CN104944452A - 高表面积层状双氢氧化物及其制备方法 - Google Patents
高表面积层状双氢氧化物及其制备方法 Download PDFInfo
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- CN104944452A CN104944452A CN201510126181.7A CN201510126181A CN104944452A CN 104944452 A CN104944452 A CN 104944452A CN 201510126181 A CN201510126181 A CN 201510126181A CN 104944452 A CN104944452 A CN 104944452A
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- hydroxide
- layered double
- charged ion
- negatively charged
- solvent
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- 238000002360 preparation method Methods 0.000 title abstract description 8
- 150000004679 hydroxides Chemical class 0.000 title abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000002904 solvent Substances 0.000 claims abstract description 30
- 239000003960 organic solvent Substances 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 150000002500 ions Chemical class 0.000 claims description 46
- 239000006185 dispersion Substances 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 229910052782 aluminium Inorganic materials 0.000 claims description 20
- 230000032683 aging Effects 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 11
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- 229910052802 copper Inorganic materials 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 238000005507 spraying Methods 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- -1 bicarbonate radical Chemical class 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 9
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
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- 239000001301 oxygen Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 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 5
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims description 4
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- 125000000129 anionic group Chemical group 0.000 claims description 4
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- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
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- 239000000243 solution Substances 0.000 description 20
- 238000001878 scanning electron micrograph Methods 0.000 description 8
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
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- 239000002243 precursor Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- 230000001133 acceleration Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
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- 239000011734 sodium Substances 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 125000002091 cationic group Chemical group 0.000 description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 2
- 229960001545 hydrotalcite Drugs 0.000 description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- 238000001694 spray drying Methods 0.000 description 2
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- LOIYMIARKYCTBW-OWOJBTEDSA-N trans-urocanic acid Chemical compound OC(=O)\C=C\C1=CNC=N1 LOIYMIARKYCTBW-OWOJBTEDSA-N 0.000 description 2
- LOIYMIARKYCTBW-UHFFFAOYSA-N trans-urocanic acid Natural products OC(=O)C=CC1=CNC=N1 LOIYMIARKYCTBW-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 239000011248 coating agent Substances 0.000 description 1
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- 239000013078 crystal Substances 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
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- 238000010899 nucleation Methods 0.000 description 1
- ILUJQPXNXACGAN-UHFFFAOYSA-N ortho-methoxybenzoic acid Natural products COC1=CC=CC=C1C(O)=O ILUJQPXNXACGAN-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- 238000002459 porosimetry Methods 0.000 description 1
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- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
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Abstract
本发明涉及高表面积层状双氢氧化物及其制备方法。所述层状双氢氧化物具有至少125m2/g的高表面积以及式(I),其中M和M’是不同的且各自是带电荷的金属阳离子且必须存在,z=1或2;y=3或4,0<x<0.9,b是0至10,c是0至10,X是阴离子,n是阴离子上的电荷,且a=z(1-x)+xy-2;AMO-溶剂是与水混溶的有机溶剂。本发明还描述了制备所述高表面积层状双氢氧化物的方法。所述高表面积产物具有低粒度并且特别适合用作催化剂、催化剂载体、吸附剂和涂层。[Mz+ 1-xM’y+ x(OH)2]a+(X n-)a/n·bH2O·c(AMO-溶剂) (I)。
Description
技术领域
本发明涉及高表面积层状双氢氧化物(layered double hydroxide)(LDH)及其制备方法。
背景技术
层状双氢氧化物(LDH)是一类包括两种金属阳离子并且具有层状结构的化合物。在Structure and Bonding;Vol 119,2005,Layered DoubleHydroxides ed.X Duan and D.G.Evans中提供了LDH的综述。水滑石(hydrotalcite)(或许是LDH的最知名的例子),已经研究了多年。LDH能在该结构的层之间嵌入阴离子。WO99/24139公开了利用LDH来分离阴离子,包括芳香族和脂肪族的阴离子。
由于LDH相对高的表面电荷和亲水性,常规合成的LDH的颗粒或晶体一般是高度聚集的。这样的结果是,当制备时,LDH聚集形成具有最高达到几百微米的较大粒度以及一般为5至15m2/g的低比表面积的“石状”、无孔体(例如Wang等人在Catal.Today 2011,164,198中公开的)。例如Adachi-Pagano等人(Chem.Commun.2000,91)报道的相对高表面积的LDH具有比表面积不高于5到120m2/g。
在某些应用中(例如吸附剂或催化剂载体),提供具有比目前所知更高表面积的LDH也是有利的。相对高的表面积可导致更多数量的活性位点以及促进从表面到本体的质量传输(mass transport)。
发明内容
我们已经发现高表面积的LDH能够以成本有效的方式通过简单方法制备,与其他已知方法相比该方法涉及更少的操作步骤以及使用更少量的有机溶剂。这种简单方法比先前已知的方法更适合大规模生产。
因此,本发明提供了制备比表面积为至少120m2/g并且具有下式的层状双氢氧化物A的方法:
[Mz+ 1-xM’y+ x(OH)2]a+(X n-)a/n·bH2O·c(AMO-溶剂) (I)
其中M和M’是不同的且各自是带电荷的金属阳离子(且必须存在),z=1或2;y=3或4,0<x<0.9,b是0至10,c是0至10,X是阴离子,n是阴离子上的电荷,且a=z(1-x)+xy-2;AMO-溶剂是可与水混溶的有机溶剂,
所述方法包括
a)从含有金属M和M’的阳离子和阴离子Xn-的溶液中沉淀具有下式的层状双氢氧化物B
[Mz+ 1-xM’y+ x(OH)2]a+(X n-)a/n·bH2O,
其中M、M’、z、y、x、a、b和X如上面定义;
b).在原始溶液中老化在步骤a)中获得的层状双氢氧化物B沉淀物;
c).收集,然后洗涤该层状双氢氧化物B沉淀物;
d).将湿的层状双氢氧化物B分散在AMO-溶剂中以便在该溶剂中生成层状双氢氧化物A的浆液;
e).保持在步骤d)中得到的分散体;以及,
f).回收并干燥该层状双氢氧化物A。
在本发明方法的步骤a)中,层状双氢氧化物B通常通过将含有金属M和M’离子的前体水溶液添加到含有阴离子X的溶液中而制备,该含有阴离子X的溶液可还含有NaOH或将NaOH溶液单独地加入到该溶液中用以调节溶液PH到预定值,通常大于7,优选大于9,更优选10-12。根据优选的实施方式,理想的是在强烈搅拌下将金属前体溶液快速加入阴离子溶液,因为这促进LDH快速成核。我们已经发现这种快速添加和快速共沉淀阶段引起LDH胶体形成以具有更小且更薄的粒度。该LDH在原始反应液中进行老化,并且,优选地,含有沉淀的LDH的溶液老化少于24小时,优选少于16小时,并且更优选少于3小时。在该方法的步骤c)中,将沉淀的层状双氢氧化物B收集并洗涤。通常,沉淀物通过过滤收集。收集之后,洗涤沉淀物至洗涤液具有大体中性的PH,例如,PH±0.5。通常用去离子水洗涤。优选地,水洗涤之后,该沉淀的LDH用AMO-溶剂冲洗。
根据本发明的方法,将收集并洗涤过的LDH重新分散在AMO-溶剂中以便制备处于溶剂中的LDH的浆液。该AMO-溶剂是一种可与水混溶的溶剂。优选地,AMO-溶剂具有的溶剂极性(P)在3.8至9范围内。溶剂极性(P)是基于Snyder和Kirkland报道的实验溶解度数据限定的(Snyder,L.R.;Kirkland,J.J.in Introduction to modern liquidchromatography,2nd ed.;John Wiley and Sons:New York,1979;pp248-250)。一般来讲,可使用任何合适的有机溶剂但是优选选自丙酮、乙腈、二甲基甲酰胺、二甲基亚砜、二氧杂环己烷、乙醇、甲醇、正丙醇、异丙醇或四氢呋喃中的一种。根据特别优选的实施方式,有机溶剂是丙酮。
LDH在有机溶剂中的分散体优选保持至少三小时。优选分散体在搅拌和/或搅动下保持。搅动可使用磁力搅拌器实施,其搅拌速度优选至少300rpm并且更优选至少100rpm。可替代地,可使用具有圆周速率至少0.5m/s的旋桨式搅拌器。这种老化处理是得到具有高表面积的LDH必不可少的。我们已经发现最终产物的表面积取决于LDH在有机溶剂中的分散体老化的时间长度。优选地,LDH在有机溶剂中的浆液老化最长达96小时,例如从1天到4天的时间。更优选地,老化时间将在1天到3天的范围内,因为我们已经发现在老化的首个72小时之后的老化期间出现的LDH表面积的增长不明显。通常,LDH在有机溶剂中的分散体将老化48到72小时。我们还发现如果在处于有机溶剂中的LDH的分散体进行老化之后,去除有机溶剂,并且将LDH重新分散在新的有机溶剂中,对最终产物是有益的。当LDH重新分散时,该LDH在新有机溶剂中的新的分散体可以保持最长达2小时。
该LDH在有机溶剂中的老化的分散体,或者如果LDH重新分散在新的有机溶剂中,然后重新分散体经历一种过程,从而回收并干燥LDH。我们已经发现最终干燥产物的比表面积取决于所使用的干燥过程。
根据一个优选的实施方式,回收并干燥LDH的步骤d)包括从有机溶剂中过滤LDH然后干燥所收集的LDH。干燥可在真空或非真空烘箱中进行。通常,烘箱干燥将在相对低的温度下进行,该温度取决于有机溶剂挥发的温度。优选地,当AMO-溶剂是丙酮时,干燥步骤将在室温(20℃)到60℃范围内的温度下进行。在根据丙酮用作有机溶剂的优选实施方式中,我们发现约60℃的烘箱温度可用于干燥收集的LDH。我们发现尽管在60℃烘箱中干燥过夜的产物具有约142m2/g的比表面积,在真空烘箱中在开放容器中干燥过夜的类似产物具有180m2/g或更大的比表面积。
根据一个不同的优选实施方式,该方法的步骤d)包括将LDH在有机溶剂中的分散体传送到喷雾干燥装置中然后喷雾干燥该分散体,一般使用如氮气的惰性氛围从而制备喷雾干燥的LDH。
我们已经发现使用喷雾干燥过程从处于AMO-溶剂中的分散体得到干燥LDH产物,最终LDH产物的表面积比通过过滤然后烘箱干燥过滤的材料得到的LDH产物显著增加。此外,从我们所得到的结果中可见,所得到的最终LDH的比表面积取决于分散体到喷雾干燥器的进料速率以及喷雾干燥器进出口的温度。在所给的例子中展示,使用进料速率在10-15mL/min范围内,进口温度87℃以及出口温度58℃喷雾干燥的在丙酮中LDH的分散体(仅老化1小时),给出最终喷雾干燥产物具有比表面积约316m2/g,而使用进料速率在20-25mL/min范围内,进口温度95℃以及出口温度57℃喷雾干燥的相同分散体,给出最终喷雾干燥产物具有比表面积约333m2/g。因此,根据优选的实施方式,在AMO-溶剂中LDH分散体进料到喷雾干燥器的进料速率为至少12mL/min,更加优选18mL/min,并且最优选约24mL/min。
在针对LDH给出的式(I)中,M可以是单个金属阳离子或不同金属阳离子的混合物。例如,当z是2时,M可选自Mg、Ca或Zn或者过渡金属阳离子如Fe、Ni、Co、Mn或Cu,而当z是1时,M可以是Li。优选M是Mg、Zn、Fe、Ca、Ni、Co、Mn、Cu或者它们的两种以上的混合物。
M’可以是单个金属阳离子或不同金属阳离子的混合物。例如,当y=3时,M’可选自Al、Ga、Y、In、Fe、Co、Ni、Mn、Cr、Ti、V或La,并且当y=4时,M’可选自Sn、Ti或Zr或者它们的混合物。优选的M’是Al。y的优选值是3。
优选地,z是2且M是Ca或Mg或Zn或Fe。
优选的LDH是Mg/Al、Ca/Al、Ni/Al、Cu/Al或Zn/Al。
x的优选值是0.2到1,优选0.22到0.5,更优选0.23到0.4。
LDH中的阴离子可以是任何适当的有机或无机阴离子,例如卤化物(如氯化物)、无机含氧阴离子(oxyanion)(如XmOn(OH)p -q;m=1-5;n=2-10;p=0-4;q=1-5;X=B、C、N、S、P:如碳酸根、碳酸氢根、磷酸氢根、磷酸二氢根、亚硝酸根、硼酸根、硝酸根、磷酸根、硫酸根)、阴离子型表面活性剂(如十二烷基硫酸钠、脂肪酸盐或硬脂酸钠)、阴离子发色团、和/或阴离子型UV吸收剂,例如,4-羟基-3-10甲氧基苯甲酸、2-羟基-4-甲氧基二苯甲酮-5-磺酸(HMBA)、4-羟基-3-甲氧基-肉桂酸、对-氨基苯甲酸、以及或咪唑丙烯酸(urocanic acid)。根据本发明的一个实施方式,c的值大于0。以下的例子展示了LDH化合物的制备,其中c是0.1。
本发明还涉及通过以下方法制备的层状双氢氧化物A,所述方法包括
a)从含有金属M和M’的阳离子和阴离子Xn-的溶液中沉淀层状双氢
氧化物B,其具有下式
[Mz+ 1-xM’y+ x(OH)2]a+(X n-)a/n·bH2O
其中M和M’是不同的且各自是带电荷的金属阳离子,z=1或2;y=3
或4,0<x<0.9,b是0至10,X是阴离子,n是阴离子上的电荷,且
a=z(1-x)+xy-2;
b)在原始溶液中老化在步骤a)中得到的层状双氢氧化物B沉淀物;
c)收集,然后洗涤层状双氢氧化物B沉淀物;
d)将湿的层状双氢氧化物B分散在AMO-溶剂中,以便生成处于该溶剂中的层状双氢氧化物A的浆液;
e)保持在步骤d)的分散体;以及,
f)回收并干燥该层状双氢氧化物A;其中该层状双氢氧化物A具有的比表面积为至少125m2/g。
优选地,当z是2时,M是Mg、Zn、Fe、Ca、Zn、Ni、Cu、Co、Mn或Cd或者它们的两种或更多种的混合物,或当z是1时,M是Li。优选地,当y=3时,M’是Al、Ga、Y、In、Fe、Co、Ni、Mn、Cr、Ti、V或La,或当y=4时,M’是Sn、Ti或Zr或者它们的混合物。
根据优选的实施方式,M’是Al。该层状双氢氧化物A将特别地是选自Zn/Al、Mg/Al、Ca/Al、Ni/Al、以及Cu/Al中的物质。最优选地,该层状双氢氧化物A是Mg/Al层状双氢氧化物。
通常,X是选自卤化物、无机含氧阴离子、阴离子型表面活性剂、阴离子发色团、以及阴离子型UV吸收剂中至少一种的阴离子。无机含氧阴离子的例子包括碳酸根、碳酸氢根、磷酸氢根、磷酸二氢根、亚硝酸根、硼酸根、硝酸根、硫酸根或磷酸根、或者它们的两种或更多种的混合物。
本发明的层状双氢氧化物A具有比表面积为至少125m2/g,优选至少240m2/g。
本发明的层状双氢氧化物A优选具有BET孔体积(N2)为至少0.5cc/g,更优选至少1.0cc/g。
本发明的层状双氢氧化物A优选具有粒度小于150μm,更优选粒度小于30μm。
当层状双氢氧化物A在步骤f)中通过喷雾干燥进行干燥时,通常具有聚结粒度小于100μm,优选小于30μm。
根据一个不同的方面,本发明提供了Mg-Al-CO3层状双氢氧化物A,其具有比表面积为至少300m2/g,优选至少314m2/g,更优选至少330m2/g。
根据本发明的材料特别适用于各种各样的应用,例如作为催化剂、催化剂载体、吸附剂和涂层。
在以下的实施例中,所使用的表征方法是:
X射线衍射(XRD)—使用Cu Ka辐射在反射模式下在PANalyticalX’Pert Pro仪器上记录XRD图案。使用狭缝尺寸为1/4度,从1°至70°在0.01°s-1下,使用40mA电流(λ=1.542°)在40kV下设定加速电压。
透射电子显微镜(TEM)—在加速电压为400kV的JEOL 2100显微镜上进行TEM分析。使用超声将样品分散在乙醇中然后浇铸到涂覆有lacey碳膜的铜TEM栅格上。
扫描电子显微镜(SEM)—在加速电压为20kV的JEOL JSM 6100扫描电镜上进行SEM分析。将粉末样品涂布到附着在SEM平台(SEM stage)的碳带(carbon tape)上。在观察前,样品用厚的铂层溅射涂覆以防止带电荷并且提高图像质量。
BET比表面积—BET比表面积是通过从Quantachrome Autosorb-6B表面积和孔径分析仪上收集的77K下的N2吸附和脱附等温线测量的。在每次测量之前,LDH样品首先在110℃下脱气过夜。
附图说明
图1是干燥前由实施例1获得的Mg3Al-CO3LDH的TEM图像。
图2是喷雾干燥后由实施例1获得的Mg3Al-CO3LDH的SEM图像。
图3是干燥前由实施例1获得的Mg3Al-CO3LDH的XRD图案,a)仅用水洗涤,b)分散在丙酮中持续48小时。
图4是通过烘箱干燥后由实施例2获得的Mg3Al-CO3LDH的SEM图像。
图5是通过喷雾干燥后由实施例2获得的Mg3Al-CO3LDH的SEM图像。
图6是通过烘箱干燥后由实施例3获得的Mg3Al-CO3LDH的SEM图像。
图7是通过喷雾干燥后由实施例3获得的Mg3Al-CO3LDH的SEM图像。
具体实施方式
实施例
实施例1
通过将9.6g Mg(NO3)2·6H2O和4.68g Al(NO3)3·9H2O溶解在50mL去离子水中来制备金属前体(metal precursor)溶液。通过将4g NaOH和2.65g Na2CO3溶解在200mL去离子水中来制备碱溶液。在强烈搅动下将金属前体溶液快速加入到碱溶液中。30min后,所得的浆液通过过滤收集并依次用水和丙酮彻底洗涤。在60℃下在搅拌下将洗涤过的滤饼重新分散在丙酮(200mL)中。48h后,去除悬浮液中的丙酮并引入新丙酮(200mL)。所得到的新的悬浮液在室温下搅拌2h。将悬浮液过滤以收集LDH固体,然后用丙酮彻底洗涤所收集的LDH固体。最终产物[Mg0.75Al0.25(OH)2](CO3)0.125·0.4H2O·0.1(丙酮)=(Mg3Al-CO3LDH)在60℃烘箱中干燥过夜。
所得的Mg3Al-CO3LDH的BET表面积和孔体积在表1中显示。干燥前的Mg3Al-CO3形态在图1呈现。经喷雾干燥器干燥后的Mg3Al-CO3LDH形态的SEM图像在图2中呈现。通过X射线衍射检测所获得的Mg3Al-CO3LDH的纯度如图3所示。
表1.由实施例1获得的Mg3Al-CO3LDH的BET表面积和孔体积
实施例2
通过将200mL Mg(NO3)2·6H2O(0.15mol)和Al(NO3)3·9H2O(0.05mol)的溶液逐滴地加入到200mL Na2CO3(0.10mol)溶液中,滴加速率在0.1-3.5mol(Mz++My+)/(mol阴离子*min)范围内,来合成[Mg0.75Al0.25(OH)2](CO3)0.125·0.4H2O·0.1(丙酮)=Mg3Al-CO3LDH。利用NaOH溶液(4M)将沉淀溶液的PH值控制在10,所得的浆液在室温下放置16hrs。获得的LDH浆液过滤并用去离子水洗涤直至获得PH=7,然后通过吸滤漏斗用500mL丙酮洗涤过滤的固体。将“湿饼”重新分散在1000mL丙酮中持续1hr。
将制备、悬浮在丙酮中的一半LDH,用65℃烘箱干燥,而另一半,在N2氛围中通过喷雾干燥进行干燥。所得的[Mg0.75Al0.25(OH)2](CO3)0.125·0.4H2O·0.1(丙酮)=(Mg3Al-CO3LDH)Mg3-Al-CO3LDH的BET表面积和孔体积在表2中显示。在通过烘箱和喷雾干燥器干燥后Mg3-Al-CO3的形态的SEM图像分别地比较性地呈现在图4和图5中。
表2.由实施例2获得的Mg3-Al-CO3LDH的BET表面积和孔体积
实施例3
通过将200mL Mg(NO3)2·6H2O(0.15mol)和Al(NO3)3·9H2O(0.05mol)的溶液逐滴地加入到200mL Na2CO3(0.10mol)溶液中,滴加速率在0.1-3.5mol(Mz++My+)/(mol阴离子*min)范围内,来合成[Mg0.75Al0.25(OH)2](CO3)0.125·0.1H2O·0.1(丙酮)=Mg3Al-CO3LDH。利用NaOH溶液(4M)将沉淀溶液的PH值控制在10。在初始溶液中老化30min后,所得的浆液过滤并用去离子水洗涤直至获得PH=7。过滤的浆液通过吸滤漏斗用500mL丙酮洗涤随后分散在500mL丙酮中。搅拌16hrs后,过滤悬浮液并引入新丙酮(1000mL)再搅拌1hr。将悬浮在丙酮中的一半的LDH,用65℃烘箱干燥,而另一半,在N2气氛中通过喷雾干燥进行干燥。所获得的Mg3-Al-CO3LDH的BET表面积和孔体积在下面的表3中显示。在通过烘箱和喷雾干燥器干燥后Mg3-Al-CO3的形态的SEM图像分别地比较性地呈现在图6和图7中。
表3.由实施例3获得的Mg3-Al-CO3LDH的BET表面积和孔体积
Claims (33)
1.一种制备具有比表面积至少为125m2/g且具有下式的层状双氢氧化物A的方法:
[Mz+ 1-xM’y+ x(OH)2]a+(Xn-)a/n·bH2O·c(AMO-溶剂) (I)
其中M和M,是不同的且各自是带电荷的金属阳离子且必须存在,z=1或2;y=3或4,0<x<0.9,b是0至10,c是0至10,X是阴离子,n是所述阴离子上的电荷,且a=z(1-x)+xy-2;AMO-溶剂是可与水混溶的有机溶剂,
所述方法包括:
a).从含有金属M和M’的阳离子和阴离子Xn-的溶液中沉淀具有下式的层状双氢氧化物B
[Mz+ 1-xM’y+ x(OH)2]a+(Xn-)a/n·bH2O
其中M、M’、z、y、x、a、b和X如上面定义;
b).在原始溶液中老化在步骤a)中得到的层状双氢氧化物B沉淀物;
c).收集,然后洗涤所述层状双氢氧化物B沉淀物;
d).将湿的层状双氢氧化物B分散在AMO-溶剂中,以便在所述溶剂中生成所述层状双氢氧化物A的浆液;
e).保持在步骤d)中得到的分散体;以及,
f).回收并干燥所述层状双氢氧化物A。
2.根据权利要求1所述的方法,其中所述AMO-溶剂是可与水混溶的有机溶剂,优选具有在3.8至9范围内的溶剂极性。
3.根据权利要求1或权利要求2所述的方法,其中,在式(I)中,当z是2时,M是Mg、Zn、Fe、Ca、Zn、Ni、Cu、Co、Mn或Cd或者这些物质中的两种以上的混合物,或者当z是1时,M是Li。
4.根据权利要求1或权利要求2中任一项所述的方法,其中,在式(I)中,当y是3时,M’是Al、Ga、Y、In、Fe、Co、Ni、Mn、Cr、Ti、V或La,或者当y是4时,M’是Sn、Ti或Zr或它们的混合物。
5.根据权利要求4所述的方法,其中,M’是Al。
6.根据权利要求5所述的方法,其中所述层状双氢氧化物A选自Zn/Al、Mg/Al、Ca/Al、Ni/Al、和Cu/Al。
7.根据权利要求6所述的方法,其中所述层状双氢氧化物A是Mg/Al层状双氢氧化物。
8.根据权利要求1或权利要求2所述的方法,其中X是选自卤化物、无机含氧阴离子、阴离子型表面活性剂、阴离子发色团、以及阴离子型UV吸收剂中至少一种的阴离子。
9.根据权利要求8所述的方法,其中所述无机含氧阴离子是碳酸根、碳酸氢根、磷酸氢根、磷酸二氢根、亚硝酸根、硼酸根、硝酸根、硫酸根或磷酸根,或者它们的两种以上的混合物。
10.根据权利要求1或权利要求2所述的方法,其中在步骤a)中使用在0.1至3.5mol(Mz++My+)/(mol阴离子*min)范围内的滴加速率将所述金属Mz++My+溶液引入到所述阴离子Xn-溶液中形成所述层状双氢氧化物B沉淀物。
11.根据权利要求1或权利要求2所述的方法,其中在步骤a)中从含有所述阳离子和阴离子的溶液中沉淀所述层状双氢氧化物B,所述溶液另外地含有NaOH或者向所述溶液中单独加入NaOH溶液以调节溶液的PH至预定值。
12.根据权利要求1或权利要求2所述的方法,其中在步骤b)中在所述原始溶液中将所述层状双氢氧化物B沉淀物老化少于24小时,优选少于16小时,更优选少于3小时。
13.根据权利要求1或权利要求2所述的方法,其中在步骤c)中通过过滤收集所述层状双氢氧化物B并用水洗涤至洗液的PH基本上是中性,然后用AMO-溶剂冲洗。
14.根据权利要求1或权利要求2所述的方法,其中在步骤d)中在搅拌下将在步骤c)中获得的所述湿的层状双氢氧化物B分散并保持在AMO-溶剂中。
15.根据权利要求1或权利要求2所述的方法,其中在步骤e)中将在步骤d)中获得的所述分散体保持最长达96小时,优选最长达72小时,更优选最长达48小时。
16.根据权利要求1或权利要求2所述的方法,其中在步骤e)之后,将所述层状双氢氧化物A以湿的形式收集并分散在新鲜体积的AMO-溶剂中并将所述分散体保持至少2小时。
17.根据权利要求1或权利要求2所述的方法,其中在步骤f)中,通过过滤回收所述层状双氢氧化物A并将所述回收的层状双氢氧化物A在烘箱中干燥,优选真空烘箱或使用喷雾干燥器。
18.根据权利要求1或权利要求2所述的方法,其中在步骤f)中,回收所述层状双氢氧化物A并通过将处于所述AMO-溶剂中的所述层状双氢氧化物A的分散体在惰性气氛下喷雾干燥而进行干燥。
19.一种通过如下方法制备的层状双氢氧化物A,所述方法包括:
a).从含有所述金属M和M’的阳离子和所述阴离子Xn-的溶液中沉淀具有下式的层状双氢氧化物B
[Mz+ 1-xM’y+ x(OH)2]a+(Xn-)a/n·bH2O
其中M和M,是不同的且各自是带电荷的金属阳离子,z=1或2;y=3或4,0<x<0.9,b是0至10,X是阴离子,n是所述阴离子上的电荷,且a=z(1-x)+xy-2;
b).在原始溶液中老化在步骤a)中得到的层状双氢氧化物B沉淀物;
c).收集,然后洗涤所述层状双氢氧化物B沉淀物;
d).将湿的层状双氢氧化物B分散在AMO-溶剂中,以便生成处于所述溶剂中的所述层状双氢氧化物A的浆液;
e).保持在步骤d)中得到的分散体;以及,
f).回收并干燥所述层状双氢氧化物A;
其中所述层状双氢氧化物A具有比表面积为至少125m2/g。
20.根据权利要求19所述的层状双氢氧化物A,其中当z是2时,M是Mg、Zn、Fe、Ca、Zn、Ni、Cu、Co、Mn或Cd或者这些物质中两种以上的混合物,或者当z是1时,M是Li。
21.根据权利要求19或20中任一项所述的层状双氢氧化物A,其中当y是3时,M’是Al、Ga、Y、In、Fe、Co、Ni、Mn、Cr、Ti、V或La,或者当y是4时,M是Sn、Ti或Zr或它们的混合物。
22.根据权利要求21所述的层状双氢氧化物A,其中,M’是Al。
23.根据权利要求22所述的层状双氢氧化物A,其中所述层状双氢氧化物A选自Zn/Al、Mg/Al、Ca/Al、Ni/Al、以及Cu/Al。
24.根据权利要求23所述的层状双氢氧化物A,其中所述层状双氢氧化物A是Mg/Al层状双氢氧化物。
25.根据权利要求19或权利要求20中任一项所述的层状双氢氧化物A,其中,X是选自卤化物、无机含氧阴离子、阴离子型表面活性剂、阴离子发色团、以及阴离子型UV吸收剂中至少一种的阴离子。
26.根据权利要求25所述的层状双氢氧化物A,其中所述无机含氧阴离子是碳酸根、碳酸氢根、磷酸氢根、磷酸二氢根、亚硝酸根、硼酸根、硝酸根、硫酸根或磷酸根,或者它们的两种以上的混合物。
27.根据权利要求19或权利要求20中任一项所述的层状双氢氧化物A,其中,所述的层状双氢氧化物A具有比表面积为至少240m2/g。
28.根据权利要求19或权利要求20中任一项所述的层状双氢氧化物A,其中所述层状双氢氧化物A具有在N2下BET孔体积为至少0.5cc/g。
29.根据权利要求28所述的层状双氢氧化物A,其中所述层状双氢氧化物A具有在N2下BET孔体积为至少1.0cc/g。
30.根据权利要求19或权利要求20中任一项所述的层状双氢氧化物A,其中所述层状双氢氧化物A具有粒度小于150μm。
31.根据权利要求30所述的层状双氢氧化物A,其中所述层状双氢氧化物A具有粒度小于30μm。
32.根据权利要求19或权利要求20中任一项所述的层状双氢氧化物A,其中所述层状双氢氧化物A在步骤f)中通过喷雾干燥进行干燥并且具有聚结粒度小于100μm。
33.根据权利要求32所述的层状双氢氧化物A,其中,所述层状双氢氧化物A在步骤f)中通过喷雾干燥进行干燥,并且具有聚结粒度小于30μm。
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CN108283929A (zh) * | 2018-01-29 | 2018-07-17 | 陕西科技大学 | 一种钴钒双金属氢氧化物纳米片电解水析氧催化剂的制备方法 |
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US10040695B2 (en) | 2018-08-07 |
US20170107116A1 (en) | 2017-04-20 |
SG11201607636TA (en) | 2016-10-28 |
BR112016021996A2 (pt) | 2017-08-15 |
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JP6616782B2 (ja) | 2019-12-04 |
EP3122687A1 (en) | 2017-02-01 |
GB201405543D0 (en) | 2014-05-14 |
EA031942B1 (ru) | 2019-03-29 |
EP3536668A1 (en) | 2019-09-11 |
WO2015144778A1 (en) | 2015-10-01 |
AU2015238366A1 (en) | 2016-10-06 |
AU2019201645A1 (en) | 2019-04-04 |
ZA201606526B (en) | 2020-05-27 |
CA2942842A1 (en) | 2015-10-01 |
JP2017513791A (ja) | 2017-06-01 |
EP3122687B1 (en) | 2019-05-22 |
IL247933A0 (en) | 2016-11-30 |
EA201691938A1 (ru) | 2016-12-30 |
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