CN1894043A - 制备金属纳米颗粒的方法和由此得到的材料 - Google Patents
制备金属纳米颗粒的方法和由此得到的材料 Download PDFInfo
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- CN1894043A CN1894043A CN200480037393.8A CN200480037393A CN1894043A CN 1894043 A CN1894043 A CN 1894043A CN 200480037393 A CN200480037393 A CN 200480037393A CN 1894043 A CN1894043 A CN 1894043A
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- Prior art keywords
- precursor
- carrier
- metallic element
- clay
- sepiolite
- Prior art date
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- 239000002243 precursor Substances 0.000 claims abstract description 52
- 229910052751 metal Inorganic materials 0.000 claims abstract description 43
- 239000004927 clay Substances 0.000 claims abstract description 39
- 230000008569 process Effects 0.000 claims abstract description 20
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 238000004320 controlled atmosphere Methods 0.000 claims abstract description 8
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- 229960000892 attapulgite Drugs 0.000 claims description 32
- 239000002245 particle Substances 0.000 claims description 25
- 239000006185 dispersion Substances 0.000 claims description 24
- 229910052802 copper Inorganic materials 0.000 claims description 21
- 239000002082 metal nanoparticle Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000010790 dilution Methods 0.000 claims description 13
- 239000012895 dilution Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 9
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- 238000000518 rheometry Methods 0.000 claims description 7
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
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- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
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- 230000000630 rising effect Effects 0.000 claims description 2
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- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- 239000004599 antimicrobial Substances 0.000 claims 1
- 150000001805 chlorine compounds Chemical group 0.000 claims 1
- 150000004820 halides Chemical class 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
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- 238000000151 deposition Methods 0.000 abstract description 5
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 6
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
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- 239000004332 silver Substances 0.000 description 5
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
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- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 3
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- 238000002425 crystallisation Methods 0.000 description 3
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- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
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- 230000000845 anti-microbial effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
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- 229910044991 metal oxide Inorganic materials 0.000 description 2
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- CZTQZXZIADLWOZ-UHFFFAOYSA-O 8-oxo-3-(pyridin-1-ium-1-ylmethyl)-7-[(2-thiophen-2-ylacetyl)amino]-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid Chemical compound C1SC2C(NC(=O)CC=3SC=CC=3)C(=O)N2C(C(=O)O)=C1C[N+]1=CC=CC=C1 CZTQZXZIADLWOZ-UHFFFAOYSA-O 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910000863 Ferronickel Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- 206010067623 Radiation interaction Diseases 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
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- 238000001354 calcination Methods 0.000 description 1
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- 150000001768 cations Chemical class 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
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- 238000002848 electrochemical method Methods 0.000 description 1
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- 239000010433 feldspar Substances 0.000 description 1
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- 239000006166 lysate Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
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- 239000012466 permeate Substances 0.000 description 1
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- 238000001272 pressureless sintering Methods 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
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- 238000012163 sequencing technique Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
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- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
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Abstract
本发明涉及制备金属纳米颗粒的方法和这样得到的材料。本发明更尤其涉及制备金属纳米颗粒的方法,包括:从在低于粘土硅酸盐网络破坏温度的温度下可被还原的金属元素的盐、氢氧化物和氧化物中选择前体;和在选自伪层页硅酸盐粘土的载体上沉积所述前体。根据本发明,该方法包括:(i)在载体上沉积前体的沉积步骤;(ii)当前体选自盐和氢氧化物时,在控制气氛下的热分解步骤,其中前体经过分解处理并被转化成金属元素的氧化物;和(iii)还原步骤,其中在控制气氛下对金属元素的氧化物进行还原处理。上述方法在低于粘土硅酸盐网络破坏温度的温度下进行。
Description
发明技术领域
本发明一般涉及纳米颗粒领域,尤其涉及金属纳米颗粒领域,更尤其涉及均匀分散在载体上的纳米颗粒领域。
现有技术
纳米材料或纳米结构材料为由尺寸在1至100nm范围(10-9-10-7m)之间的颗粒构成的非均匀体系。这些体系具有与尺寸为微米晶粒的等价体系中存在的物理性质大大不同的物理性质。在纳米水平处出现的最显著物理性质中,有量子化现象(电荷、电子能级);限制现象(电子、电介质)[Flytzanis,C.,Hache,F.,Kelin,M.C.,Ricard,D.,和Roussignol,Ph.,“Nonlinear Optics in Composite Materials”,Prog.Optics,29,322(1991)];单畴的存在(晶体、铁磁体)[B.D.Cullity,“Introduction to Magnetic Materials”,Addison-Wesley,California,1972,117-119和309-311],铁电);巨磁阻(magnetorresistance)效应[J.I.Gittleman,Y.Goldstein,和S.Bozowski,Phys.Rev.B 5 3609(1972)];Hall-Petch效应或位错堆积抑制,[H.Gleiter,Progress inMater.Sci.,33,223(1989);V.G.Gryzanov和L.I.Trusov,ProgressMater.Sci.,37289(1993)]等。
目前,针对这些纳米颗粒材料的生产和特性两方面的全球R+D上付出了巨大努力,更远的目标是制造新产品和设备。
特别地,金属纳米颗粒为研究最多的纳米材料之一,因为它们表现出只有绝缘体和导体或两者的混合物才有的物理性质[H.Gleiter,Progress in Mater.Sci.,33,223(1989),V.G.Gryaznov和L.I.Trusov,Progress Mater.Sci.,37289(1993)]。这些材料目前被用于胶体和催化化学过程。另一方面,期望在不久的将来可使用金属纳米颗粒制造“光”和/或电子器件。
目前,纳米颗粒的合成通过几种方法实现,如:机械活化[EricGaffet,Fréderic Bernad,Jean-Claude Niepce,Fréderic Charlot,Chirstophe Gras,Gérard Le Caér,Jean-Louis Guichard,PierreDelcroix,Alain Mocellin和Olivier Tillement,“Some RecentDevelopments in Mechanical Activation and Mechanosynthesis”,Journal of Material Chemistry,9,305-314(1998)];湿合成方法(前体材料的水热和热分解)、溶胶-凝胶[D.G.Morris,“MechanicalBehavior of Nanostructured Materials”,Materials Science Foundations第2卷,Trans Tech Publication Ltd,(1998)];气相中合成,电化学方法[Ebrahimi,F.Bourne,G.R.Kelly,M.S.和Matthews,T.E.,Nanostruct.Mater.,1999,11343];化学外延生长[Veprek,S.J.,Vac.Sci.Technol.A,1999 17 2401];(CVD(化学气相沉积),或利用分子束[Philip Moriarty,Nanostructured Materials,Reports onProgress in Physics,64],297-381(2001))(MBE,分子束外延),离子溅射过程[J.Musil,I.Leipner,M.Kolega,Surf.Coat.Tech,115,32-37,(1999)]等。
根据得到的材料类型,这些技术分为外延技术(MBE,CVD和烧蚀)和大规模技术(所有其它的)。但是,制备这些材料时碰到的一个主要问题是它们群集的趋势,导致纳米尺寸固有的性质消失。在其中实现微结构良好控制的唯一情况下(如在MBE中),制备的材料的数量非常少,这大大增加了可能的制造成本和妨碍了可行的工业开发。这是促进几个集团投入大量努力以在氧化基质中获得完美分散纳米晶体的原因[K.Niihara,“New Design Concept of StructuralCeramics-Ceramic Nanocomposites”,J.Ceram.Soc.Jpn.99(1991)974;S.T.Oh,M.Sando和K,Niihara,“Mechanical and magneticproperties of Ni-Co dispersed Al2O3 nanocomposites”,J.Mater.Sci.36(2001)1817;T.Sekino和K.Niihara,“Microstructural characteristicsand mechanical properties for Al2O3/metal nanocomposites”,Nanostructural Materials,第6卷(1995)663;T.Sekino,T.Nakajima,S.Ueda和K.Niihara,“Reduction and Sintering of a Nickel-Dispersed-Alumina Composite and its Properties”,J.Am.Ceram.Soc.,80,5(1997)1139;M.Nawa,T.Sekino和K.Niihara,“Fabricationand Mechanical Properties of Al2O3/Mo Nancomposites”,J.Mater.Sci.,29(1994)3183;S.T.Oh,T.Sekino和K.Niihara,“Fabricationand Mechanical Properties of 5%vol Copper Dispersed AluminaNanocomposite”,J.Eur.Ceram.Soc.,18(1998)31;R.Z.Chen和W.H.TUan,“Pressureless Sintering of Al2O3/Ni Nanocomposites”,J.Eur.Ceram.Soc.,19(1999)463;K.Niihara,T.Sekino,Y.H.Choa,T.Kusunose,Y.Hayashi,K.Akamatsu,N.Bamba,T.Hirano和S.Ueda“Nanocomposite Structural Ceramics with Advanced Properties”,Proc.4th Japan International SAMPE(1995);K.Niihara,T.Sekino,Y.H.Choa,T.Kusunose,Y.Hayashi,K.Akamatsu,N.Bamba,T.Hirano和S.Ueda,“Nanocomposite Structural Ceramics with AdvancedProperties”,Proc.4th Japan International SAMPE.(1995)]。从工业角度看,在这个领域开发简单、有效和廉价的制备金属纳米颗粒的方法是相当有吸引力的,因为这允许以非常有竞争力的价格根据纳米材料的性质制造新设备。
发明公开内容
本发明的目的是通过均匀分散接触载体的金属化合物在工业规模上实施制备纳米颗粒的简单、经济和可行工序来克服现有技术中存在的大多数障碍,其中载体为选自伪层页硅酸盐粘土的具有硅酸盐网络的至少一种粘土。根据本发明,粘土可为海泡石粘土,包括天然矿物海泡石和处理的海泡石,如流变级海泡石(如TOLSA S.A.,Madrid,Spain以PANGEL牌子销售的那些和通过基本避免纤维断裂并描述在例如专利申请EP-A-0170299和EP-A-0454222中的专用微粉化方法由天然海泡石得到的那些)、矿物或处理的凹凸棒石,如流变级凹凸棒石(如在由美国Engelhard公司制造和商品化的ATTAGEL产品系列中存在的一种,和Floridin公司提供的MINU-GEL产品系列,或通过用专利EP-A-0170299中描述的方法处理凹凸棒石得到的那些)。通常,载体为粒度小于44μm并优选小于5μm的粉末。
海泡石和凹凸棒石或坡缕石属于伪层页硅酸盐粘土,也称为坡缕石-海泡石族,其结构决定了微纤维或针状形貌。
因此,海泡石为水合含镁硅酸盐,但也有含铝海泡石(其中19%的八面体位被铝离子占据)、含铁海泡石(称为铁石棉)、含镍铁海泡石(falcondoite)和含钠海泡石(loughlinite)。坡缕石或凹凸棒石为水合铝镁硅酸盐,具有类似于海泡石结构的结构。根据Brauner和Preisinger,通过由氧原子连接到镁八面体中心层的两层硅四面体组成的滑石型绞线在结构上形成海泡石。这些滑石型绞线以这种方式排列,即硅四面体层是连续的,但硅四面体在六个单元的间隔处被反转。这种结构决定了海泡石颗粒的针状形貌,沿轴c伸长,并存在通道,称为沸石通道,取向于针状颗粒c轴方向上,大小为3.7×10.6,水和其它液体可在这里渗透。由于这种结构,海泡石具有非常高的比表面积,这不仅由于高的外表面,而且由于源于沸石通道的内表面。按照结构模型计算,海泡石的理论总比表面积为900m2/g,其中400m2/g属于外部面积,500m2/g属于内部面积。但是,不是所有的海泡石表面同等地接近全部分子。海泡石的可接近表面取决于使用的吸附质、它的尺寸和它的极性,其决定了吸附质分子到粘土微孔和沸石通道的可接近性。N2可到达的BET表面超过300m2/g,是在天然化合物中发现的最高表面。
凹凸棒石具有类似的结构,但在这种情况下,硅四面体的反转每隔四个四面体发生,而不是海泡石时的每隔六个。结果,凹凸棒石的沸石通道具有3.7×6.4的截面,即小于海泡石通道的那些截面,因此,凹凸棒石的比表面为大约150m2/g,尽管高,但还是小于海泡石的比表面。
海泡石和凹凸棒石的微纤维颗粒在它们的天然状态下成簇排列,簇以类似于干草堆的结构形成随机排列的针状颗粒的巨大束。这样形成的结构极其多孔,并具有高的中孔和大孔体积。通过使用特殊的研磨和微粉化技术,如专利EA-A-0170299中描述的那些,可以解聚这些微纤维束成独立的微纤维颗粒,同时保持高的“长径比”,即长度/直径比。这些程序允许吸收的分子更容易地进入到外部表面,因此增加了吸附可到达的表面。为了消除表面上吸附的水尤其是通过氢键连接到结晶水分子上的水,热处理海泡石和凹凸棒石,结晶水分子构成位于结构边缘的镁原子的配位-在为海泡石时,或构成位于结构边缘的镁和铝原子的配位-在为凹凸棒石时,两者都在内部沸石通道中,如同在位于结构边缘的开放通道中,热处理还用于提高这些粘土的吸附能力。
可使用坡缕石-海泡石粘土中的任何一种实现在粘土表面上得到金属纳米颗粒,例如海泡石、凹凸棒石和它们的组合,和海泡石和/凹凸棒石矿物,只要它们以总和超过50%的浓度,优选超过85%存在,因为其它矿物如方解石、白云石、长石、云母、石英或蒙脱石引起的污染除了稀释可在其上形成纳米颗粒的粘土外,还影响产品的最终性质,以及方法本身的开发,这两种情况既在盐、氢氧化物或氧化物的沉淀过程中,又在为还原金属而应用的热处理过程中。
另外,金属化合物为至少选自金属元素的盐、氢氧化物和氧化物的前体,并且金属元素选自在低于粘土硅酸盐网络坍缩的温度的温度下易于还原的金属元素。一些适当的金属元素为Fe、Co、Ni、Cu、Mo、Ru、Rh、Pd、Ag、W、Re、Os、Ir、Pt、Au和它们的合金或它们的组合。这些金属元素存在于前体如水溶性盐(氯化物、硝酸盐和硫酸盐)中。
本发明描述的程序(方法)还包括在载体上沉积前体的沉积阶段,当所述前体选自盐和氢氧化物时,该程序还需要在控制气氛下的热分解阶段,其中前体分解成所选金属元素的氧化物。然后,进行还原阶段,其中在控制的氧分压(PO2)和温度条件下对金属元素的氧化物进行完全还原过程,最终得到沉积在载体上的金属纳米颗粒。
在低于粘土硅酸盐网络破坏温度的温度下进行该程序,并优选在低于850℃的温度下,因为在更高的温度下,海泡石和凹凸棒石面临完全的结构转换,这导致硅酸盐网络的破坏和在海泡石的玻璃相时可能出现其它态如clinosteatite。
沉积阶段的一种实施方案需要在水中溶解前体得到前体的稀释液,在所述前体稀释液中分散载体得到前体/载体分散体,和干燥前体/载体分散体得到干的前体/载体颗粒。为了提高粘土的分散程度,优选的方法是用高功率剪切叶片施加机械搅拌。
优选地,并根据所需的结果,调整前体稀释液到5-15%的前体浓度,调整稀释在水中或前体稀释液中的载体至5-15%浓度。另外,方便地,作为要在载体表面上得到的所需纳米颗粒密度的函数,可调整载体/前体分散体的金属元素/载体比在0.1∶100至100∶100的范围内,更优选在5∶100至50∶100范围内,按重量计。
当目标是通过升高载体/前体分散体的pH在载体上沉淀前体时,这通过在干燥阶段前用碱实现。必须以控制的方式进行前体的沉淀以便颗粒均匀地沉积在粘土表面上。
而且,在进入干燥阶段前过滤前体/载体分散体,和/或在干燥阶段前通过固/液分离技术来分离。优选进行过滤或固/液分离以分离粘土和沉积在溶液表面上的包含所用金属盐离子的金属前体,但可进行直接干燥以蒸发分散体中存在的全部水。在一些情况下,当通过过滤分离来对粘土和沉积的金属前体进行分离时,建议洗涤粘土以消除任何痕量的可溶性盐。下一步骤是在控制气氛条件下进行的热处理,以实现金属盐或氢氧化物分解成合适的氧化物,条件是沉积在粘土上的前体不是所述氧化物;下一步骤是将金属氧化物还原成合适的金属。还原条件(温度和氧分压)取决于所用的金属元素。
利用上述技术,可以得到沉积在载体上的单分散金属纳米颗粒,通常尺寸小于30nm,并且经常可得到在10nm和5nm之间的控制尺寸,因此形成用于各种应用的纳米颗粒化的“纳米复合材料”材料。因此,当金属元素选自Cu、Ag、Au、Rh、Pd、Ir、Ni、Pt和它们的组合时,纳米颗粒化的“纳米复合材料”材料用作例如催化剂的组分,而当选择的金属元素为Ag时,纳米颗粒化的“纳米复合材料”材料用作抗微生物剂或作为抗微生物剂的组分。按照相同的方式,当选择的金属元素为Cu时,纳米颗粒化的“纳米复合材料”材料用作杀真菌剂或作为杀真菌剂产品的组分。
另外,当金属元素选自Cu、Ag、Au和它们的组合时,纳米颗粒状“纳米复合材料”材料用作光电子材料的组分,而当金属元素选自Fe、Ni、Co和它们的组合时,纳米颗粒状“纳米复合材料”材料用作铁磁流体的组分。
在这种方法中,使用的粘土可具有任何粒度,但当在粘土颗粒表面上形成纳米颗粒时,建议使用粒度尽可能最小的粘土产品,以便纳米颗粒形成可用的颗粒表面为最大可能尺寸。按照这种方式,可加入粒度小于44μm的碎粉形式的粘土。也可使用流变级产品如流变级海泡石,这通过湿微粉化法如专利申请EP-A-0170299中描述的那些得到,利用该方法得到自由针状颗粒同时保持高的颗粒“长径比”,并且其中解聚过程留下沉积可达到的更多自由表面。另外,按照这种微粉化方法处理的粘土的胶体性质具有更高的稳定性,能在金属盐稀释液中更好地分散,允许更均匀的涂层。
上述信息表明,本发明中描述的过程基于在这些金属盐、氧化物或氢氧化物粘土表面上的沉积,然后还原处理得到相应的金属。通过在控制气氛条件下进行热处理完成还原过程。可观察到通过这种方法形成的纳米颗粒的尺寸小于30nm,通常尺寸为大约3nm,并在表面上具有均匀分布和不群集。纳米颗粒线性分布并沿微纤维化颗粒的纵轴取向。对于这种特定排列的金属纳米颗粒的形成,可能的解释是海泡石和凹凸棒石在热处理过程中发生的转换。在350℃下,海泡石失去水合水四个分子中的二个,产生海泡石结构的折叠和沸石通道的坍缩,以便位于硅酸盐八面体层边缘的阳离子完成它们与邻近硅的四面体层的氧分子的配位。这种变化是可逆的。可通过再水合使海泡石复原原始结构。在500℃的温度下,海泡石失去二个剩余的结晶水分子,但没有额外的结构变化,结构的折叠在此时变得不可逆。凹凸棒石在热处理过程中经历类似的结构变化。认为在进行分解金属盐或氢氧化物成它们相应氧化物的过程中和随后还原金属氧化物颗粒的步骤中,这些颗粒在位于结构边缘处的开放通道的折叠和坍缩过程中被捕获,阻止了金属纳米颗粒的迁移和它们的聚并和生长过程,这些过程会形成更大尺寸的颗粒。因此,可以得到尺寸小于30nm的单分散纳米颗粒,可作为金属盐、氢氧化物和氧化物的浸渍条件的函数和作为还原条件的函数控制单分散纳米颗粒,以得到可保持在10nm和5nm之间的控制粒度,甚至得到小于5nm的粒度。这种机理解释了纳米颗粒沿微纤维化颗粒轴的线形排列,然后是位于针状颗粒表面上结构边缘处的开放通道。
附图简述
这段包含本发明实施方案的一些实施例的说明,它们将引用下列图:
图1a为根据实施例1所述方法得到的负载在海泡石上的铜纳米颗粒的显微照片;
图1b为同样根据实施例1所述方法得到的负载在海泡石上的纳米颗粒的稍微放大的显微照片;
图2a为根据实施例1在海泡石载体上作为铜硝石(gerhardite)沉淀的铜的X-射线衍射图;
图2b为根据实施例1的最终产品的X-射线衍射图;
图3显示了通过按实施例1得到的最终产品的漫反射测量的以Kulbeka-Munk单位表示的吸收光谱。
图4a为根据实施例2所述方法得到的负载在海泡石上的银纳米颗粒的显微照片。
图4b为根据实施例2所述方法得到的负载在海泡石上的纳米颗粒的稍微放大的显微照片;
图5a为根据实施例2在海泡石载体上沉淀的氧化银的X-射线衍射图;
图5b为根据实施例2的最终产品的X-射线衍射图;和
图6显示了通过按实施例2得到的最终产品的漫反射测量的以Kulbeka-Munk单位表示的吸收光谱。
图7a为根据实施例3所述方法得到的负载在凹凸棒石上的铜纳米颗粒的显微照片;
图7b为根据实施例3所述方法得到的负载在凹凸棒石上的纳米颗粒的稍微放大的显微照片;
图8a为根据实施例3在凹凸棒石载体上作为氢氧化铜硫酸盐沉淀的铜的X-射线衍射图。
图8b为根据实施例3的最终产品的X-射线衍射图。
本发明不同实施方案的实施例
实施例1
对于5%的理论浸渍水平,过程以制备1升铜溶解液开始(28,51g硝酸铜/升)。然后酸化溶解液至pH 2以确保铜盐被溶解。
在混合器中制备微粉化海泡石在水中的分散体,其中99.9%的颗粒的尺寸小于44μm,95%的尺寸小于5μm。分散体的浓度为10%固体(150g干海泡石基用于1500g预凝胶),并且借助机械搅拌器在5分钟内混合分散体。然后将pH为大约9.0的粘土的这种预分散体酸化至pH 2,然后加入铜稀释液,并再搅拌混合物5分钟以确保稀释液和海泡石之间的接触是完全的。铜稀释液中的海泡石分散体具有6%的海泡石浓度。
然后,通过加入1M氢氧化钠直到达到最终的pH=5.3,使铜沉淀为铜硝石(Cu4(NO3)2(OH)6)(图2a)。在机械搅拌混合物的同时缓慢加入氢氧化钠稀释液。一旦氢氧化铜沉淀,就在真空中过滤分散体,洗涤并在150℃下烘干。在这个过程中,观察到海泡石的BET比表面从439m2/g减小到121m2/g。
然后在控制气氛为10%H2/90%Ar的管形截面烘箱中对具有前体的海泡石进行还原处理。烘箱配备有程序化设备以控制温度(±1℃)。还原循环需要在10℃/min的渐增间隔中加热混合物直到达到500℃的温度,并保持该温度2小时,然后是在烘箱内的自由冷却期。
由于这种方法,在海泡石纤维载体上得到小的铜纳米颗粒。纳米颗粒看上去是单分散的,并平行于海泡石纤维的方向排列,这可在所附的显微照片(图1a和图1b)中观察到。
最后,在H2气氛中进行的煅烧过程进一步减小表面直到它达到87m2/g的值。
还原样品的X-射线衍射图显示,材料实际上由海泡石和金属铜组成(图2b)。
通过在可见紫外范围内分析漫反射光谱得到这样获得的纳米颗粒的金属特性的更多证据,以及它们的散布图。当细碎(具有小于波长的尺寸)和分散的金属与电磁辐射相互作用时,就提供清晰的频率,一种集体电子激发现象,称为表面等离子体振子[C.F.Bohren和D.R.Huffman,“Absorption and Scattering of Light by Small Spheres”,Ed.John Wiley and Sons,New York,1983,325页]。在出现这种现象的频率中,证实金属介电常数的实数部分等于基质介电常数的负二倍(E(W)=-2EM)。由于在实验上可被最大吸收识别的这种频率对每种金属都是特定的,因此它能为我们服务作为纳米颗粒金属特性的识别。在为铜时,实验光谱在2.2eV处表现出最大吸收(图3),这与在空气中的铜纳米颗粒相对应的值一致[“Handbook of Optical Constants ofSolids”,E.D.Palik编辑,Academic Press,1985,Orlando,USA]。
实施例2
制备每升包含35.45g硝酸银的银稀释液,然后使用NO3H酸化至pH=2。然后向硝酸银稀释液中加入具有10%固体浓度的海泡石预分散体。通过在机械搅拌器中用高功率剪切叶片在5分钟内分散海泡石制备海泡石预分散体来确保粘土颗粒的良好分散。这个实施例中使用的海泡石为TOLSA S.A.生产的PANGEL流变级海泡石。一旦将海泡石预分散体加入到硝酸银稀释液中使Ag/海泡石关系为15/100比,就在高剪切设定下再在5分钟内搅拌混合物,然后在搅拌的同时缓慢加入1M NaOH溶液直到pH=12。提高pH产生银前体的沉淀,其接着均匀地沉积在海泡石表面上。随后,在真空中过滤分散体并在150℃下烘干。
在这个过程中,海泡石的BET比表面从439m2/g减少到204m2/g。
在类似于前述情形中所述的管形截面烘箱中对具有银前体(在这种具体情况下为Ag2O)的海泡石(图5a)进行还原处理,温度设在400℃。
由此过程得到的颗粒为细长的海泡石颗粒,在其上面沿平行于海泡石纤维长轴的方向出现小的银纳米颗粒。可在图4a和图4b中看到这些颗粒的图象。在这种情况下,可看到约15nm的一些颗粒和几nm的小纳米颗粒。
一旦氧化银颗粒被还原,则粉末的最终比表面降低到112m2/g。
还原样品的X-射线衍射图显示,材料实际上由海泡石和银组成(图5b)。
按与前面实施例相同的方式,利用在紫外光可见范围内的漫反射以Kulbeka-Munt单位测量具有银的海泡石样品的光吸收。在这种情况下,等离子体振子也是可见的,但在较高的频率(3.4eV)下,并显示出正是银纳米颗粒的不规则形貌(图6)。
实施例3
首先制备每升包含79.11g硫酸铜的硫酸铜溶液,然后通过加入SO4H2酸化直到得到2的pH值。然后加入固体浓度=10%的凹凸棒石的预分散体。通过在机械搅拌器中用高功率剪切叶片在5分钟内分散凹凸棒石制备凹凸棒石预分散体来确保粘土颗粒的良好分散。使用的凹凸棒石为Engelhard Corporation的ATTAGEL 40,其已按照专利EP-A-0170299中描述的过程在湿条件下被微粉化。一旦将凹凸棒石预分散体加入到硫酸铜稀释液中使Cu/凹凸棒石关系为15/100比,就在高剪切设定下再在5分钟内搅拌混合物,在仍搅拌的同时缓慢加入1MNaOH溶液直到pH=5.5。提高pH产生氢氧化铜硫酸盐(copperhydroxido sulfate)一种相的沉淀(图8a),其接着均匀地沉积在凹凸棒石表面上。随后,在真空中过滤分散体并在150℃下烘干。
然后在控制气氛条件为10%H2/90%Ar的管形截面烘箱中对具有前体的凹凸棒石进行还原处理。还原循环为加热过程,其中以10℃/min增加温度直到达到500℃的最终温度,并保持该温度2小时,然后是在烘箱内的自由冷却期。
由此过程得到的颗粒为负载在凹凸棒石纤维上的铜纳米颗粒。在这种情况下,针状纳米颗粒出现在沿凹凸棒石纤维方向的平行排列中。它们的大小为大约30nm长乘以几nm宽(图7b)。当观察处于深处的它们时,可看到这些纳米颗粒由大约3nm的纳米颗粒簇形成。
还原样品的X-射线衍射图显示,材料实际上由凹凸棒石和金属铜组成(图8b)。
Claims (27)
1.一种制备金属纳米颗粒的方法,在所述纳米颗粒中金属化合物通过均匀地分散在载体上而被接触,
特征在于:
载体为选自伪层页硅酸盐粘土的具有硅酸盐网络的至少一种粘土,所述金属化合物为选自金属元素的盐、氢氧化物和氧化物中的至少一种前体,和
金属元素选自在低于引起粘土硅酸盐网络坍缩或破坏的那些温度的温度下易于还原的金属元素,
和特征还在于该方法另外包括:
前体被沉积在载体上的沉积阶段,
当前体选自盐和氢氧化物时,在控制气氛条件下进行的热分解阶段,并且其中对前体进行分解处理,此时前体被转化成金属元素的氧化物,和
在控制条件下进行的热还原阶段,其中对金属元素的氧化物进行还原处理得到沉积在载体上的金属元素的纳米颗粒,
在低于粘土硅酸盐网络破坏温度的温度下进行该方法。
2.根据权利要求1的方法,特征在于热分解阶段和还原阶段在低于850℃的温度下进行。
3.根据权利要求1的方法,特征在于所述粘土为海泡石粘土。
4.根据权利要求1的方法,特征在于所述粘土为流变级海泡石。
5.根据权利要求1的方法,特征在于所述粘土为凹凸棒石。
6.根据权利要求1的方法,特征在于所述粘土为流变级凹凸棒石。
7.根据权利要求1的方法,特征在于所述金属元素选自Fe、Co、Ni、Cu、Mo、Ru、Rh、Pd、Ag、W、Re、Os、Ir、Pt、Au和它们的合金。
8.根据权利要求1的方法,特征在于前体为金属元素的水溶性盐。
9.根据权利要求8的方法,特征在于盐选自氯化物、硝酸盐、硫酸盐、乙酸盐、磷酸盐和卤化物。
10.根据权利要求1的方法,特征在于沉积阶段需要:
在水中溶解前体得到前体的溶液,
在前体溶液中分散载体得到前体/载体分散体,
干燥前体/载体分散体得到干的前体/载体颗粒。
11.根据权利要求10的方法,特征在于在干燥前过滤前体/载体分散体。
12.根据权利要求10的方法,特征在于在干燥前通过固/液分离技术分离前体/载体。
13.根据权利要求10的方法,特征在于分散前体稀释液调整到5-15%的前体/载体浓度。
14.根据权利要求10的方法,特征在于载体/前体分散体调整到按重量计范围从0.1∶100至100∶100的金属元素/载体比。
15.根据权利要求10的方法,特征在于载体/前体分散体调整到按重量计范围从5∶100至50∶100的金属元素/载体比。
16.根据权利要求10的方法,特征在于:在干燥前,通过加入碱升高载体/前体分散体的pH在载体上沉淀前体。
17.根据权利要求1的方法,特征在于载体具有超过50%的所述至少一种粘土的浓度。
18.根据权利要求1的方法,特征在于载体具有超过85%的所述至少一种粘土的浓度。
19.根据权利要求1的方法,特征在于载体为粒度小于44μm的粉末。
20.根据权利要求1的方法,特征在于金属纳米颗粒具有小于30nm的尺寸。
21.根据权利要求1的方法,特征在于金属纳米颗粒的尺寸在10nm和3nm之间。
22.一种复合材料,其具有沉积在载体表面上的金属纳米颗粒,特征在于它是通过前述权利要求的任意一项所限定的方法得到的。
23.一种催化剂,特征在于它包括通过前述权利要求1-6和8-21中任意一项所限定的方法得到的复合材料,并且特征在于金属元素选自Cu、Ag、Au、Rh、Pd、Ir、Ni、Pt和它们的组合。
24.一种抗微生物剂材料,特征在于它包括通过前述权利要求1-6和8-21中任意一项所限定的方法得到的材料,并且特征在于金属元素为Ag。
25.一种杀真菌剂材料,特征在于它包括通过前述权利要求1-6和8-21中任意一项所限定的方法得到的材料,并且特征在于金属元素为Cu。
26.一种光电子材料,特征在于它包括通过前述权利要求1-6和8-21中任意一项所限定的方法得到的复合材料,并且特征在于金属元素选自Cu、Ag、Au和它们的组合。
27.一种铁磁流体,特征在于它包括通过前述权利要求1-6和8-21中任意一项所限定的方法得到的复合材料,并且特征在于金属元素选自Fe、Ni、Co和它们的组合。
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ITMI20110974A1 (it) * | 2011-05-30 | 2012-12-01 | Pirelli | Pneumatico ad alte prestazioni per ruote di veicoli |
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US7053021B1 (en) * | 2004-04-22 | 2006-05-30 | The Research Foundation Of The State University Of New York | Core-shell synthesis of carbon-supported alloy nanoparticle catalysts |
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CN102218545A (zh) * | 2011-05-30 | 2011-10-19 | 陶栋梁 | 化学法制备纳米铝的方法 |
CN102218545B (zh) * | 2011-05-30 | 2012-11-28 | 陶栋梁 | 化学法制备纳米铝的方法 |
CN103420387A (zh) * | 2013-08-13 | 2013-12-04 | 浙江大学 | 一种管状粘土矿物-磁性金属纳米复合材料及其制备方法 |
CN103420387B (zh) * | 2013-08-13 | 2015-05-06 | 浙江大学 | 一种管状粘土矿物-磁性金属纳米复合材料及其制备方法 |
CN104308171A (zh) * | 2014-07-18 | 2015-01-28 | 江苏启弘新材料科技有限公司 | 一种核壳结构金属/凹凸棒土导电粒子的制备方法 |
CN107445176A (zh) * | 2017-08-30 | 2017-12-08 | 合复新材料科技(无锡)有限公司 | 锡锑掺杂浅色电绝缘激光活化可金属化粉末的制备方法 |
CN107500304A (zh) * | 2017-08-30 | 2017-12-22 | 饶伟锋 | 一种浅色电绝缘激光活化可金属化粉末的制备方法 |
CN107445176B (zh) * | 2017-08-30 | 2019-11-19 | 合复新材料科技(无锡)有限公司 | 锡锑掺杂浅色电绝缘激光活化可金属化粉末的制备方法 |
CN107500304B (zh) * | 2017-08-30 | 2020-02-04 | 饶伟锋 | 一种浅色电绝缘激光活化可金属化粉末的制备方法 |
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EP1681097A1 (en) | 2006-07-19 |
JP4963608B2 (ja) | 2012-06-27 |
JP2007509234A (ja) | 2007-04-12 |
ES2229940B1 (es) | 2006-06-01 |
ES2539629T3 (es) | 2015-07-02 |
WO2005035124A1 (es) | 2005-04-21 |
US7829493B2 (en) | 2010-11-09 |
US7910511B2 (en) | 2011-03-22 |
CN100464856C (zh) | 2009-03-04 |
US20100261005A1 (en) | 2010-10-14 |
ES2229940A1 (es) | 2005-04-16 |
US20060293171A1 (en) | 2006-12-28 |
EP1681097B1 (en) | 2015-03-18 |
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