CN1233466C - Method for gqually distributing liquid phase method prepared metal atomic cluster with active composition smaller than 5 nm on porous oxide carrier - Google Patents
Method for gqually distributing liquid phase method prepared metal atomic cluster with active composition smaller than 5 nm on porous oxide carrier Download PDFInfo
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- CN1233466C CN1233466C CN 02130932 CN02130932A CN1233466C CN 1233466 C CN1233466 C CN 1233466C CN 02130932 CN02130932 CN 02130932 CN 02130932 A CN02130932 A CN 02130932A CN 1233466 C CN1233466 C CN 1233466C
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Abstract
The present invention belongs to the technical field of the preparation of nanometer metal catalysts in a liquid phase method, particularly to a liquid phase preparation method of metal atomic clusters whose active constituents are less than 5 nanometers, and the metal atomic clusters are uniformly distributed on porous oxide carriers. A solution of organic aluminium or silicon compounds-porous oxide is mixed with a solution of the precursors of noble metal atomic clusters to form a transparent and uniform solution, and then, porous hydroxide is generated by a hydrolysis method. Reducing agents are added, the solution of the precursors of the noble metal atomic clusters is reduced to be nanometer metal atomic clusters, and the noble metal atomic clusters uniformly distributed on alumina or silicon oxide carriers can be obtained after separation, drying and high temperature calcination, wherein the particle size of the noble metal atomic clusters is less than 5 nanometers. The method of the present invention can obtain the most effective active surfaces, and the catalytic activity of the nanometer catalysts is improved.
Description
Technical field
The invention belongs to liquid phase method and prepare the technical field of metallic catalyst, specially refer to liquid phase method and prepare active component and be evenly distributed on method on the porous oxide carrier less than the metal atomic cluster of 5 nanometers.
Background technology
By Al
2O
3, SiO
2Noble metal catalyst Deng oxide supports has great use value in many application such as purifying vehicle exhaust and gas utilization.
In the preparation of metallic catalyst, nano-metal particle is evenly distributed on the surface of oxide, be a key technology in the Preparation of Catalyst.Because liquid phase method is than vapor phase method (the colloid chemistry outline that Jiang Long writes, Beijing: Science Press, advantages such as preparation method P73 in 2002) has that equipment is simple, the grain structure that is easy to control noble metal and granular size, therefore, liquid phase method has obtained extensive use in industrial production.
The most solid catalyst is general, and what adopt is the method that solid carrier and metal nanoparticle are mixed, as Al
2O
3Mix with Pt; Or solid carrier is immersed in the precursor solution of metal nanoparticle, as be immersed in H
2PtCl
6(Lopez T., Reat.Kinet.Catal.Lett., 1992,47 (1) 21-27 in the solution; Lopez, T., Romero A, Gomez R, J.Non-Cryst, Solids, 1991,127,307), but the coalescent metal atomic cluster that often can not get grain fineness less than 5 nanometers of particle in these methods because in preparation and roasting process, and often have quantum size effect less than the metal atomic cluster of 5 nanometers, have the characteristic that the common metal catalyst is not had.
Summary of the invention
The objective of the invention is to overcome the defective of prior art, provide a kind of liquid phase method to prepare active component and be evenly distributed on method on the porous oxide carrier less than the metal atomic cluster of 5 nanometers, thereby obtain the most effective active surface, improve the catalytic activity of nanocatalyst.
Characteristics of the present invention are that organic aluminium alcoholates or silane oxide are mixed with certain density alcoholic solution, the precursor solution that adds template agent and catalyst activity component metals cluster then, mix to form the solution of a transparent homogeneous, just can obtain high-purity, equal, the ultra-fine porous hydroxide that contains metal ion or metal complex solion by the hydrolysis way then.Add reducing agent again and directly reduce these metal ions or metal complex ion, reduction becomes the nano metal cluster, the nano metal cluster that generates is adsorbed on the hydroxide gel, and this gel just can make the metal atomic cluster less than 5 nanometers of high degree of dispersion on porous oxide carrier through vacuumizing filtration, washing, drying, high-temperature roasting.The effect of template agent is specific surface and the pore structure that control generates oxide, generally is made up of cation or neutral surface active agent.
Liquid phase method of the present invention prepares active component and is evenly distributed on method on the porous oxide carrier less than the metal atomic cluster of 5 nanometers,
One. utilize the method step of organic aluminium alcoholates to comprise:
(1). organic pure aluminum solutions is mixed with the precursor solution of metal atomic cluster, form the mixed solution of transparent homogeneous; The organic aluminium alcoholates that wherein contains in the mixed liquor is 5mmol-90mmol, and the weight percent values of the aluminium oxide in the precursor solution in the content of metal atomic cluster and the organic aluminium alcoholates is 0.5%～5%;
The precursor solution of described metal atomic cluster is mixed with by water or organic solvent and metal ion or metal complex ion;
(2). add the template agent in the mixed solution of step (1), wherein the molar ratio of template agent and aluminium is between 1: 1～1: 10, with hydrolyzate fully be hydrolyzed react finish after, obtain the gel aluminum hydroxide of ultra-fine porous; Or add reducing agent again, and make metal ion or metal complex ion in the precursor solution of metal atomic cluster be reduced into the nano metal cluster, the nano metal cluster of generation is adsorbed on the gel aluminum hydroxide; The molar ratio of described reducing agent and metal atomic cluster is between 5: 1～20: 1;
(3). the gel aluminum hydroxide of the ultra-fine porous that step (2) is obtained or be adsorbed on nano metal cluster on the gel aluminum hydroxide through vacuumizing filtration, washing, drying, roasting under 300 ℃～600 ℃ high temperature, can obtain equally distributed metal atomic cluster on porous oxide carrier, its particle diameter is below 5 nanometers.
Or
Two. utilize the method step of silane oxide to comprise:
(1) former with silane oxide as silicon, the solution of the mixing transparent and homogeneous that preparation is made up of ethanol, ammoniacal liquor and template agent; To slowly splash into by the mixed solution that silane oxide and metal atomic cluster presoma are formed in the solution of the mixing transparent and homogeneous of forming by ethanol, ammoniacal liquor and template agent then, hydrolysis while stirring, wherein, the mol ratio of component is a silane oxide in the mixed system: ethanol: NH
4OH: template agent=1: 40-100: 0.5-2: 0.5-5, the content of metal atomic cluster and the weight percent values of the oxide in the silane oxide are 0.5%-5%; With finish afterreaction tens of hours of hydrolyzate hydrolysis, obtain the silicon hydroxide gel of ultra-fine porous; Or add reducing agent again, and make metal ion or metal complex ion in the precursor solution of metal atomic cluster be reduced into the nano metal cluster, the nano metal cluster of generation is adsorbed on the silicon hydroxide gel; Wherein reducing agent and metal atomic cluster molar ratio are between 5: 1～20: 1;
(2). the silicon hydroxide gel of the ultra-fine porous that step (1) is obtained or be adsorbed on nano metal cluster on the silicon hydroxide gel through vacuumizing filtration, washing, drying, roasting under 300 ℃～600 ℃ high temperature, can obtain equally distributed metal atomic cluster on porous oxide carrier, its particle diameter is below 5 nanometers.
Described metal atomic cluster is that the atom of transition elements gold, silver, copper, cobalt, nickel or platinum family is formed.
Described organic solvent is ethanol, cyclohexane, n-hexane, chloroform or acetone etc.
Described hydrolyzate can be ammoniacal liquor or organic alcohol solution, determine the component of hydrolyzate according to the organic aluminium alcoholates hydrolysis rate of difference, the concentration of wherein said ammoniacal liquor is 3-10wt%, and the water yield in organic alcohol solution is controlled at the mol ratio of organic aluminium alcoholates and water between 1: 0.5～1: 5.
Described organic aluminium alcoholates is aluminium ethylate, aluminium isopropoxide, aluminium secondary butylate, tert-butyl alcohol aluminium or isobutanol aluminum etc.
Described alcohol is ethanol, isopropyl alcohol, sec-butyl alcohol, the tert-butyl alcohol or isobutanol etc.
Described silane oxide is that methyl silicate, ethyl orthosilicate, positive silicic acid propyl ester or butyl silicate etc. (are C
4-C
16Esters of silicon acis).
Surfactant or cationic surfactant that described template agent is a nonionic.
The surfactant of described nonionic is the polyethylene glycol type surfactant or contains polyethylene glycol groups (being the rare base of polyoxy second) (CH
2CH
2O)
nThe type surfactant.
The described polyethylene glycol fundamental mode surfactant that contains is (a) OP type polyoxyethylene alkylphenol ether, (b) Pluronic type polypropylene glycol and poly-ethanol replace addition compound product, (c) Tergitol type (TMN) AEO, (d) aliphatic acid-polyoxyethylene-type, (e) other polyethylene glycol type.
Described cationic surfactant is softex kw (CTAB), hexadecyltrimethylammonium chloride (CTAC) or C
10～C
20The chain alkyl ammonium.
Described reducing agent is hydrazine, hydrazine sulfate or boron hydride etc.
Described boron hydride is potassium borohydride or sodium borohydride.
The present invention utilizes the liquid phase method preparation can make the precious metal atom high degree of dispersion on porous oxide carrier less than 5 metallic catalysts, this method equipment simply is easy to control the nano particle size, thereby obtain the most effective active surface, improve the catalytic activity of nanocatalyst.
Description of drawings
Fig. 1. pt atom of the present invention is at Al
2O
3Electromicroscopic photograph on the carrier.
The specific embodiment
Embodiment 1.
Aluminium isopropoxide is as the parent of aluminium, to form Pt/Al
2O
3Catalyst.
Take by weighing 3 gram aluminium isopropoxides (AIP) and be dissolved in the 120ml absolute ethyl alcohol and transfer pH=2, add the mixed solution that chloroplatinic acid 3ml (0.0337mol/L) aqueous solution forms transparent homogeneous then with hydrochloric acid; Add alkylphenol polyoxydivinyl ether (OP) 5ml again, under fully stirring, slowly join in the above-mentioned solution with 14ml (3wt%) ammonia spirit, make slowly hydrolysis of aluminium isopropoxide, control pH=4.7 treats that hydrolysis finishes, and obtains light yellow gel aluminum hydroxide, continue reaction 3 hours, with 6ml (0.3mol/L) sodium borohydride (NaBH
4) aqueous solution reduces, the nano metal platinum that the reduction back generates is adsorbed on the gel aluminum hydroxide, obtains the pitchy gel aluminum hydroxide, continues reaction 2 hours, ageing at room temperature at last 10 hours, vacuum filtration.The platinum complex ion is dispersed in gel aluminum hydroxide fully and is become metallic atom by sodium borohydride reduction in the chloroplatinic acid at this moment.Filter out filtrate and do not have the platinum complex ion.Unnecessary reducing agent washs three to four times with distilled water, use absolute ethanol washing at last again two to three times, obtaining product can be that gel drying, roasting or gel are dispersed in the absolute ethyl alcohol again, with the miniature whirlwind spray dryer of Japanese GB-22 type Pulvis, spray-drying obtains product dried 2 hours down at 100 ℃, 500 ℃ of roastings 5 hours, so just can make less than 5nm metal platinum high degree of dispersion again in porous Al
2O
3On the carrier.
Embodiment 2
Taking by weighing 3 gram aluminium isopropoxides is dissolved in the 120ml absolute ethyl alcohol, transfer pH=2 with hydrochloric acid, adding concentration is 0.04mol/L aqueous solution of chloraurate 4ml, add non-ionic surface active agent alkylphenol polyoxydivinyl ether (OP) 10ml again, fully mix to stir forming the faint yellow AIP of homogeneous transparent, gold chloride, surfactant mixed solution.Ammonia spirit with 5wt% is hydrolyzed then, slowly drips the 15ml hydrolyzate, treats that hydrolysis finishes, and obtains faint yellow thickness gel aluminum hydroxide, continues reaction after 3 hours, uses 0.3mol/L NaBH
4Aqueous solution 6ml reduces, and the nano metal gold that the reduction back generates is adsorbed on the gel aluminum hydroxide, obtains even aubergine gel aluminum hydroxide; Continue reaction 2 hours, ageing at high temperature 10 hours through vacuumizing filtration, washing, drying, again 500 ℃ of roastings 5 hours, obtains less than 5nm metallic gold high degree of dispersion at porous Au/Al
2O
3On the carrier.
Embodiment 3
Aluminium secondary butylate is made the parent of aluminium to form Pt/Al
2O
3Catalyst.
Because the very easily moisture absorption, hydrolysis of aluminium secondary butylate, so preparation aluminium secondary butylate solution has two kinds of methods: a kind ofly directly be dissolved in aluminium secondary butylate in the sec-butyl alcohol; Another kind is dissolved in aluminium secondary butylate in the cyclohexane, and chloroplatinic acid is dissolved in the acetone soln.Taking by weighing 7.4 gram aluminium secondary butylates is dissolved in the 60ml sec-butyl alcohol, the acetone soln and the 10ml OP that add 2ml (0.04mol/L) chloroplatinic acid then are mixed with homogeneous transparent ATB, chloroplatinic acid and OP mixed solution, use hydrolyzate (15ml sec-butyl alcohol+1.5ml water) to be hydrolyzed again, hydrolysis obtains faint yellow gel aluminum hydroxide after 3 hours; Continue to stir 3 hours again, slowly add 15ml (0.3mol/L) sodium borohydride aqueous solution and reduce, the nano metal platinum that the reduction back generates is adsorbed on the gel aluminum hydroxide, obtains the pitchy gel aluminum hydroxide; Ageing at room temperature 24 hours through vacuumizing filtration, washing, drying, again 500 ℃ of roastings 5 hours, obtains less than 5nm metal platinum high degree of dispersion at porous Pt/Al
2O
3On the carrier.
Embodiment 4
Take by weighing ATB 8.1 grams and be dissolved in the 8ml cyclohexane, add non-ionic surface active agent OP 0.6ml and form transparent homogeneous solution, slowly drip chloroplatinic acid (concentration is 0.07mol/L) acetone soln 2.5ml again, obtain faint yellow transparent mixed solution through fully stirring.With preparing hydrolyzate (its content 10ml OP+15ml absolute ethyl alcohol+1.5ml H in advance
2O) be hydrolyzed.With the dilution of 20ml absolute ethyl alcohol, reacted 3 hours, with the dilution of 40ml absolute ethyl alcohol, use NaBH again
40.3mol/L the aqueous solution reduces, the nano metal platinum that the reduction back generates is adsorbed on the gel aluminum hydroxide, obtain pitchy gel aluminum hydroxide precipitation, continue reaction 3 hours, ageing is 24 hours under the room temperature, through vacuumizing filtration, washing, drying, again 600 ℃ of roastings 5 hours, obtain less than 5nm metal platinum high degree of dispersion at porous Pt/Al
2O
3On the carrier.
Embodiment 5
Take by weighing aluminium isopropoxide 3 gram and be dissolved in the 120ml absolute ethyl alcohol, transfer pH=2, add surfactant OP 5ml again and 0.5mol/L copper nitrate aqueous solution 0.6ml obtains the transparent mixed liquor of light green color with hydrochloric acid.Be hydrolyzed with the 3.3wt% ammonia spirit, sky blue gel aluminum hydroxide appears in Dropwise 5 ml, for abundant hydrolysis, adds the 7ml hydrolyzate altogether, reacted 3 hours, ageing is 12 hours under the room temperature, carries out the vacuum filtration washing, spray-drying, obtain powder, oven dry is 2 hours under 100 degree, and roasting is 7 hours under 600 degree, obtains CuO/Al
2O
3Solid catalyst.
Embodiment 6
Take by weighing aluminium isopropoxide 4 grams and be dissolved in the 160ml absolute ethyl alcohol, transfer pH=2 with hydrochloric acid, again with non-ionic surface active agent TMN
1010ml and 0.1mol/L palladium bichloride (PdCl
2) aqueous solution 1ml, to form the homogeneous transparent mixed liquor; Be hydrolyzed with the 3.3wt% ammonia spirit, hydrolysis finishes, and continues reaction 3 hours, adds reducing agent hydrazine hydrate (H
4N
2H
2O) 3ml reduces, and obtains the Pd atom and is dispersed on the gel aluminum hydroxide, and gel ageing at room temperature 12 hours through vacuumizing filtration, washing, drying, again 500 ℃ of roastings 5 hours, obtains Pd/Al
2O
3Solid catalyst
Embodiment 7
Prepare Pt/SiO with ethyl orthosilicate
2Catalyst
Getting 150ml ethanol adds after 15ml (28wt%) ammoniacal liquor mixes, add surfactant Pluronic (F127) 6 grams, under constantly stirring, ethyl orthosilicate and very long the splashing in the above-mentioned mixed liquor of 3ml (0.05mol/L) chloroplatinic acid acetone soln mixed liquor with 10ml, hydrolysis finishes, reacted 4 hours, use 6ml (0.3mol/L) sodium borohydride aqueous solution to reduce again, the nano metal platinum that the reduction back generates is adsorbed on the silicon hydroxide gel, obtains the platinum/silica dioxide gel of pitchy; Through vacuumizing filtration, centrifugation, cleaning, oven dry, roasting is 1 hour under 100 degree, and roasting is 3 hours under 300 degree, just obtains Pt/SiO
2Catalyst.
Claims (6)
1. a liquid phase method prepares active component and is evenly distributed on method on the porous oxide carrier less than the metal atomic cluster of 5 nanometers, it is characterized in that described method is:
One. utilize the method step of organic aluminium alcoholates to comprise:
(1). organic pure aluminum solutions is mixed with the precursor solution of metal atomic cluster, form the mixed solution of transparent homogeneous; The organic aluminium alcoholates that wherein contains in the mixed liquor is 5mmol-90mmol, and the weight percent values of the aluminium oxide in the precursor solution in the content of metal atomic cluster and the organic aluminium alcoholates is 0.5%～5%;
The precursor solution of described metal atomic cluster is mixed with by water or organic solvent and metal ion or metal complex ion;
(2). add the template agent in the mixed solution of step (1), wherein the molar ratio of template agent and aluminium is between 1: 1～1: 10, with hydrolyzate fully be hydrolyzed react finish after, obtain the gel aluminum hydroxide of ultra-fine porous; Or add reducing agent again, and make metal ion or metal complex ion in the precursor solution of metal atomic cluster be reduced into the nano metal cluster, the nano metal cluster of generation is adsorbed on the gel aluminum hydroxide; The molar ratio of described reducing agent and metal atomic cluster is between 5: 1～20: 1;
(3). the gel aluminum hydroxide of the ultra-fine porous that step (2) is obtained or be adsorbed on nano metal cluster on the gel aluminum hydroxide through vacuumizing filtration, washing, drying, roasting under 300 ℃～600 ℃ high temperature, obtain equally distributed metal atomic cluster on porous oxide carrier, its particle diameter is below 5 nanometers;
Or
Two. utilize the method step of silane oxide to comprise:
(1) former with silane oxide as silicon, the solution of the mixing transparent and homogeneous that preparation is made up of ethanol, ammoniacal liquor and template agent; To slowly splash into by the mixed solution that silane oxide and metal atomic cluster presoma are formed in the solution of the mixing transparent and homogeneous of forming by ethanol, ammoniacal liquor and template agent then, hydrolysis while stirring, wherein, the mol ratio of component is a silane oxide in the mixed system: ethanol: NH
4OH: template agent=1: 40-100: 0.5-2: 0.5-5, the content of metal atomic cluster and the weight percent values of the oxide in the silane oxide are 0.5%-5%; Fully be hydrolyzed after reaction finishes with hydrolyzate, obtain the silicon hydroxide gel of ultra-fine porous; Or add reducing agent again, and make metal ion or metal complex ion in the precursor solution of metal atomic cluster be reduced into the nano metal cluster, the nano metal cluster of generation is adsorbed on the silicon hydroxide gel; Wherein reducing agent and metal atomic cluster molar ratio are between 5: 1～20: 1;
(2). the silicon hydroxide gel of the ultra-fine porous that step (1) is obtained or be adsorbed on nano metal cluster on the silicon hydroxide gel through vacuumizing filtration, washing, drying, roasting under 300 ℃～600 ℃ high temperature, obtain equally distributed metal atomic cluster on porous oxide carrier, its particle diameter is below 5 nanometers;
Described metal atomic cluster is that the atom of transition elements gold, silver, copper, cobalt, nickel or platinum family is formed;
Described silane oxide is methyl silicate, ethyl orthosilicate, positive silicic acid propyl ester or butyl silicate;
Surfactant or cationic surfactant that described template agent is a nonionic;
The surfactant of described nonionic is the polyethylene glycol type surfactant or contains the polyethylene glycol based surfactants;
Described cationic surfactant is softex kw, hexadecyltrimethylammonium chloride or C
10～C
20The chain alkyl ammonium.
3. the method for claim 1, it is characterized in that: described organic solvent is ethanol, cyclohexane, n-hexane, chloroform or acetone.
4. the method for claim 1, it is characterized in that: described hydrolyzate is ammoniacal liquor or organic alcohol solution, the concentration of wherein said ammoniacal liquor is 3-10wt%, and the water yield in organic alcohol solution is controlled at the mol ratio of organic aluminium alcoholates and water between 1: 0.5～1: 5.
5. the method for claim 1, it is characterized in that: described organic aluminium alcoholates is aluminium ethylate, aluminium isopropoxide, aluminium secondary butylate, tert-butyl alcohol aluminium or isobutanol aluminum.
6. the method for claim 1, it is characterized in that: the described polyethylene glycol fundamental mode surfactant that contains is (a) polyoxyethylene alkylphenol ether, (b) polypropylene glycol and poly-ethanol replace addition compound product, (c) AEO or (d) aliphatic acid-polyoxyethylene-type.
7. the method for claim 1, it is characterized in that: described reducing agent is hydrazine, hydrazine sulfate or boron hydride.
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| CN100560492C (en) * | 2006-11-09 | 2009-11-18 | 中国科学院大连化学物理研究所 | A kind of difunctionalization mesopore silica material and preparation method and application |
| CN101469139B (en) * | 2007-12-26 | 2011-11-16 | 中国科学院大连化学物理研究所 | Preparation of silicon oxide supported monodisperse nanoparticle nano complex |
| CN102380376B (en) * | 2010-08-30 | 2014-02-12 | 中国中化股份有限公司 | Method for loading noble metal on silicon oxide, aluminum oxide or titanium oxide |
| CN102513542B (en) * | 2011-11-21 | 2014-03-26 | 南京师范大学 | Method for preparing porous Pd nanospheres with liquid phase reduction method and prepared nanospheres |
| CN103889889A (en) * | 2011-12-28 | 2014-06-25 | 株式会社村田制作所 | Method for manufacturing functional material, and electronic component |
| ES2529377B2 (en) * | 2013-06-07 | 2015-11-12 | Universidad Complutense De Madrid | Method for the production of metallic atomic clusters using porphyrins and their immobilization on the surface of metal oxide nanoparticles and in core @ cortex systems. |
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| CN105903978B (en) * | 2016-04-20 | 2017-12-15 | 中国科学院新疆理化技术研究所 | The preparation method and purposes of a kind of stable fluorescence copper clusters of silane |
| CN107398271B (en) * | 2016-05-19 | 2020-05-05 | 中国科学院大连化学物理研究所 | Carbon-supported gold cluster catalyst and application thereof in catalytic oxidation of glucose |
| US10159960B2 (en) * | 2016-10-25 | 2018-12-25 | GM Global Technology Operations LLC | Catalysts with atomically dispersed platinum group metal complexes |
| CN110015676B (en) * | 2018-01-09 | 2021-08-31 | 中国石油天然气股份有限公司 | Alumina material and preparation method thereof |
| CN108889325A (en) * | 2018-06-28 | 2018-11-27 | 陕西科技大学 | A kind of synthetic method of Pt nanoparticle catalyst |
| CN110124664B (en) * | 2019-06-18 | 2020-09-22 | 中国科学院长春应用化学研究所 | Metal platinum black nanocluster catalyst and preparation method thereof |
| CN112973660B (en) * | 2019-12-14 | 2022-04-22 | 中国科学院大连化学物理研究所 | High-dispersion non-noble metal catalyst and preparation method and application thereof |
| CN112403512B (en) * | 2020-11-27 | 2023-08-15 | 中科南京绿色制造产业创新研究院 | Platinum-based catalyst loaded by nano titanium-silicon molecular sieve, preparation method and application thereof |
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