
根据本发明的多孔整料具有小于0.19 g/ml，优选小于0.16 g/ml的堆密度。通过多孔整料的重量与其几何体积的比率计算堆密度。
有利地，所述多孔整料可含有独自或作为混合物的至少一种选自元素周期表的第IA、IIA、VIIIB、IB和IIIA族元素的元素M，其为金属或氧化状态。优选地，元素M的总含量为多孔整料的总重量的0.001重量%至20重量%。
有利地，多孔整料可用选自金属元素，例如元素V、Ni、Cr、Mo、Fe、Sn、Mn、Co、Re、Nb、Sb、La、Ce、Ta或Ti，非金属元素，例如C、N、S、F或P的一种或多种元素，或用金属和非金属元素的混合物掺杂。掺杂元素的含量为多孔整料的总重量的0.001重量%至5重量%。
根据一个变体，所述多孔整料具有对于0.2至50 nm的孔径而言0.01至1 ml/g，优选0.05至0.5 ml/g的介孔体积。
根据一个变体，所述多孔整料具有0.1至3 ml/g，优选0.2至2.5 ml/g的I型大孔体积，即其孔径大于50 nm和小于或等于1000 nm（1 µm）。
根据一个变体，所述多孔整料具有0.1至8 ml/g，优选0.5至8 ml/g的II型大孔体积，即其孔径大于1 µm和小于或等于10 µm。
根据一个优选变体，所述多孔整料具有介孔率和/或I型大孔率和/或II型大孔率。
根据一个变体，所述多孔整料也具有对于大于10 µm的孔径而言小于0.5 ml/g的大孔体积。
根据一个变体，所述多孔整料具有150至700 m2/g的BET表面积。
本发明还描述了制备所述多孔整料的方法，以在与硅和/或铝氧化物前体不同的步骤中引入Ti前体；
a) 将含表面活性剂的溶液与酸性水溶液混合以获得含表面活性剂的酸性水溶液；
b) 将至少一种硅和/或铝前体添加到在步骤a)中获得的溶液中；
c) 将至少一种与在步骤b)中获得的溶液不混溶的液体有机化合物添加到在步骤b)中获得的溶液中以形成乳液；
d) 在步骤c)中获得的乳液在湿状态下熟化以获得凝胶；
e) 用有机溶液洗涤在步骤d)中获得的凝胶；
f) 将在步骤e)中获得的凝胶干燥和煅烧以获得多孔整料；
g) 将包含至少一种可溶性钛前体的溶液浸渍在步骤f)中获得的多孔整料的孔隙中；
h) 任选地，在步骤g)中获得的多孔整料在湿状态下熟化；
i) 将在步骤g)或h)中获得的多孔整料干燥和煅烧以获得含TiO2的多孔整料。
下面详细描述这些步骤。
步骤a) (含表面活性剂的酸性水溶液的制备)
在根据本发明的方法的步骤a)的过程中，将含表面活性剂的溶液与酸性水溶液混合以获得含表面活性剂的酸性水溶液。这一步骤优选在环境温度下进行。
表面活性剂可以是阴离子型、阳离子型、两性或非离子型。表面活性剂优选是阳离子表面活性剂。表面活性剂非常优选是溴化十六烷基三甲基铵或溴化十四烷基三甲基铵。酸性水溶液优选选自无机酸性水溶液，如硝酸、硫酸、磷酸、盐酸或氢溴酸，或有机酸，如羧酸或磺酸，独自或作为混合物。酸性水溶液优选选自盐酸水溶液或硝酸水溶液。在步骤a)中获得的溶液的pH优选小于4。
步骤b) (至少一种硅酮和/或铝前体的添加)
在根据本发明的方法的步骤b)的过程中，将至少一种硅和/或铝前体添加到在步骤a)中获得的溶液中。
优选选择一种或多种醇盐类型的铝和/或硅前体。非常优选地，一种或多种铝和/或硅前体选自异丙醇铝、叔丁醇铝、原硅酸四乙酯或原硅酸四甲酯。
优选地，“前体/表面活性剂”重量比为0.1至10，优选0.2至5。
步骤c) (乳液的形成)
在根据本发明的方法的步骤c)的过程中，将至少一种与在步骤b)中获得的溶液不混溶的液体有机化合物添加到在步骤b)中获得的溶液中以形成乳液。这一步骤优选在环境温度下进行。
优选地，该液体有机化合物是具有5至15个碳原子的烃或烃混合物；例如，可以提到十二烷。优选地，“液体有机化合物/在步骤b)中获得的溶液”重量比为0.2至5，优选0.3至3。
步骤d) (凝胶的形成)
在根据本发明的方法的步骤d)的过程中，在步骤c)中获得的乳液在湿状态下熟化以获得凝胶。
优选地，在5至80℃，优选20至70℃的温度下进行熟化。优选地，熟化进行1至30天，优选1至15天。
步骤e) (洗涤)
在根据本发明的方法的步骤d)的过程中，用有机溶液洗涤在步骤d)中获得的凝胶。这一步骤优选在环境温度下进行。
优选地，该有机溶液是丙酮、乙醇、甲醇、异丙醇、四氢呋喃、乙酸乙酯或乙酸甲酯，独自或作为混合物。优选地，该洗涤步骤重复至少两次。
步骤f) (干燥和煅烧)
在根据本发明的方法的步骤f)的过程中，在步骤e)中获得的凝胶在空气下干燥和煅烧以获得多孔整料。
优选地，在5至80℃，优选20至75℃的温度下进行干燥。优选地，干燥进行1至30天，优选1至15天。
通常在优选包含0至80克水/千克空气、5体积%至25体积%的氧气含量和0体积%至10体积%的二氧化碳含量的空气下进行干燥；例如，该空气是来自烃，优选甲烷的燃烧的空气，或在加热空气下进行干燥。
优选地，在空气下在300至1000℃，优选350至900℃的温度下进行煅烧。优选地，煅烧进行1至72小时，优选2至48小时。
再更优选地，在两个步骤中进行煅烧：在120至250℃之间1至10小时的第一温度稳定期，然后在300至950℃之间2至24小时的第二温度稳定期。
通常，在燃烧空气，优选包含40至80克水/千克燃烧空气、5体积%至15体积%的氧气含量和4体积%至10体积%的CO2含量的来自甲烷燃烧的空气下进行煅烧步骤。
步骤g) (Ti前体的浸渍)
在根据本发明的方法的步骤g)的过程中，将包含至少一种可溶性钛前体的溶液浸渍在步骤f)中获得的多孔整料的孔隙中。
优选地，钛前体选自醇钛；非常优选地，钛前体选自异丙醇钛或原钛酸四乙酯，独自或作为混合物。
任选地，可以独自或与醇钛前体一起使用至少一种其它无机钛前体，其为离子类型或溶胶形式。
步骤h) (任选熟化步骤)
在根据本发明的方法的步骤h)的过程中，在步骤g)中获得的多孔整料在湿状态下熟化。
优选地，熟化步骤然后在5至80℃，优选20至75℃的温度下进行0.5至30天，优选1至15天。
步骤i) (干燥和煅烧)
在根据本发明的方法的步骤h)的过程中，在步骤g)或h)中获得的多孔整料在空气下干燥和煅烧以获得含TiO2的多孔整料。
优选地，在5至80℃，优选20至75℃的温度下进行干燥。优选地，干燥进行1至30天，优选1至15天。
通常在包含0至80克水/千克燃烧空气、5体积%至25体积%的氧气含量和0体积%至10体积%的二氧化碳含量的来自烃，优选甲烷的燃烧的空气或加热空气下进行干燥。
优选地，在空气下在300至1000℃的温度下进行煅烧。优选地，煅烧进行1至72小时，优选2至48小时。
优选地，在空气下煅烧的步骤用在80至150℃之间1至10小时的第一温度稳定期，然后在大于150和小于或等于250℃ 1至10小时的第二温度稳定期和最后在300至700℃之间0.5至24小时的第三温度稳定期进行。
通常，在燃烧空气，优选包含40至80克水/千克燃烧空气、5体积%至15体积%的氧气含量和4体积%至10体积%的CO2含量的来自甲烷燃烧的空气下进行煅烧步骤。
根据一个变体，TiO2可在所述方法的任一步骤中和通过本领域技术人员已知的任何方法用选自金属离子，例如元素V、Ni、Cr、Mo、Fe、Sn、Mn、Co、Re、Nb、Sb、La、Ce、Ta或Ti，非金属元素，例如C、N、S、F或P，或金属和非金属元素的混合物的一种或多种元素掺杂。
根据一个变体，在步骤a)、b)和/或g)中，任选在步骤i)后加入金属或氧化状态的选自元素周期表的第IA、IIA、VIIIB、IB和IIIA族元素的元素M的前体。该前体可为溶解在溶液中的形式、固体粉末形式或溶胶形式。
当试图获得完全或部分为其金属形式的元素M时，有可能在步骤i)后进行在氢气料流下在100至600℃的温度下还原0.5至24h的步骤。
非限制性地，根据本发明的含TiO2的多孔整料可有利地用于通过水的解离生产氢气(dihydrogen)的光催化。
下列实施例例示本发明而不限制其范围。
实施例
实施例1: 固体A（非根据本发明）TiO2整料
将1克聚乙二醇（AldrichTM，MW = 20 000）添加到2毫升蒸馏水中，然后与1毫升盐酸溶液（37重量%，AldrichTM，纯度97%）混合。在环境温度下将1.1克异丙醇钛（AldrichTM，纯度97%）添加到该混合物中并搅拌所得混合物直至获得明显单相混合物。
然后将该混合物倒入内径5.5厘米的Petri培养皿，将其置于饱和器（由饱和器根据蒸气压定律调节水蒸气含量）7天以在环境温度下胶凝。
所得凝胶然后用异丙醇（AldrichTM，纯度> 99.5%）相继洗涤两次，然后在环境温度下干燥2天。最后，凝胶在马弗炉中在空气下在180℃下煅烧2小时，然后在350℃下煅烧6小时。
然后以TiO2基多孔整料的形式获得固体A。
固体A具有0.16 ml/g的介孔体积、0.19 ml/g的I型大孔体积和2.3 ml/g的II型大孔体积。固体A具有94 m2/g的比表面积。
多孔整料A具有0.23 g/ml的堆密度。
实施例2: 固体B（非根据本发明）TiO2整料
将1.12克溴化十四烷基三甲基铵（AldrichTM，纯度> 99%）添加到2毫升蒸馏水中，然后与1毫升盐酸溶液（37重量%，AldrichTM，纯度97%）混合。在环境温度下将2.2克异丙醇钛（AldrichTM，纯度97%）添加到该混合物中并搅拌所得混合物直至获得明显单相混合物。
将7克庚烷（AldrichTM，纯度> 99%）在搅拌下缓慢引入该混合物直至形成乳液。
然后将0.4毫升氨水溶液（AldrichTM，ACS试剂，28.0-30.0% NH3基础）添加到该乳液中。
然后将该乳液倒入内径5.5厘米的Petri培养皿，将其置于饱和器7天以在环境温度下胶凝。
所得凝胶然后第一次用无水四氢呋喃（AldrichTM，纯度> 99%）洗涤，然后用按体积计70/70的无水四氢呋喃/丙酮混合物（VWRTM，ACS级）相继洗涤两次。
该凝胶然后在环境温度下干燥7天。最后，凝胶在马弗炉中在空气下在200℃下煅烧2小时，然后在450℃下煅烧6小时。
然后以TiO2基多孔整料的形式获得固体B。
固体B具有0.29 ml/g的介孔体积、0.30 ml/g的I型大孔体积和小于0.4 ml/g的II型大孔体积。固体B具有135 m2/g的比表面积。
多孔整料B具有1.1 g/ml的堆密度。
实施例3: 固体C（根据本发明）TiO2/SiO2整料
将1.12克溴化十四烷基三甲基铵（AldrichTM，纯度>99%）添加到2毫升蒸馏水中，然后与1毫升盐酸溶液（37重量%，AldrichTM，纯度97%）混合。在环境温度下将1.02克原硅酸四乙酯（AldrichTM，纯度> 99%）添加到该混合物中并搅拌所得混合物直至获得明显单相混合物。
将7克十二烷（AldrichTM，纯度> 99%）在搅拌下缓慢引入该混合物直至形成乳液。
然后将该乳液倒入内径5.5厘米的Petri培养皿，将其置于饱和器7天以在环境温度下胶凝。
所得凝胶然后第一次用无水四氢呋喃（AldrichTM，纯度> 99%）洗涤，然后用按体积计70/30的无水四氢呋喃/丙酮混合物（VWRTM，ACS级）相继洗涤两次。
该凝胶然后在环境温度下干燥7天。最后，凝胶在马弗炉中在空气下在180℃下煅烧2小时，然后在650℃下煅烧5小时。然后获得总孔隙体积为10.5 ml/g的SiO2基多孔整料。
在搅拌下制备含有34毫升蒸馏水、44.75毫升异丙醇（AldrichTM，纯度> 99.5%）、10.74毫升盐酸（37重量%，AldrichTM，纯度97%）和10.50毫升异丙醇钛（AldrichTM，纯度97%）的溶液。将与总孔隙体积对应的一部分这种溶液浸渍在整料的孔隙中，然后在环境温度下熟化12小时。该整料然后在环境气氛下干燥24小时。二次重复该步骤。最后，该整料在马弗炉中在空气下在120℃下煅烧2小时，然后在180℃下煅烧2小时，最后在400℃下煅烧1小时。然后获得包含在SiO2基质中的TiO2的多孔整料。
固体C具有0.20 ml/g的介孔体积、1.15 ml/g的I型大孔体积和5.8 ml/g的II型大孔体积。固体C具有212 m2/g的比表面积。通过ICP-AES测得的Ti元素的含量为27.35重量%，其等同于在固体C中52.1重量%的TiO2半导体。
多孔整料C具有0.14 g/ml的堆密度。
实施例4: 固体用于通过在气相中的水解离光催化生产氢气的用途
对多孔整料A、B和C施以在配有由石英制成的光学窗口和在光学窗口对面的玻璃料（将固体沉积在其上）的流通床连续钢反应器中通过在气相中的水解离光催化生产氢气的试验。
将整料置于玻璃料上，它们的直径等于反应器的直径。所有光催化剂的辐照表面积为8.042477 x 10-04 m2。在环境温度下在大气压下进行试验。3 ml/min的氩气流速在分配到反应器中之前经过水饱和器。每4分钟通过微型气相色谱法分析流出物，以监测由在饱和器中夹带的水的光催化还原制成的氢气气体的产量。由Xe-Hg灯（AsahiTM，MAX302TM）提供UV-可见光辐照源。对于315至400 nm的波长范围，辐照功率始终保持在80 W/m2。该试验的持续时间为20小时。
光催化活性以µmol制成的氢气/小时/克TiO2表示。它们是在试验的整个持续期间的平均活性。结果列在下表1中。
表1: 就用于由氩气和H2O的混合物在气相中生产氢气的平均活性计的光催化剂
的性能水平
活性值表明根据本发明的固体在用于通过水的解离光催化生产氢气时表现出更好的性能水平。
Claims (15)
1.一种多孔整料，其包含相对于整料的总重量计20重量%至70重量%的TiO2、相对于整料的总重量计30重量%至80重量%的选自二氧化硅、氧化铝或二氧化硅-氧化铝的耐火氧化物，其特征在于所述多孔整料包含小于0.19 g/ml的堆密度。
2.如权利要求1中所述的整料，其特征在于所述多孔整料包含小于0.16 g/ml的堆密度。
3.如权利要求1或权利要求2中所述的整料，其特征在于其包含对于0.2至50 nm的孔径而言0.1至1 ml/g的介孔体积。
4.如权利要求1或权利要求2中所述的整料，其特征在于其包含0.1至3 ml/g的I型大孔体积，其孔径大于50 nm和小于或等于1000 nm。
5.如权利要求1或权利要求2中所述的整料，其特征在于其包含0.1至8 ml/g的II型大孔体积，其孔径大于1 µm和小于或等于10 µm。
6.如权利要求 1至5任一项中所述的整料，其特征在于其包含介孔率和/或I型大孔率和/或II型大孔率。
7.如权利要求 1至6任一项中所述的整料，其特征在于其也包含对于大于10 µm的孔径而言小于0.5 ml/g的大孔体积。
8.如权利要求 1至7任一项中所述的整料，其特征在于其包含150至700 m2/g的BET比表面积。
9.如权利要求 1至8任一项中所述的整料，其特征在于其还包含独自或作为混合物的至少一种选自元素周期表的第IA、IIA、VIIIB、IB和IIIA族元素的元素M，其为金属或氧化状态。
10.如权利要求9中所述的整料，其中元素M的含量为多孔整料的总重量的0.001重量%至20重量%。
11.如权利要求 1至10任一项中所述的整料，其特征在于其还包含选自金属元素，例如元素V、Ni、Cr、Mo、Fe、Sn、Mn、Co、Re、Nb、Sb、La、Ce、Ta或Ti，非金属元素，例如C、N、S、F或P，或金属和非金属元素的混合物的一种或多种掺杂元素。
12.如权利要求11中所述的整料，其中掺杂元素的含量为多孔整料的总重量的0.001重量%至5重量%。
13.一种制备如权利要求 1至12任一项中所述的多孔整料的方法，其包括下列步骤：
a) 将含表面活性剂的溶液与酸性水溶液混合以获得含表面活性剂的酸性水溶液；
b) 将至少一种硅和/或铝前体添加到在步骤a)中获得的溶液中；
c) 将至少一种与在步骤b)中获得的溶液不混溶的液体有机化合物添加到在步骤b)中获得的溶液中以形成乳液；
d) 在步骤c)中获得的乳液在湿状态下熟化以获得凝胶；
e) 用有机溶液洗涤在步骤d)中获得的凝胶；
f) 将在步骤e)中获得的凝胶干燥和煅烧以获得多孔整料；
g) 将包含至少一种可溶性钛前体的溶液浸渍在步骤f)中获得的多孔整料的孔隙中；
h) 任选地，在步骤g)中获得的多孔整料在湿状态下熟化；
i) 将在步骤g)或h)中获得的多孔整料干燥和煅烧以获得含TiO2的多孔整料。
14.如权利要求13中所述的方法，其中在步骤i)中，在5至80℃的温度下进行干燥并在300至1000℃的温度下进行煅烧。
15.如权利要求13或权利要求14中所述的方法，其中在步骤i)中，在两个相继步骤中进行煅烧：在120至250℃之间1至10小时的第一温度稳定期，然后在300至950℃之间2至24小时的第二温度稳定期。
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| CN104150525A (zh) * | 2014-08-21 | 2014-11-19 | 安徽理工大学 | 氧化物多孔材料及其普适性制备方法 |
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| GB2199541A (en) | 1986-10-16 | 1988-07-13 | Rig Design Services | Production of engineering drawings |
| US5322821A (en) * | 1993-08-23 | 1994-06-21 | W. R. Grace & Co.-Conn. | Porous ceramic beads |
| FR2937970B1 (fr) | 2008-10-30 | 2012-06-15 | Univ Paris Curie | Procede de preparation d'un monolithe de carbone ou de ceramique alveolaire comportant un reseau poreux hierarchise |
| FR2975309A1 (fr) | 2011-05-19 | 2012-11-23 | Centre Nat Rech Scient | Monolithe macrocellulaire de dioxyde de titane, procede de preparation, utilisation a titre de photocatalyseur et procede de decontamination |
| FR3011547B1 (fr) * | 2013-10-03 | 2015-12-11 | Centre Nat Rech Scient | Materiau composite solide alveolaire comportant des nanoparticules metalliques, procede de preparation et utilisations pour le stockage reversible de l'hydrogene |
| FR3016813B1 (fr) | 2014-01-27 | 2017-11-24 | Total Sa | Materiau a base de ti02 absorbant dans le visible et procede pour sa fabrication |
| JP2016143742A (ja) * | 2015-01-30 | 2016-08-08 | シャープ株式会社 | 波長変換部材、発光装置、および波長変換部材の製造方法 |
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Also Published As
| Publication number | Publication date |
|---|---|
| US11077427B2 (en) | 2021-08-03 |
| JP2020517443A (ja) | 2020-06-18 |
| FR3065649A1 (fr) | 2018-11-02 |
| EP3615210A1 (fr) | 2020-03-04 |
| FR3065649B1 (fr) | 2020-05-29 |
| JP7203755B2 (ja) | 2023-01-13 |
| US20210101133A1 (en) | 2021-04-08 |
| AU2018258982A1 (en) | 2019-10-17 |
| WO2018197432A1 (fr) | 2018-11-01 |
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