CN101670286B - Supported transition metal or transition metal alloy nanocluster catalyst and preparation method and application thereof - Google Patents
Supported transition metal or transition metal alloy nanocluster catalyst and preparation method and application thereof Download PDFInfo
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- CN101670286B CN101670286B CN2008102222788A CN200810222278A CN101670286B CN 101670286 B CN101670286 B CN 101670286B CN 2008102222788 A CN2008102222788 A CN 2008102222788A CN 200810222278 A CN200810222278 A CN 200810222278A CN 101670286 B CN101670286 B CN 101670286B
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Abstract
The invention discloses a transition metal or an alloy nanocluster catalyst and preparation method and application thereof. The invention prepares a supported transition metal or an alloy nanocluster catalyst by a new method in which a transition metal or an alloy nanocluster which is synthesized by an alkali-polyol method and stabilized by solvent and simple ions is supported on a carbon or oxide carrier. The content of the transition metal or alloy nanocluster in the catalyst is 0.1-50wt%, and the particle size is 0.7-5nm. The transition metal or alloy nanocluster in the catalyst is distributed on the outer surface or in mesopores and macropores of the carrier material, and the atoms on the surface of the metal or alloy nanocluster have high availability. The catalyst has good catalytic performance on the hydrogenation of 2,3,5-trimethylquinone, and the catalytic activity of the prepared Pt/Al2O3 and Pt/C supported metal nanocluster catalyst on the hydrogenation of the 2,3,5-trimethylquinone is much higher than that of the corresponding commercially available catalysts.
Description
Technical field
The present invention relates to one type of carrier-borne transition metal or transition metal alloy nanocluster catalyst and preparation method thereof and application.
Background technology
Transition metal or alloy nanocluster (be that size is little, the transition metal of narrow diameter distribution or alloy nano particle) be one type and have the nano material that extensive use is worth, be the important structure primitive of constructing multiple functional material (Y.Wangand Y.Wei, " Metal Nanoclusters " be in H.S.Nalwa (Chapter); Ed.; Encyclopedia ofNanoscience and Nanotechnology, Vol.5,337-367; 2004, American Scientific Publishers).Applicant of the present invention had once invented " alkali-how pure method " of one type of " non-protection type " transition metal or its alloy nanocluster and synthetic this type of nano-cluster.This metalloid nano-cluster only with simple ion and organic solvent molecule as stabilizing agent; Not only size is little, narrow diameter distribution, can be synthetic in enormous quantities by efficiently; And through reducing the pH value of the synthetic metal nanometre cluster colloid of institute, can easily metal nanometre cluster be come out with the isolated in form that precipitates and carry out purifying, the gained metal nanometre cluster precipitates to be scattered in once more and forms stable colloid (Wang Yuan etc. in many solvents again; Chinese invention patent, ZL99100052.8; Chem.Mater.2000,12,1622-1627; Top.Catal.2005,35,35-41).In view of above-mentioned plurality of advantages, this type of " non-protection type " metal nanometre cluster and synthetic method thereof have received extensive concern, and become one of important foundation of development new catalyst.
The inventor is a structural motif with " non-protection type " metal nanometre cluster and inorganic, metal oxide colloidal particle, has set up a kind of new method (Wang Yuan etc., Chinese invention patent, ZL200410086479.1 for preparing the metal nano compound catalyst; J.Catal.2004,222,493-498; J.Catal.2005,229,114-118; J.Catal.2008,255,335-342).The principal character of this process is with " non-protection type " transition metal or alloy nanocluster colloid and the mixing of inorganic, metal oxide colloid; Form composite nanoparticle colloidal sol; Make the complex sol gelation through regulating methods such as pH value, thereby obtain transition metal or alloy nanocluster based compound catalyst.Compare with traditional complex phase metallic catalyst preparation methods such as infusion processes; Because this method has at first been carried out effective control to the metal of institute's load and the particle diameter of carrier, thereby makes the narrow diameter distribution of metal nanometre cluster in the catalyst that is synthesized and be in the high degree of dispersion state.Simultaneously, this method has avoided removing this complex steps of protective agent.The synthetic method of this preparation metal nano compound provides the new way of preparation multiphase catalyst, is with a wide range of applications.This type of catalyst has good dispersiveness, but the bonding between oxide nano-particles a little less than, as catalyst, its mechanical strength and high temperature resistant character await further raising.
The hard people of grade is in " alkali-how pure method " that synthesizes transition metal or its alloy nanocluster; Before the heating reduction step, in system, add carbon or oxide carrier; The transition metal that forms in the heating process or a part of metal nanometre cluster in the alloy nanocluster colloid are carried on the carrier, and setting accelerator is done in the acid that adds 0.1-10mol/L again, and it is (hard etc. that the transition metal nano-cluster is carried on the carrier fully; Chinese invention patent, ZL0114423.2; Hard etc., Chinese invention patent, ZL02106201.3; Hard etc., Chinese invention patent, ZL03143681.1).They adopt this method to prepare multiple is the complex phase transition metal or the alloy catalyst of carrier with carbon, and this type of catalyst shows excellent catalytic performance in Proton Exchange Membrane Fuel Cells.Yet; This preparation method uses acid to impel the metal nanometre cluster sedimentation, and this is prone to cause metal nanometre cluster in colloid, reunite (Y.Wang, et al. during high metals content catalysts in preparation; Chem.Mater.2000; 12,1622-1627), have simultaneously that synthetic metal nanometre cluster makes the size of metal nanometre cluster and the influence that distribution is vulnerable to carrier under the situation at carrier.In addition, when using some metal oxides as carrier, the short heavy agent of acid possibly cause corrosion to carrier.
(S.Mao, G.Mao US6686308B2) disclose a kind of method for preparing high capacity amount Pt/C and Pt-Ru/C catalyst to United States Patent (USP).It is characterized in that in " non-protection type " Pt of inventor invention or Pt-Ru nano-cluster colloid, adding carbon carrier, add rare nitric acid afterwards and reduce the pH value, Pt or Pt-Ru nano-cluster are deposited on the carbon carrier.This method can be used for preparing the fuel-cell catalyst that the Pt load capacity surpasses 30wt% (annotate: wt% is the quality percentage composition, down together), and its metal and alloy particle diameter can obviously not increase with the raising of load capacity.Prepared Pt/C and Pt-Ru/C catalyst show good electrocatalysis characteristic in Proton Exchange Membrane Fuel Cells.This catalytic preparation method uses inorganic acid as short heavy agent, also causes noble metal nano bunch in colloid or on the carrier surface, to be assembled easily, uses a large amount of acid also to be unfavorable for protecting environment as precipitating reagent in addition.
2,3, the 5-TMHQ is the important intermediate of synthesising complex E, can be through 2,3, and the reduction of 5-trimethylbenzoquinone preparation.Characteristics such as it is low that catalytic hydrogenation process has a cost, and product quality is high, and the three wastes are few have been most of larger 2,3, and 5-TMHQ manufacturer adopts.And catalytic activity, stability and the service life of improving catalyst are one of important topics of improving this manufacturing process.
Summary of the invention
The purpose of this invention is to provide one type of carrier-borne transition metal or transition metal alloy nanocluster catalyst and preparation method thereof and application.
The method for preparing carrier-borne transition metal or transition metal alloy nanocluster catalyst provided by the invention comprises the steps:
1) according to " alkali-how pure method " preparation transition metal or alloy nanocluster colloid: the soluble-salt of at least a transition metal or the acid that contains transition metal are dissolved in alcohol or the pure water mixed solution, and being mixed with concentration is the transistion metal compound solution of 0.01-200g/L;
The alcoholic solution of the hydroxide of alkali metal (lithium, sodium or potassium) or the aqueous solution or alcohol-water mixture are mixed with above-mentioned transistion metal compound solution; The gained mixed liquor is heated at 343-473K, obtain transition metal nano-cluster colloid or transition metal alloy nano-cluster colloid; Used alcohol is the mixture of ethylene glycol or glycerine or its arbitrary proportion; The volumn concentration of water is 0-50% in the used alcohol-water mixture; Alkali-metal hydroxide and transition metal salt or the mol ratio that contains the acid of transition metal are 3-20:1;
2) dispersible carrier: with nitrogen-doped carbon nanometer pipe, CNT, activated carbon, carbon black, α-Fe
2O
3, Al
2O
3, SiO
2, TiO
2, SnO
2, CeO
2, ZrO
2, ZnO is scattered in the mixed liquor of water or organic solvent that can be water-soluble or this organic solvent and water, stirs or ultrasonic dispersion formation carrier suspension; The quality of the carrier that is wherein disperseed in every liter of suspension is 0.1-1000g, preferred 1-100g, more preferably 3-100g;
3) transition metal or alloy nanocluster colloid and the step 2 that step 1) are prepared) prepared carrier suspension stir or ultrasonic condition under mix; Handle 0.1-200h at 273-473K then; Isolate sediment; Washing, dry under the 290-523K condition, obtain transition metal provided by the invention or alloy nanocluster catalyst.
In above-mentioned preparation method's the step 1), transition metal is Pt, Rh, Ru, Ir or Os.
Step 2) in, can water-soluble organic solvent be monohydric alcohol, dihydroxylic alcohols or the trihydroxylic alcohol of 1-4 for the carbon atom number, acetone, oxolane and N, the mixture of a kind of or its arbitrary proportion in the dinethylformamide.
In the step 3), the mass ratio of carrier is 1:1-1000 in the nano-cluster colloid of transition metal or transition metal alloy and the carrier suspension.
Among the above-mentioned preparation method; In step 2) before; Can be earlier with reacting in the step 1) in the transition metal nano-cluster colloid or transition metal alloy nano-cluster colloid that obtains that finish; Add concentration and be hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, the oxalic acid of 0.1-10mol/L, the aqueous solution of acid or glacial acetic acid; Obtain transition metal or transition metal alloy nano-cluster deposition, again this transition metal or transition metal alloy nano-cluster deposition is scattered in the aqueous slkali or organic solvent solution that can be water-soluble of ethylene glycol, obtain transition metal nano-cluster colloid or transition metal alloy nano-cluster colloid.Wherein, can comprise methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol, glycerine, acetone, oxolane or N, dinethylformamide by water-soluble organic solvent.
In addition, utilize transition metal that above-mentioned preparation method obtains or alloy nanocluster catalyst and this catalyst, as Application of Catalyst, also belong to protection scope of the present invention in the 5-trimethylbenzoquinone hydrogenation reaction 2,3.
In transition metal provided by the invention or alloy nanocluster catalyst, the quality percentage composition of transition metal or alloy nanocluster is 0.1-50%, is preferably 0.5-40%, and particle diameter is 0.7-5nm, is preferably 1-4nm.
The present invention adopts new method; Through having prepared one type of carrier-borne transition metal or alloy nanocluster catalyst with " alkali-how pure method " the synthetic approach that is carried on carbon or the oxide carrier by stable transition metal of solvent and simple ion or alloy nanocluster; Transition metal in such catalyst or alloy nanocluster are distributed in the outer surface of carrier material; Or in mesoporous and the macropore, transition metal or alloy nanocluster surface atom have very high availability.
The present invention has the following advantages:
1) the present invention utilizes the contribution different character of different solvents to the static stabilization of " non-protection type " metal or alloy nano-cluster of inventor's invention; Make metal nanometre cluster be easy to be adsorbed in the surface of said carrier; Make that the metal or alloy nano-cluster has very high decentralization in the prepared catalyst, improved the utilization ratio of metal or alloy nano-cluster surface atom; Meanwhile, adopt method of the present invention that " non-protection type " metal or alloy nano-cluster carry out complex phaseization, can not cause metal nanometre cluster or carrier particle size generation obvious variation, thereby make catalyst structure be easy to control.In traditional infusion process of synthetic catalyst; Be difficult in the metal load ranges of broad, the metal nanometre cluster size carried out effectively control; And metal can get in the micropore of carrier, can supply the space of catalytic reaction very little around the metallic in the micropore, is unfavorable for the carrying out of catalytic reaction.In the catalyst of the present invention, the metal or alloy nano-cluster is distributed in the outer surface or mesoporous and macropore of carrier material, and metal or alloy nano-cluster surface atom has very high availability, thereby catalyst of the present invention has higher catalytic activity.For example: by the inventive method preparation is that the load type metal nanocluster catalyst that contains 5wt%Pt of carrier is to 2 with carbon; 3; The catalytic hydrogenation activity of 5-trimethylbenzoquinone hydrogenation be purchased the Pt/C catalyst (5wt%Pt, Acros) 1.5 times, and by the inventive method preparation with Al
2O
3For the load type metal nanocluster catalyst that contains 1wt%Pt of carrier to 2,3, the catalytic hydrogenation activity of 5-trimethylbenzoquinone hydrogenation is to be purchased Pt/Al
2O
34 times of (1wt%Pt, Alfa Aesar) catalyst.
2) synthetic method of the present invention is not used the short heavy agent of acid, can not cause corrosion to said oxide carrier, helps environmental protection simultaneously yet.Metal nanometre cluster complex phase method provided by the invention can make metal nanometre cluster be carried on said carbon or oxide carrier surface fully.
3) synthetic method of the present invention has good universality, selects carbon or oxide carrier such as nitrogen-doped carbon nanometer pipe, CNT, activated carbon, carbon black, α-Fe
2O
3, Al
2O
3, SiO
2, TiO
2, SnO
2, CeO
2, ZrO
2, ZnO etc., can prepare corresponding carrier-borne transition metal or alloy nanocluster catalyst.
Description of drawings
Fig. 1 is the electromicroscopic photograph of Pt metal nanometre cluster in the Pt metal nanometre cluster colloid.
Fig. 2 is the electromicroscopic photograph of the Pt/C load type metal nanocluster catalyst of embodiment 1.
Fig. 3 is the electromicroscopic photograph of the Pt/C load type metal nanocluster catalyst of embodiment 2.
Fig. 4 is the electromicroscopic photograph of the Pt/C load type metal nanocluster catalyst of embodiment 3.
The specific embodiment
Below in conjunction with specific embodiment the present invention is described further, but the present invention is not limited to following examples.Method therefor is conventional method if no special instructions among the following embodiment.
First prepares carrier-borne transition metal or alloy nanocluster catalyst
Embodiment 1: preparation contains the Pt/C load type metal nanocluster catalyst of 5wt%Pt
1g six hydration chloroplatinic acids are dissolved in the 50ml ethylene glycol; Under agitation it is joined in the ethylene glycol solution (0.26mol/L) of 50ml NaOH; At room temperature continue to stir 30min; The gained reactant is made " non-protection type " platinum nano-cluster colloid in 433K backflow 3h under nitrogen protection, it is subsequent use to be cooled to room temperature, and wherein the concentration of metal Pt is 3.75g/L.
Tem study shows that the average grain diameter of Pt metal nanometre cluster is 2nm, and particle diameter is distributed as 1-3nm.The electromicroscopic photograph of Pt metal nanometre cluster is as shown in Figure 1.
Get Ketjen EC-300J type carbon black (specific area, 950m
2/ g) 2.0g is scattered in the 30ml ethanol ultrasonic dispersion.
The concentration of getting the metal Pt of the above-mentioned preparation of 28.1ml is the Pt metal nanometre cluster colloid of 3.75g/L; Under stirring fast, it is added drop-wise in the ethanol of the above-mentioned 2.0g of being dispersed with carbon carrier (Ketjen EC-300J); Continue to stir 3h, deposition is washed through decompress filter; In air,, promptly make the Pt/C load type metal nanocluster catalyst of platiniferous 5wt% in the dry 12h of 353K.
The electromicroscopic photograph of Pt/C metal nano cluster catalyst is as shown in Figure 2, and transmission electron microscope (TEM) analysis shows that the average grain diameter of Pt metal nanometre cluster is 2nm in the prepared Pt/C load type metal nanocluster catalyst, and particle diameter is distributed as 1-3nm.Above-mentioned characterization result shows that metal Pt is scattered on the carbon carrier preferably, does not take place significantly to assemble.
This catalyst is 2,3,5-trimethylbenzoquinone hydrogenation Synthetic 2, and 3, show excellent catalytic performance (seeing embodiment 15) in the reaction of 5-TMHQ.
Embodiment 2: preparation contains the Pt/C load type metal nanocluster catalyst of 50wt%Pt
1.3282g six hydration chloroplatinic acids are dissolved in the 10ml ethylene glycol; Under agitation it is joined in the ethylene glycol solution (1.69mol/L) of 10ml NaOH; At room temperature continue to stir 30min; The gained reactant is made " non-protection type " platinum nano-cluster colloid in 433K backflow 3h under nitrogen protection, it is subsequent use to be cooled to room temperature, and wherein the concentration of metal Pt is 25.0g/L.
Get Vulcan XC-72R type carbon black (specific area, 256m
2/ g) 0.4g is scattered in the 55ml water ultrasonic dispersion.
Get the prepared Pt metal nanometre cluster colloid of 16.0ml; Under stirring fast, be added drop-wise in the water of the above-mentioned 0.4g of being dispersed with carbon carrier (Vulcan XC-72R); Continue to stir 12h, deposition is washed through decompress filter; In 353K vacuum drying 12h, promptly make the Pt/C metal nano cluster catalyst of platiniferous 50wt%.
The electromicroscopic photograph of prepared Pt/C load type metal nanocluster catalyst is as shown in Figure 3; Tem study shows; The average grain diameter of Pt metal nanometre cluster is 2.5nm in the prepared Pt/C load type metal nanocluster catalyst, and particle diameter is distributed as 1-4nm.Above-mentioned characterization result shows that metal Pt nano-cluster is scattered on the carbon carrier preferably, does not take place between the Pt nano-cluster on the carrier significantly to assemble.
This catalyst 2,3,5-trimethylbenzoquinone hydrogenation Synthetic 2,3, show excellent catalytic performance in the reaction of 5-TMHQ.
Embodiment 3: preparation contains the Pt/C load type metal nanocluster catalyst of 40wt%Pt
By the method identical with embodiment 2, regulate the mass ratio of Pt metal nanometre cluster and carbon carrier (Vulcan XC-72R) in the Pt metal nanometre cluster colloid, prepare the Pt/C load type metal nanocluster catalyst of platiniferous 40wt%.
The electromicroscopic photograph of prepared Pt/C load type metal nanocluster catalyst is as shown in Figure 4; Tem study shows; The average grain diameter of Pt metal nanometre cluster is 2.5nm in the prepared Pt/C load type metal nanocluster catalyst, and particle diameter is distributed as 1-4nm.Above-mentioned characterization result shows that metal Pt nano-cluster is scattered on the carbon carrier preferably, does not take place between the Pt nano-cluster on the carrier significantly to assemble.
This catalyst 2,3,5-trimethylbenzoquinone hydrogenation Synthetic 2,3, show excellent catalytic performance (seeing embodiment 15) in the reaction of 5-TMHQ.
Embodiment 4: preparation contains the Pt/C load type metal nanocluster catalyst of 1wt%Pt
Get the ethylene glycol solution (0.50mol/L) of 50ml potassium hydroxide; Under agitation add and contain in the 50ml ethylene glycol of 1g six hydration chloroplatinic acids, at room temperature continue to stir 10min, with the gained reactant at the 433K 3h that refluxes; Pass through reaction system with nitrogen stream in the course of reaction; Make " non-protection type " platinum nano-cluster colloid, it is subsequent use to be cooled to room temperature, and wherein the concentration of metal Pt is 3.75g/L.
Tem study shows that the average grain diameter of Pt metal nanometre cluster is 1.3nm in the platinum nano-cluster colloid, and particle diameter is distributed as 0.8-2.0nm.
Get active carbon (specific area, 1050m
2/ g) 2.0g is scattered in the 50ml ethanol, and vigorous stirring is uniformly dispersed it.
Get the Pt metal nanometre cluster colloid of the above-mentioned preparation of 5.4ml; To wherein adding 1mol/L HCl20ml; To contain NaOH quality percentage composition be to form Pt metal nanometre cluster colloid again in 1% the ethylene glycol with being scattered in 5ml after the metal nanometre cluster precipitation and centrifugal separation again, then with gained Pt metal nanometre cluster colloid ultrasonic, stir down and be added drop-wise in the ethanol of the above-mentioned 2.0g of being dispersed with active carbon, continue stirring 2h under the room temperature; Deposition is through centrifugation; Washing in 353K vacuum drying 12h, promptly makes the Pt/C load type metal nanocluster catalyst of platiniferous 1wt%.
Tem study shows that the average grain diameter of Pt metal nanometre cluster is 1.3nm in the prepared Pt/C load type metal nanocluster catalyst, and particle diameter is distributed as 0.8-2.0nm.
This catalyst hydrogenation 2,3,5-trimethylbenzoquinone hydrogenation Synthetic 2,3, show excellent catalytic performance (seeing embodiment 15) in the reaction of 5-TMHQ.
Embodiment 5: preparation contains the Pt/ nitrogen-doped carbon nanometer pipe load type metal nanocluster catalyst of 10wt%Pt
Prepare Pt metal nanometre cluster colloid by embodiment 1 method.
Method preparation (R.Sen, et al., B-C-N in the nitrogen-doped carbon nanometer pipe reference literature; C-N and B-Nnanotubes produced by the pyrolysis of precursor molecules over Co catalysts.Chem.Phys.Lett.; 1998,287,671-676).The 2g nitrogen-doped carbon nanometer pipe is scattered in the HNO of 25ml50%
3In, under 343K, handle 2h, after the cooling that the precipitate with deionized water washing is extremely neutral, subsequent use behind dry 12h under the 353K.
Get the prepared Pt metal nanometre cluster colloid of 29.6ml; Under stirring fast, be added drop-wise in the ethanol water that 30ml is dispersed with the above-mentioned nitrogen-doped carbon nanometer pipe of 1.0g (the ethanol/water volume ratio=1:1); Continue to stir 12h, deposition is washed through decompress filter; In 353K vacuum drying 12h, promptly make the Pt/ nitrogen-doped carbon nanometer pipe load type metal nanocluster catalyst of platiniferous 10wt%.
Tem study shows that the average grain diameter of Pt metal nanometre cluster is 2nm in the prepared Pt/ nitrogen-doped carbon nanometer pipe load type metal nano-cluster, and particle diameter is distributed as 1-3nm.
This catalyst 2,3,5-trimethylbenzoquinone hydrogenation Synthetic 2,3, show excellent catalytic performance (seeing embodiment 16) in the reaction of 5-TMHQ.
Embodiment 6: preparation contains the carbon nanotube loaded type alloy nanocluster catalyst of Pt-Ru/ (mol ratio of Pt:Ru is 3:1) of 20wt% noble metal
0.5179g six hydration chloroplatinic acids and 0.0105g hydrate ruthenium trichloride are dissolved in the 25ml ethylene glycol; Get the ethylene glycol solution (0.35mol/L) of 25ml NaOH; Under agitation the ethylene glycol solution with above-mentioned chloroplatinic acid and ruthenic chloride mixes, and at room temperature continues to stir 5min, and the gained reactant is made " non-protection type " Pt-Ru alloy nanocluster colloid at 453K backflow 3h; It is subsequent use to be cooled to room temperature, and wherein the concentration of metal Pt-Ru is 3.97g/L.
Tem study shows that the average grain diameter of Pt-Ru alloy nanocluster is 1.9nm in the Pt-Ru alloy nanocluster colloid, and particle diameter is distributed as 1.4-2.4nm, and EDX analyzes and shows that prepared alloy nanocluster particle is made up of Pt, Ru.
Get the dense HNO that the multi-walled carbon nano-tubes 1g that is purchased is scattered in 25ml60%
3In, under 343K, handle 2h, after the cooling that the precipitate with deionized water washing is extremely neutral, subsequent use behind dry 12h under the 353K.
Get the Pt-Ru alloy nanocluster colloid of the above-mentioned preparation of 12.6ml; Under stirring fast, join 35ml and be dispersed with in the glycol water of the above-mentioned treated carbon nanotube carrier of 0.2g (glycol/water volume ratio=1:1); Continue to stir 10h, deposition is through centrifugalizing washing; In 400K vacuum drying 12h, promptly make the carbon nanotube loaded type alloy nanocluster catalyst of the Pt-Ru/ that contains noble metal 20wt%.
Tem study shows that the average grain diameter of Pt-Ru alloy nanocluster is 1.9nm in the carbon nanotube loaded type alloy nanocluster catalyst of prepared Pt-Ru/, and particle diameter is distributed as 1.4-2.4nm
This catalyst is 2,3,5-trimethylbenzoquinone hydrogenation Synthetic 2, and 3, show good catalytic performance in the reaction of 5-TMHQ.
Embodiment 7: preparation contains the Pt/Al of 1wt%Pt
2O
3The load type metal nanocluster catalyst
Prepare Pt metal nanometre cluster colloid by embodiment 1 method.
Al
2O
3Carrier prepares by following method: the 10.2g aluminium isopropoxide is scattered in the 135ml deionized water, stirs 1h down in 353K, after wherein add the 1ml red fuming nitric acid (RFNA), under 353K, continuing to stir 2h; Temperature rising reflux 12h is cooled to room temperature, with gained sediment suction filtration, and washing; At 353K air drying 10h, again with its in air in 823K roasting 3h, be cooled to room temperature; Grind, sieve, choose 50-100 order Al
2O
3Subsequent use.
Get the prepared Pt metal nanometre cluster colloid of 5.4ml, under stirring fast, Pt metal nanometre cluster colloid drops is added to 50ml and is dispersed with the above-mentioned Al of 2.0g
2O
3Ethanol in, continue to stir 1h at 298K, sediment is centrifugalized from dispersion, washing in 353K vacuum drying 12h, promptly makes the Pt/Al of platiniferous 1wt%
2O
3The load type metal nanocluster catalyst.
Tem study shows, prepared Pt/Al
2O
3The average grain diameter of Pt metal nanometre cluster is 2nm in the load type metal nanocluster catalyst, and particle diameter is distributed as 1-3nm, carrier A l
2O
3The primary particle average grain diameter is 15nm, and particle diameter is distributed as 6-25nm, Al
2O
3Combine closely between the primary particle, form mesh structural porous structure.
This catalyst is to 2,3,5-trimethylbenzoquinone hydrogenation Synthetic 2, and 3, the reaction of 5-TMHQ has excellent catalytic performance (seeing embodiment 17).
Embodiment 8: preparation contains Pt/ α-Fe of 0.5wt%Pt
2O
3The load type metal nanocluster catalyst
The 1g platinum tetrachloride is dissolved in the ethylene glycol solution that obtains platinum tetrachloride in the 50ml ethylene glycol; Get the ethylene glycol solution (0.23mol/L) of 50ml NaOH, under agitation join in the ethylene glycol solution of this platinum tetrachloride, at room temperature continue to stir 15min; With the gained reactant liquor at the 433K 3h that refluxes; Make " non-protection type " platinum nano-cluster colloid, it is subsequent use to be cooled to room temperature, and wherein the concentration of metal Pt is 5.76g/L.
Tem study shows that the average grain diameter of Pt metal nanometre cluster is 3.8nm in the platinum nano-cluster colloid, and particle diameter is distributed as 2.5-5.0nm.
α-Fe
2O
3Carrier prepares by following method: the configuration quality percent concentration is 10% ammoniacal liquor and 4% iron chloride (0.25mol/L) aqueous solution respectively, gets an amount of ammonia spirit and slowly is added drop-wise in the 100ml ferric chloride solution, finally controls pH about 7.5, aging 5min.The ferric hydroxide precipitate that generates is filtered, washed to there not being Cl
-Ion, with filter cake after the 353K drying, again in the air in 673K roasting 3h, be cooled to room temperature, promptly obtain α-Fe
2O
3
Get the Pt metal nanometre cluster colloid of the above-mentioned preparation of 2.8ml, to wherein adding 0.5mol/L HNO
32ml forms Pt metal nanometre cluster colloid again with being scattered in after the metal nanometre cluster precipitation and centrifugal separation again in the 5ml ethylene glycol, then with gained Pt metal nanometre cluster colloid ultrasonic, be added drop-wise to 30ml under stirring and be dispersed with above-mentioned 2.0 α-Fe
2O
3The N of carrier in the dinethylformamide, continues to stir 10h, and deposition in the dry 12h of 523K, promptly makes Pt/ α-Fe of platiniferous 0.5wt% through filtration under diminished pressure, washing under argon shield
2O
3The load type metal nanocluster catalyst.
Tem study shows, prepared Pt/ α-Fe
2O
3The average grain diameter of Pt metal nanometre cluster is 3.8nm in the load type metal nanocluster catalyst, and particle diameter is distributed as 2.5-5.0nm, carrier α-Fe
2O
3The primary particle average grain diameter is 16nm, and particle diameter is distributed as 12-20nm, α-Fe
2O
3Combine closely between the primary particle, form mesh structural porous structure.
This catalyst is to 2,3,5-trimethylbenzoquinone hydrogenation Synthetic 2, and 3, the reaction of 5-TMHQ has excellent catalytic performance.
Embodiment 9: preparation contains the Pt/SiO of 0.1wt%Pt
2The load type metal nanocluster catalyst
0.1g six hydration chloroplatinic acids are dissolved in the 50ml ethylene glycol; Get the aqueous solution (0.077mol/L) of 50ml NaOH; Under agitation add in the ethylene glycol solution of chloroplatinic acid, continue to stir 25min, the gained reactant is made " non-protection type " platinum nano-cluster colloid in 403K backflow 3h under argon shield in room temperature; It is subsequent use to be cooled to room temperature, and wherein the concentration of metal Pt is 0.375g/L.
Tem study shows that the average grain diameter of Pt metal nanometre cluster is 2.4nm in the platinum nano-cluster colloid, and particle diameter is distributed as 1.4-4.5nm.
SiO
2Carrier prepares by following method: get the 45.0ml ethyl orthosilicate, add the hydrochloric acid of 47.0ml absolute ethyl alcohol, 7.2ml deionized water, 6.0ml1.0mol/L, 343K reaction 2h obtains water white silica sol then.Regulate SiO
2The pH to 7 of colloidal sol makes it gel, and washing, vacuum 343K desiccant gel obtain white SiO then
2Powder is with SiO
2Powder is handled 3h at 673K, promptly makes SiO
2
Get 5.4ml gained Pt nano-cluster colloid; To wherein adding 1mol/L formic acid 5.0ml; With being scattered in again after the metal nanometre cluster precipitation and centrifugal separation in the 5.0ml oxolane, under stirring fast, gained metal nanometre cluster colloid drops being added to 20ml and being dispersed with the above-mentioned SiO of 2.0g
2Acetone in, continue to stir 90min, deposition through centrifugation, wash after in 353K air drying 12h, promptly make the Pt/SiO of platiniferous 0.1wt%
2The load type metal nanocluster catalyst.
Tem study shows, prepared Pt/SiO
2The average grain diameter of Pt metal nanometre cluster is 2.4nm in the load type metal nanocluster catalyst, and particle diameter is distributed as 1.5-4.5nm, carrier S iO
2The primary particle average grain diameter is 30nm, and particle diameter is distributed as 15-50nm, SiO
2Combine closely between the primary particle, form mesh structural porous structure.
This catalyst is to 2,3,5-trimethylbenzoquinone hydrogenation Synthetic 2, and 3, the reaction of 5-TMHQ has excellent catalytic performance.
Embodiment 10: preparation contains the Rh/TiO of 2wt%Rh
2The load type metal nanocluster catalyst
With 0.079g RhCl
33H
2O (99.9%) is dissolved in the 100ml ethylene glycol, under electromagnetic agitation, it is joined in the ethylene glycol solution (0.25mol/l) of 10ml NaOH, continues to stir 30min under the room temperature; The gained reactant liquor is heated to 433K and keeps this heating, stirring condition; Continue reaction 3h, pass through reaction system with Ar gas in the whole heating process, make " non-protection type " rhodium metal nano-cluster colloid; It is subsequent use to be cooled to room temperature, and wherein the concentration of metal Rh is 0.31g/l.
Tem study shows that the average grain diameter of Rh metal nanometre cluster is 1.3nm in the rhodium metal nano-cluster colloid, and particle diameter is distributed as 0.7-2.1nm.
Carrier TiO
2Prepare by following method: in glove box, measure the 10.0ml isopropyl titanate, add 10.0ml absolute ethyl alcohol dilution (heat release in the dilution), to be cooled to room temperature, it dropwise joins the HNO that 60.0ml concentration is 0.2mol/L in vigorous stirring decline
3In, then at 353K peptization 10h, sonicated 30min obtains translucent TiO again
2Colloidal sol.Regulate TiO
2The pH to 7 of colloidal sol makes its gelation, then detergent gel, in 343K vacuum drying 10h, obtain white TiO
2Powder is with TiO
2Powder is handled 3h at 673K, promptly makes TiO
2
Get the prepared Rh metal nanometre cluster colloid of 19.7ml, under stirring fast, Rh metal nanometre cluster colloid drops is added to 50ml and is dispersed with the above-mentioned TiO of 0.3g
2Ethanol water in (ethanol/water volume ratio=1:1) continues to stir 1h at 298K, and sediment is centrifugalized from dispersion, and washing in 353K vacuum drying 12h, promptly makes the Rh/TiO of rhodium-containing 2wt%
2The load type metal nanocluster catalyst.
Tem study shows, prepared Rh/TiO
2The average grain diameter of Rh metal nanometre cluster is 1.3nm in the load type metal nanocluster catalyst, and particle diameter is distributed as 0.7-2.2nm, carrier TiO
2The primary particle average grain diameter is 17nm, and particle diameter is distributed as 10-30nm, TiO
2Combine closely between the primary particle, form mesh structural porous structure.
This catalyst is to 2,3,5-trimethylbenzoquinone hydrogenation Synthetic 2, and 3, the reaction of 5-TMHQ has good catalytic performance.
Embodiment 11: preparation contains the Ru/SnO of 3wt%Ru
2The load type metal nanocluster catalyst
Take by weighing 0.095g RuCl
36H
2O (99.9%) is dissolved in the 100ml ethylene glycol, under electromagnetic agitation, to wherein adding 10ml sodium hydrate aqueous solution (0.5mol/l), continues to stir 30min under the room temperature; The gained reactant liquor is heated to 433K and keeps this heating, stirring condition; Continue reaction 3h, pass through reaction system with Ar gas in the whole heating process, make " non-protection type " ruthenium metal nanometre cluster colloid; It is subsequent use to be cooled to room temperature, and wherein the concentration of metal Ru is 0.32g/l.
Tem study shows that the average grain diameter of Ru metal nanometre cluster is 1.1nm in the ruthenium metal nanometre cluster colloid, and particle diameter is distributed as 0.7-2.2nm.
Carrier S nO
2By the preparation of following method: be added drop-wise to the 10.0ml anhydrous stannic chloride in the 40.0ml propyl alcohol, exothermic heat of reaction, treat that it is cooled to room temperature after, the mixed solution of 20.0ml propyl alcohol and 5.0ml water is added drop-wise in this solution.Again to the mixed solution that wherein adds 40.0ml isopropyl alcohol and 10.0ml water, continue to stir 1h and make SnO behind the stirring at room 1h
2Colloidal sol.Regulate SnO
2The pH to 7 of colloidal sol makes its gelation, then detergent gel, in 343K vacuum drying gel, obtain white SnO
2Powder is with SnO
2Powder is handled 3h at 673K, promptly makes SnO
2
Get the prepared Ru metal nanometre cluster colloid of 48.3ml, under stirring fast, Ru metal nanometre cluster colloid drops is added to 50ml and is dispersed with the above-mentioned SnO of 0.5g
2Ethanol water in (ethanol/water volume ratio=1:3) continues to stir 1h at 298K, and the sediment of decompress filter separation system, and spend deionised water in 363K vacuum drying 12h, promptly makes the Ru/SnO that contains ruthenium 3wt%
2The load type metal nanocluster catalyst.
Tem study shows, prepared Ru/SnO
2The average grain diameter of Ru metal nanometre cluster is 1.1nm in the load type metal nanocluster catalyst, and particle diameter is distributed as 0.7-2.2nm, carrier S nO
2The primary particle average grain diameter is 20nm, and particle diameter is distributed as 5-50nm, SnO
2Combine closely between the primary particle, form mesh structural porous structure.
This catalyst is to 2,3,5-trimethylbenzoquinone hydrogenation Synthetic 2, and 3, the reaction of 5-TMHQ has good catalytic performance.
Embodiment 12: preparation contains the Pt/CeO of 3wt%Pt
2The load type metal nanocluster catalyst
Prepare Pt metal nanometre cluster colloid by embodiment 1 method.
CeO
2Method preparation (Q.Fu, et al., Nanostructured Au-CeO in the carrier reference literature
2Catalystsfor low-temperature water-gas shift.Catalysis Letters2001,77,87-95).
Get the prepared Pt metal nanometre cluster colloid of 16.5ml, under stirring fast, Pt metal nanometre cluster colloid drops is added to 50ml and is dispersed with the above-mentioned CeO of 2.0g
2Oxolane, water mixed solvent (in the volume ratio=1:2), continue to stir 1h at 298K, sediment is centrifugalized from dispersion, washing in 373K vacuum drying 12h, promptly makes the Pt/CeO of platiniferous 3wt%
2The load type metal nanocluster catalyst.
Tem study shows, prepared Pt/CeO
2The average grain diameter of Pt metal nanometre cluster is 2nm in the load type metal nanocluster catalyst, and particle diameter is distributed as 1-3nm, support C eO
2The primary particle average grain diameter is 40nm, and particle diameter is distributed as 25-100nm, CeO
2Combine closely between the primary particle, form mesh structural porous structure.
This catalyst is to 2,3,5-trimethylbenzoquinone hydrogenation Synthetic 2, and 3, the reaction of 5-TMHQ has excellent catalytic performance (seeing embodiment 18).
Embodiment 13: preparation contains the Pt-Ir/ZrO of 1wt% noble metal
2Support type alloy nanocluster catalyst (mol ratio of Pt:Ir is 5:1)
0.4990g six hydration chloroplatinic acids and 0.0679g hydration iridous chloride are dissolved in the 50ml ethylene glycol; The ethylene glycol solution (NaOH concentration is 0.6mol/L) of getting 50ml NaOH under agitation joins in the above-mentioned solution; At room temperature continue to stir 15min; The gained reactant is made " non-protection type " Pt-Ir alloy nanocluster colloid in 453K backflow 3h under argon shield, it is subsequent use to be cooled to room temperature, and wherein the concentration of metal Pt-Ir is 2.25g/L.Tem study shows that the average grain diameter of Pt-Ir alloy nanocluster is 1.5nm in the Pt-Ir alloy nanocluster colloid, and particle diameter is distributed as 1-3nm.
Carrier ZrO
2Method preparation (J.Santiesteban, et al., Influence of the preparativemethod on the activity of highly acidic WO in the reference literature
x/ ZrO
2And the relative acid activity comparedwith zeolites.J.Catal.1997,168,431-441).
Get 4.5ml gained Pt-Ir alloy nanocluster colloid, under ultrasound condition, join 20ml and be dispersed with the above-mentioned ZrO of 1.0g
2(ethanol/water volume ratio=1:1), continue to stir 60min, with precipitation and centrifugal separation, washing in the dry 12h of 353K, promptly makes the Pt-Ir/ZrO that contains noble metal 1wt% under argon shield in the ethanol water of carrier
2The support type alloy nanocluster catalyst.
Tem study shows, prepared Pt-Ir/ZrO
2The average grain diameter of Pt-Ir alloy nanocluster is 1.5nm in the support type alloy nanocluster catalyst, and particle diameter is distributed as 1-3nm, ZrO
2The primary particle average grain diameter is 35nm, and particle diameter is distributed as 20-70nm, ZrO
2Combine closely between the primary particle, form mesh structural porous structure.
This catalyst is to 2,3,5-trimethylbenzoquinone hydrogenation Synthetic 2, and 3, the reaction of 5-TMHQ has excellent catalytic performance.
Embodiment 14: preparation contains the Pt-Rh-Ir/ZnO support type alloy nanocluster catalyst (mol ratio of Pt:Rh:Ir is 4:1:1) of 3wt% noble metal
The mixed solution that 0.5179g six hydration chloroplatinic acids, 0.0658g rhodium trichloride hydrate and 0.0882g hydration iridous chloride are dissolved in 50ml ethylene glycol and glycerine is (in the ethylene glycol/glycerin volume ratio=5:1); Under agitation the ethylene glycol solution (0.16mol/L) with 50ml NaOH joins wherein; At room temperature continue to stir 5min; The gained reactant is made " non-protection type " Pt-Rh-Ir alloy nanocluster colloid in 453K backflow 3h under nitrogen protection; It is subsequent use to be cooled to room temperature, and wherein the concentration of metal Pt-Rh-Ir is 2.69g/L.
Transmission electron microscope is analyzed Pt-Rh-Ir and is shown that the average grain diameter of Pt-Rh-Ir alloy nanocluster is 2nm in the Pt-Rh-Ir alloy nanocluster colloid, and particle diameter is distributed as 1-3nm, and EDX analyzes and shows that the Pt-Rh-Ir alloy nanocluster is made up of above-mentioned three kinds of metals.
Method preparation in the carrier ZnO reference literature (L Vayssieres, et al., Growth of arrayed nanorodsand nanowires of ZnO from aqueous solutions.Adv.Mater.2003,15,464-466).
Get 23.0ml gained Pt-Rh-Ir alloy nanocluster colloid; To wherein adding 0.5mol/L sulfuric acid 95ml; Again form Pt-Ru-Ir alloy nanocluster colloid in the 25ml oxolane with being scattered in again after the metal nanometre cluster precipitation and centrifugal separation, then gained Pt-Ru-Ir alloy nanocluster colloid is joined 20ml down and is dispersed with (ethanol/water volume ratio=1:1), continue stirring 90min in the ethanol water of the above-mentioned ZnO carrier of 2.0g stirring fast; The centrifugation deposition; Washing in 353K vacuum drying 12h, promptly makes the Pt-Rh-Ir/ZnO support type alloy nanocluster catalyst that contains noble metal 3wt%.
Tem study shows; The average grain diameter of Pt-Rh-Ir alloy nanocluster is 2nm in the prepared Pt-Rh-Ir/ZnO support type alloy nanocluster catalyst, and particle diameter is distributed as 1-3nm, and it is bar-shaped that ZnO is; Diameter is 100-200nm, and length reaches about 10 μ m.
This catalyst is to 2,3,5-trimethylbenzoquinone hydrogenation Synthetic 2, and 3, the reaction of 5-TMHQ has excellent catalytic performance.
Select the soluble-salt of Pt, Rh, Ru, Ir, Os etc. or in the acid two or more, adopt and the similar method of embodiment 1-14, can prepare the catalyst of the support type alloy nanocluster that contains these transition metal.
Second portion carrier-borne transition metal or alloy nanocluster catalyst catalytic reaction embodiment
Carrier-borne transition metal provided by the invention or alloy nanocluster catalyst have excellent catalytic performance, thereby are with a wide range of applications.
Transition metal in carrier-borne transition metal provided by the invention or the alloy nanocluster catalyst or alloy nanocluster are adsorbed in the outer surface or bigger hole of carrier; Have very high decentralization and can reach the space; Improved the utilization ratio of transition metal or alloy nanocluster surface atom; 2,3, show excellent catalytic activity in the 5-trimethylbenzoquinone hydrogenation.Carrier-borne transition metal of the present invention or alloy nanocluster catalyst are scattered in the appropriate amount of organic, under hydrogen atmosphere, make catalyst activation, 2; 3; The organic solution of 5-trimethylbenzoquinone adds in the reactor, under agitation implements hydrogenation reaction, and product is used gas chromatographic detection.Can adopt modes such as centrifugal or filtration with catalyst and reactants separate after reaction finishes, reuse.Generally, hydrogenation condition: temperature, 273-353K; Pressure, 0.1-10MPa; Solvent can adopt ethyl acetate, alcohol or other organic solvents (for example, oxolane (THF), N, dinethylformamide (DMF), toluene etc.).
Embodiment 15:Pt/C load type metal nanocluster catalyst be purchased Pt/C catalyst 2,3, the contrast of 5-trimethylbenzoquinone hydrogenation property
1) Pt/C load type metal nanocluster catalyst that contains 1wt%Pt and the performance comparison that is purchased the Pt/C catalyst
The Pt/C load type metal nanocluster catalyst of the platiniferous 1wt% that 0.1g embodiment 4 is prepared is scattered in the 10ml ethyl acetate, at 303K, makes catalyst activation 0.5h under the 0.1MPa Hydrogen Vapor Pressure; With 3mmol2,3, the 5-trimethylbenzoquinone is dissolved in the 10ml ethyl acetate; Joining above-mentioned 10ml is dispersed with in the ethyl acetate of Pt/C load type metal nanocluster catalyst; At Hydrogen Vapor Pressure is 0.1MPa, and temperature is to carry out catalytic reaction under 303K and the stirring condition, and product is used gas chromatographic analysis.The Pt/C catalyst (Acros) of the platiniferous 1wt% that is purchased is tested under identical condition.Experimental result is listed in table 1.
2) Pt/C load type metal nanocluster catalyst that contains 5wt%Pt and the performance comparison that is purchased the Pt/C catalyst
The Pt/C load type metal nanocluster catalyst of the platiniferous 5wt% that 0.03g embodiment 1 is prepared is scattered in the 10ml ethyl acetate, at 303K, makes catalyst activation 0.5h under the 0.1MPa Hydrogen Vapor Pressure; With 3mmol2,3, the 5-trimethylbenzoquinone is dissolved in the 10ml ethyl acetate; Joining above-mentioned 10ml is dispersed with in the ethyl acetate of Pt/C load type metal nanocluster catalyst; At Hydrogen Vapor Pressure is 0.1MPa, and temperature is to carry out catalytic reaction under 303K and the stirring condition, and product is used gas chromatographic analysis.The Pt/C catalyst (Acros) of the platiniferous 5wt% that is purchased is tested under identical condition.Experimental result is listed in table 1.
3) Pt/C load type metal nanocluster catalyst that contains 40wt%Pt and the performance comparison that is purchased the Pt/C catalyst
The Pt/C load type metal nanocluster catalyst of the platiniferous 40wt% that 0.005g embodiment 3 is prepared is scattered in the 10ml ethyl acetate, places autoclave, at 303K; Make catalyst activation 0.5h under the 1MPa Hydrogen Vapor Pressure; Contain 20mmol2 to wherein adding 10ml then, 3, the ethyl acetate solution of 5-trimethylbenzoquinone; At Hydrogen Vapor Pressure is that 1.3MPa, temperature are to carry out catalytic reaction under 303K and the stirring condition, and product is used gas chromatographic analysis.The Pt/C catalyst (Aldich) of the platiniferous 40wt% that is purchased is tested under identical condition.Experimental result is listed in table 1.
Show 1Pt/C load type metal nanocluster catalyst and be purchased Pt/C catalyst 2,3, the hydrogenation property contrast of 5-trimethylbenzoquinone
Embodiment 16:Pt/ nitrogen-doped carbon nanometer pipe load type metal nanocluster catalyst catalysis 2,3,5-trimethylbenzoquinone hydrogenation property
The Pt/ nitrogen-doped carbon nanometer pipe load type metal nanocluster catalyst of the platiniferous 10wt% that 0.01g embodiment 5 is prepared is scattered in the 10ml ethyl acetate, places autoclave, at 303K; 0.5MPa make catalyst activation 0.5h under the Hydrogen Vapor Pressure, contain 3mmol2,3 to wherein adding 10ml then; The ethyl acetate solution of 5-trimethylbenzoquinone; At Hydrogen Vapor Pressure is 1.0MPa, and temperature is to carry out catalytic reaction under 303K and the stirring condition, and negate answers the product behind the 15min to use gas chromatographic analysis.This catalyst catalytic performance result lists in table 2.
Table 2Pt/ nitrogen-doped carbon nanometer pipe load type metal nanocluster catalyst catalysis 2,3, the hydrogenation property of 5-trimethylbenzoquinone
Embodiment 17:Pt/Al
2O
3The load type metal nanocluster catalyst be purchased Pt/Al
2O
3Catalyst 2,3, the contrast of 5-trimethylbenzoquinone hydrogenation property
The Pt/Al of the platiniferous 1wt% that 0.03g embodiment 7 is prepared
2O
3The load type metal nanocluster catalyst is scattered in the 10ml ethyl acetate, at 0.1MPa hydrogen, makes catalyst activation 0.5h under the 303K, with 3mmol2, and 3, the 5-trimethylbenzoquinone is dissolved in the 10ml ethyl acetate, joins above-mentioned 10ml and is dispersed with this Pt/Al
2O
3In the ethyl acetate of load type metal nanocluster catalyst, be 0.1MPa at Hydrogen Vapor Pressure, temperature is to carry out catalytic reaction under 303K and the stirring condition, and product is used gas chromatographic analysis.Pt/Al with the platiniferous 1wt% that is purchased
2O
3Catalyst (AlfaAesar) is tested under identical condition.
Pt/Al
2O
3The load type metal nanocluster catalyst be purchased Pt/Al
2O
3Catalyst 2,3,5-trimethylbenzoquinone hydrogenation property is as shown in table 3.
Table 3Pt/Al
2O
3The load type metal nanocluster catalyst be purchased Pt/Al
2O
3Catalyst 2,3, the hydrogenation property contrast of 5-trimethylbenzoquinone
Embodiment 18:Pt/CeO
2Load type metal nanocluster catalyst catalysis 2,3,5-trimethylbenzoquinone hydrogenation property
The Pt/CeO of the platiniferous 3wt% that 0.02g embodiment 12 is prepared
2The load type metal nanocluster catalyst is scattered in the 10ml ethyl acetate, places autoclave, at 313K; 0.5MPa make catalyst activation 0.5h under the Hydrogen Vapor Pressure, contain 3mmol2,3 to wherein adding 10ml then; The ethyl acetate solution of 5-trimethylbenzoquinone; At Hydrogen Vapor Pressure is 1.5MPa, and temperature is to carry out catalytic reaction under 333K and the stirring condition, and negate answers the product behind the 30min to use gas chromatographic analysis.This catalyst catalytic performance result lists in table 4.
Table 4Pt/CeO
2Load type metal nanocluster catalyst catalysis 2,3,5-trimethylbenzoquinone hydrogenation property
Catalysis experimental result in the foregoing description shows, carrier-borne transition metal of the present invention or alloy nanocluster catalyst be 2,3,5-trimethylbenzoquinone hydrogenation Synthetic 2, and 3, show excellent catalytic performance in the reaction of 5-TMHQ.
Claims (13)
1. a method for preparing transition metal or transition metal alloy nanocluster catalyst comprises the steps:
1) salt or the acid with one or more transition metal is dissolved in alcohol or the alcohol-water mixture, obtains transistion metal compound solution; The alcohol and/or the aqueous solution of alkali-metal hydroxide are mixed with said transistion metal compound solution, obtain transition metal nano-cluster colloid or transition metal alloy nano-cluster colloid after reaction finishes;
Said transition metal is Pt, Rh, Ru, Ir or Os, and said alcohol is ethylene glycol and/or glycerine; Said alkali metal is lithium, sodium or potassium;
2) carrier is scattered in the solvent, obtains carrier suspension;
Wherein, said carrier is CNT, activated carbon, carbon black, α-Fe
2O
3, Al
2O
3, SiO
2, TiO
2, SnO
2, CeO
2, ZrO
2Or ZnO;
Said solvent is water and/or the water-soluble organic solvent of ability;
The water-soluble organic solvent of said ability is selected from the mixture of any one or its arbitrary proportion in the following solvents: the monohydric alcohol of C1-C4, dihydroxylic alcohols or trihydroxylic alcohol, acetone, oxolane, N, dinethylformamide;
3) the transition metal nano-cluster colloid or transition metal alloy nano-cluster colloid and the said step 2 that said step 1) are obtained) the carrier suspension mixing that obtains, obtain said transition metal or transition metal alloy nanocluster catalyst after separating drying.
2. method according to claim 1 is characterized in that: in the said step 1), transition metal nano-cluster colloid is Pt, Rh, Ru or Ir nano-cluster colloid; Said transition metal alloy nano-cluster is the alloy nanocluster colloid that any two or more element among Pt, Rh, Ru, Ir or the Os forms;
Said step 2) in, carrier is the nitrogen-doped carbon nanometer pipe in the CNT, or CeO
2
3. method according to claim 1 is characterized in that: in the said step 1), the concentration of said transistion metal compound solution is 0.01-200g/L, and the volumn concentration of water is 0-50% in the said alcohol-water mixture; The mol ratio of the salt of said alkali-metal hydroxide and said transition metal or acid is 3-20: 1;
Said step 2) in, the quality of the carrier that is disperseed in said every liter of carrier suspension is 0.1-1000g;
In the said step 3), the mass ratio of carrier is 1 in said transition metal nano-cluster colloid or transition metal alloy nano-cluster colloid and the said carrier suspension: 1-1000.
4. method according to claim 1 is characterized in that: in the said step 1), reaction temperature is 343-473K;
Said step 2) in, the quality of the carrier that is disperseed in said every liter of carrier suspension is 1-100g.
5. method according to claim 1 is characterized in that: in the said step 3), said separating step is after 273-473K handles 0.1-200h, to isolate sediment; Said drying steps is that the sediment that said separating step obtains is carried out drying in 290-523K.
6. method according to claim 1 is characterized in that: said step 2), saidly be separated into ultrasonic or dispersed with stirring;
In the said step 3), said mixing carries out under ultrasonic or stirring condition.
7. method according to claim 1; It is characterized in that: in the said step 1); After said reaction finishes; The aqueous solution that in said transition metal nano-cluster colloid or transition metal alloy nano-cluster colloid, adds hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, oxalic acid, acid or glacial acetic acid; Obtain transition metal or transition metal alloy nano-cluster deposition, the aqueous slkali that more said transition metal or transition metal alloy nano-cluster deposition is scattered in ethylene glycol maybe can dissolve in the solution of organic solvent of water, obtains transition metal nano-cluster colloid or transition metal alloy nano-cluster colloid.
8. method according to claim 7 is characterized in that: in the said step 1), the concentration of the aqueous solution of hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, oxalic acid, acid or glacial acetic acid is 0.1-10mol/L; The water-soluble organic solvent of said ability comprises methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol, glycerine, acetone, oxolane or N, dinethylformamide.
9. the transition metal or the transition metal alloy nanocluster catalyst that obtain of the arbitrary described preparation method of claim 1-8.
10. catalyst according to claim 9 is characterized in that: in said transition metal or the transition metal alloy nanocluster catalyst, comprise transition metal or transition metal alloy nano-cluster and carrier;
Wherein, said carrier is CNT, activated carbon, carbon black, α-Fe
2O
3, Al
2O
3, SiO
2, TiO
2, SnO
2, CeO
2, ZrO
2Or ZnO.
11. catalyst according to claim 10 is characterized in that: said CNT is a nitrogen-doped carbon nanometer pipe.
12. according to claim 9 or 10 or 11 described catalyst, it is characterized in that: in said transition metal or the alloy nanocluster catalyst, the quality percentage composition of transition metal or transition metal alloy nano-cluster is 0.1-50%; Particle diameter is 0.7-5nm.
13. arbitrary described transition metal of claim 9-12 or transition metal alloy nanocluster catalyst be 2,3, the application in the 5-trimethylbenzoquinone hydrogenation reaction.
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| US5208207A (en) * | 1990-09-29 | 1993-05-04 | Tanaka Kikinzoku Kogyo K.K. | Electrocatalyst |
| CN1259395A (en) * | 1999-01-04 | 2000-07-12 | 北京大学 | Nanometer grade transtion metal and its alloy colloid and prepn. method thereof |
| CN1448216A (en) * | 2002-04-03 | 2003-10-15 | 中国科学院大连化学物理研究所 | Prep. of high-load bi-and multi-component precious metallic catalyst |
| US6686308B2 (en) * | 2001-12-03 | 2004-02-03 | 3M Innovative Properties Company | Supported nanoparticle catalyst |
| CN1577928A (en) * | 2003-07-29 | 2005-02-09 | 中国科学院大连化学物理研究所 | High electrocatalytic active fuel battery platinum-base noble metal catalyst and producing process thereof |
| CN1593754A (en) * | 2004-07-11 | 2005-03-16 | 昆明贵金属研究所 | Catalyst combination and preparation method thereof |
| CN1762590A (en) * | 2004-10-21 | 2006-04-26 | 北京大学 | Transition metal-gamma-Fe2o3 nano material, its preparation method and application |
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5208207A (en) * | 1990-09-29 | 1993-05-04 | Tanaka Kikinzoku Kogyo K.K. | Electrocatalyst |
| CN1259395A (en) * | 1999-01-04 | 2000-07-12 | 北京大学 | Nanometer grade transtion metal and its alloy colloid and prepn. method thereof |
| US6686308B2 (en) * | 2001-12-03 | 2004-02-03 | 3M Innovative Properties Company | Supported nanoparticle catalyst |
| CN1448216A (en) * | 2002-04-03 | 2003-10-15 | 中国科学院大连化学物理研究所 | Prep. of high-load bi-and multi-component precious metallic catalyst |
| CN1577928A (en) * | 2003-07-29 | 2005-02-09 | 中国科学院大连化学物理研究所 | High electrocatalytic active fuel battery platinum-base noble metal catalyst and producing process thereof |
| CN1593754A (en) * | 2004-07-11 | 2005-03-16 | 昆明贵金属研究所 | Catalyst combination and preparation method thereof |
| CN1762590A (en) * | 2004-10-21 | 2006-04-26 | 北京大学 | Transition metal-gamma-Fe2o3 nano material, its preparation method and application |
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