CN1171670C - Prep. of high-load bi-and multi-component precious metallic catalyst - Google Patents
Prep. of high-load bi-and multi-component precious metallic catalyst Download PDFInfo
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- CN1171670C CN1171670C CNB021062013A CN02106201A CN1171670C CN 1171670 C CN1171670 C CN 1171670C CN B021062013 A CNB021062013 A CN B021062013A CN 02106201 A CN02106201 A CN 02106201A CN 1171670 C CN1171670 C CN 1171670C
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Abstract
The present invention relates to a preparation method of an element and multi-element noble metal catalyst with a high carrying capacity, which is suitable for preparing loading carrying type catalysts of double element and multi-element containing various noble metal with higher carrying capacities. Noble metal is one or a plurality of kinds of Pt, Pd, Ru, Os, Ir, Rh, Re, etc., and other metal comprises one or a plurality of kinds of other transition metal except the selected metal. The viscosity of a solvent is enhanced by changing the components of the solvent in a dispersion system, which can effectively reduce the diffusion rate of metal particles in the solvent and prevent the mutual polymerization from increasing among the metal particles. At the same time, a macro molecule surface active agent is not needed, which can obtain various loading carrying type nanometer stage double element catalysts and multi-element catalysts of the noble metal and taking the noble metal as a base. The present invention can once carry a plurality of kinds of metal onto carriers, and even if under the condition of a hither metal carrying capacity, the present invention can also be guaranteed to have higher metal dispersity.
Description
Technical field
The invention belongs to the technical field of producing catalyst with the chemical method, relate in particular to support type double elements and multicomponent Preparation of catalysts method based on noble metal.
Background technology
Load type metal catalyst for low content, very ripe preparation method has been arranged at present, also be easy to make the metal that supports to reach high degree of dispersion, this class catalyst is relatively easily preparation also, relatively Chang Yong method is at first noble metal precursor to be immersed on the carrier, reduces at a certain temperature then to get final product.But be not easy to make the metal that supports to realize high degree of dispersion for the load type metal catalyst that the high loadings of extensive use is more arranged especially double elements multicomponent metallic catalyst, thereby cause the utilization rate of noble metal not high.
The electrode catalyst that low-temperature fuel cell such as PEM types of fuel cells (PEMFCs) and DMFC (DMFCs) etc. are adopted mainly is the Pt catalyst of high loadings or based on the double elements multicomponent catalyst of Pt at present, (operating temperature of these several types of fuel cells is no more than 180 ℃) is for guaranteeing certain reaction speed under lower operating temperature, electrode catalyst requires to have higher noble metal loading, and bullion content is many between 10-90%.These noble metal resource-constraineds cost an arm and a leg, and need to improve the utilization ratio of noble metal, and to promote the low-temperature fuel cell development beyond doubt necessary and prepare nano level finely dispersed supported catalyst.
Noble metal catalyst for the high loadings of other purposes, how to improve the decentralization of noble metal effectively, improve the interaction between noble metal effectively, improve activity of such catalysts, improving the utilization rate of noble metal resource, also is the pressing issues that the Preparation of Catalyst aspect is badly in need of solving.
At the problems referred to above and requirement, many research workers have attempted several different methods and have prepared and improve the noble metal catalyst of high loadings and the noble metal catalyst of other type.With regard to these present high loadings Nobel-metal catalyst preparation methods, can be divided three classes roughly.
One class is the Pt base supported catalyst that the colloid method prepares high loadings.This method mainly is by preparing metastable metal oxide colloids, transfer on the carrier by sedimentation then, handling making again through other process.Document [1] (H.G.Petrow, R.G.Allen USP 3,992,331), document [2] (M.Watanabe, J.Electroanal.Chem.229 (1987) 395) and document [3] (A.K.Shukla, J.Appl.Electrochem., 29 (1999) 129) mainly preparing carbon by these class methods carries platinum and Pt-Ru/C catalyst.Document [1] at first is prepared into Na with chloroplatinic acid
6[Pt (SO
3)
4], then by ion-exchange, with Na
6[Pt (SO
3)
4] in sodium ion be exchanged into hydrogen ion, heating is boiled in the air, discharges unnecessary sulfite ion, the last dry at a certain temperature oxide black colloid that makes Pt, this colloid can be distributed in water or other solvent once more, thereby supports at an easy rate on all kinds of carriers.Utilize this method, can make the Pt catalyst of 1.5-2.5 nanometer, this method is owing to just fall chloride ions displace in advance simultaneously, thereby can effectively avoid trace chlorine in the catalyst to cause the loss of catalytic activity.The method for preparing catalyst in the document [2] is at first chloroplatinic acid to be prepared into Na
6[Pt (SO
3)
4], but what be different from document [1] is that this method is not with Na
6[Pt (SO
3)
4] separate separately, but directly add excessive hydrogen peroxide its oxidation Decomposition is formed a kind of stable platinum oxide colloid, take off unnecessary hydrogen peroxide rapid branches such as the compound of dropping ruthenium such as ruthenium trichloride in this colloid then, the oxide junction of also oxidized generation ruthenium-oxide of ruthenium and platinum is synthesized the oxide cluster simultaneously, by the adjusting of pH, they are deposited on the carriers such as active carbon; Can platinum wherein be reduced into metallic state by hydrogen.The catalyst that utilizes the preparation of this method be a kind of be core with the ruthenium-oxide, platinum is positioned at the metal cluster of outer surface.The method for preparing catalyst in the document [3] is at first the chloride of platinum and ruthenium all to be transformed into sulfurous acid network and thing, i.e. Na
6[Pt (SO
3)
4] and Na
6[Ru (SO
3)
4], and it is separated.Then they are mixed and resolve into the mixed oxide colloid with hydrogen peroxide oxidation again, support on the active carbon again.Perhaps as in the document [2] earlier with hydrogen peroxide with Na
6[Pt (SO
3)
4] oxidation Decomposition, add Na then
6[Ru (SO
3)
4] divide and take off unnecessary hydrogen peroxide, while Na
6[Ru (SO
3)
4] being transformed into ruthenium-oxide, the modulation by pH makes two kinds of metal oxide co-precipitations to carrier.
Another kind of method is to adopt surfactant or other organic macromolecule to prepare the nano-noble metal particle of high degree of dispersion as protective agent, perhaps supports on the carrier by the nano noble metal particles of other approach with preparation.These class methods can guarantee higher metal dispersity.But these class methods are very high to solvent, surfactant or protective agent and operating condition requirement, the while complicated operation, and cost is higher.Document [4] (USP 5,641 for H.B nnemann, et al, 723) and document [5] (USP 6,090 for H.B nnemann, et al, 746) adopt the boron hydracid quaternary ammonium salt NR that has long carbochain
4BR
3H makes reducing agent and protective agent reduction transistion metal compound, prepares the narrower nano level metal colloid of particle size distribution range.This method requires the anhydrous and oxygen-free system, and typical preparation process is finished in the oxolane system.Adopt the noble metal catalyst of this method preparation to have catalytic activity preferably.
The 3rd class preparation method's characteristic feature is that noble metal precursor is immersed in carrier surface or is deposited on carrier surface by hydrolysis, and then prepares noble metal catalyst through reduction.The key of these class methods is with noble metal precursor or noble metal and other metal precursor such as chloroplatinic acid, Ru by dipping
3CO
12Deng under the carrier surface deposition, then by liquid-phase reduction agent such as hydrazine hydrate, boron hydrohalogenic acid salt etc., perhaps vapour phase reduction agent such as hydrogen etc. reduce to the carrier that has flooded precursor, both can make all kinds of catalyst.Utilize these class methods can prepare the multicomponent catalyst, but having relatively high expectations of this class methods carrier need higher carrier specific area, and these class methods is not easy to realize the high degree of dispersion of noble metal.To the noble metal catalyst of high loadings, it is not very desirable that these class methods prepare effect.Document [6] (USP 5,208 for P.Stonehart, M.Watanabe, 207) has been introduced a kind of method for preparing the platinum ruthenium palladium three constituent element catalyst that active carbon supports.At first precursor such as the acid of chlorine palladium, chloroplatinic acid and the ruthenic chloride with three kinds of metals mixes, be reduced into opaque mixture with the more weak reducing agent of reducing power such as sodium thiosulfate etc. then, add carbon carrier then, vigorous stirring forms thick slurry, heating evaporation falls solvent between 75-80 ℃, obtain black powder, again black powder is obtained the loaded catalyst of three constituent elements with the aqueous dispersion washing and filtering.Document [7] (M.D.Moser, R.J.Lawson USP 4,677,094) introduced the Preparation of catalysts method that is used for the hydrocarbon reformation hydrogen production, its quick-reading flow sheets is the platinum ashbury metal catalyst that at first prepares support type, floods other elements such as ruthenium, cobalt, rhenium, nickel, iridium then respectively on its surface.This catalyst all is significantly improved at aspects such as active and stability with respect to other catalyst.Document [8] (USP 6,165 for E.Auer, G.Heinz et al, 635) utilizes strong alkaline substance that Pt, Rh, the hydrolysis of Fe precursor are deposited on the absorbent charcoal carrier, forms alloy structure again through water reduction or vapour phase reduction, and through high-temperature process.Utilize the Pt of this method preparation
50Rh
15Fe
35Catalyst shows certain catalytic activity to the electrochemical reduction of oxygen, and metallic is about 10 nanometers.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of high loadings double elements or multicomponent noble metal catalyst, preparation is based on the support type double elements and the multicomponent catalyst of the high metal loading of noble metal, the catalyst of preparation is not limited only to noble metal list constituent element catalyst such as Pt, Pd, Ru, Os, Ir, Rh, Re, can add the support type multicomponent nanocatalyst of more other kind metals preparations based on a kind of in the noble metal or several based on noble metal.This method does not need metal precursor is carried out preliminary treatment; also need not any generally acknowledged surfactant or other macromolecule organic and make the careful even metal loaded catalyst of distribution that protective agent can prepare high degree of dispersion, the loaded catalyst tenor of preparation can be up to 90%.Method for preparing catalyst cost provided by the invention is low, easy to operation.Utilize the double elements and the multicomponent catalyst of this method preparation to have purposes widely, be particularly suitable for doing electrode catalyst of fuel cell, catalytic hydrogenation dehydrogenation, reforming catalyst etc.
For achieving the above object, the preparation method of a kind of high loadings double elements provided by the invention or multicomponent noble metal catalyst, its core content is by changing the composition of solvent in the dispersion, improve the viscosity of solvent, reduce the diffusion rate of metallic in solution effectively, prevent between the metallic polymerization mutually and increase, the loaded nano level noble metal of the high loadings that does not need again simultaneously to adopt molecules surfactant can make high degree of dispersion and based on all kinds of double elements of noble metal, the multicomponent catalyst can reduce the cost for preparing nanocatalyst significantly.Between the various metals,, interact obviously in the while catalyst in conjunction with closely.
Key step of the present invention is as follows:
(1) the pure water mixed system with binary and/or ternary is a solvent, and selected alcohol is preferably dihydroxylic alcohols and/or the trihydroxylic alcohol of C2-C6; Wherein Chun volume content is 5-100%; 40-250 ℃ of dry a few hours, scatter before carrier used, make the carrier suspension of 0.01-0.03g/ml with selected solvent.
(2) noble metal and other metallic compound are dissolved respectively with described solvent of step (1) and/or water, the corresponding aqueous solution or alcoholic solution or pure water mixed solution are made in sonic oscillation mixing 5-60 minute, and wherein tenor is 0.01-100mg/ml.Selected noble metal is a kind of among Pt, Pd, Ru, Os, Ir, Rh, the Re etc. or several, and other metals then comprise a kind of in other transition metal beyond the selected noble metal or several.
(3) by the requirement of metal atomic ratio, the solution that step (2) is prepared mixes with carrier suspension, and sonic oscillation 5-150 minute, inert gas shielding was stirred 0.5-24 hour down.
(4) at-10-30 ℃, it is the alkaline solution of 0.01-4 mol that inert gas shielding adds concentration down, and the solution that step (3) is prepared transfers to the pH value for alkaline, sonic oscillation 5-600 minute, inert gas shielding was stirred 0.5-24 hour down, kept 0.5-12 hour down in 40-250 ℃; Aqueous slkali wherein is to use the solvent identical with preparing carrier to add alkali to make.
(5) solution with step (4) preparation is cooled to 0-50 ℃, with concentration is that to regulate pH value be acidity for the acid solution of 0.01-10 mol, stir or heat up and keep a period of time, to promote precipitation, filter hot deionized water washing, 40-200 ℃ of following vacuum drying, obtain comprising a kind of loaded catalyst of or several noble metals, its total metal content is 0.01-90%.
(6) catalyst that makes can directly use, and also can use after 0.5-24 hour in 150-1200 ℃ of processing under reducing atmosphere or inert atmosphere.
In above-mentioned steps, described aqueous slkali is preferably solution such as NaOH or potassium hydroxide.
In above-mentioned steps, described noble metal and other metal precursor solutions can be respectively single metal precursor solutions, also can be multiple metal precursor mixed solution, or a kind of or several compositions in a kind of in the noble metal or several and other transition metal.
Among the present invention, also the described solution of above-mentioned steps (2) can be regulated the pH value earlier is alkalescence, and then mixes with carrier suspension, and sonic oscillation 5-150 minute, inert gas shielding was stirred 0.5-24 hour down.Kept 0.5-12 hour down in 40-250 ℃ then.All the other same step (5) operations.
The present invention can support on the carrier several metal is disposable, even also can guarantee to have higher metal dispersity under the situation of higher metal loading.The present invention is particularly suitable for preparing the higher double elements that includes all kinds of noble metals of loading, multicomponent loaded catalyst.Noble metal can be a kind of among Pt, Pd, Ru, Os, Ir, Rh, the Re etc. or several, and other metals then comprise a kind of in other transition metal beyond the selected metal or several.The loaded catalyst of this invention preparation has characteristics such as height supports, high dispersive, using rate of metal height.The characteristics that the catalyst preparation process that this invention provides is simple to operate, with low cost.
Characteristics of the present invention are as follows:
1, the present invention can prepare the noble metal carrier catalyst of high loadings, metal loading 0.1-90%.Usually tenor is at 10-90%.
2, adopt the loaded catalyst metallic diameter distribution 0.5-8 nanometer of the present invention's preparation, usually the 1-5 nanometer.Improved using rate of metal.
3, the present invention does not adopt any surfactant or other organic protective agent can prepare the nanoscale double elements and the multicomponent catalyst of the high-load of high degree of dispersion, and metal is uniformly dispersed at carrier surface.It is low to have reduced the Preparation of catalysts cost.
4, the present invention does not need metal precursor is done any processing, and is simple and quick.
5, the present invention can prepare all kinds of loaded noble metal catalysts, and noble metal can comprise a kind of among Pt, Pd, Ru, Os, Ir, Rh, the Re etc. or several.Bullion content scope 0.1-90% is particularly suitable for preparing the higher noble metal catalyst of loading.
6, the present invention can prepare the double elements multicomponent loaded catalyst based on all kinds of noble metals easily.Total metal content scope 0.01-90% is particularly suitable for preparing the load type metal catalyst of high loadings.
Description of drawings
Fig. 1 is X-ray scattering (XRD) figure that utilizes the PtRu double elements catalyst of the different carrying capacity that the present invention prepares, wherein:
Curve 1: self-control PtRu/C (20-10wt%) (embodiment 1).
Curve 2: self-control PtRu/C (40-20wt%) (embodiment 2).
Curve 3: self-control PtRu/C (60-30wt%) (embodiment 3).
Fig. 2 is the double elements of the present invention's preparation and X-ray scattering (XRD) figure of multicomponent catalyst, wherein:
Curve 4:PtRhFe/C (embodiment 10, without high-temperature process).
Curve 5:PdCu/C (embodiment 9).
Curve 6:PtIrRu/C (embodiment 6).
Curve 7:PtCo/C (embodiment 5).
Fig. 3 is the electromicroscopic photograph of the catalyst of the present invention's preparation, wherein:
A: press embodiment 1 preparation.
B: press embodiment 2 preparations.
C: press embodiment 3 preparations.
The specific embodiment
The following examples 1-Fig. 3 have in conjunction with the accompanying drawings comparatively at large been described catalyst preparation process provided by the present invention, but method for preparing catalyst provided by the invention is not restricted to the following example.Carrier mostly is material with carbon element among the following embodiment, but the present invention is not limited in these material with carbon elements, can be generalized to other carriers.Selected in the following embodiments alcohol mostly is ethylene glycol and glycerine, but the present invention is not limited in this two kinds of alcohol, and the mixed alcohol of a kind of or several compositions in the dihydroxylic alcohols of C2-C6, the trihydroxylic alcohol all is suitable for this invention.
Embodiment 1:PtRu/C (30PtRu%, Pt/Ru=1) preparation of electrode catalyst
Active carbon XC-72R handles with the salpeter solution of 5mol/L in advance, and 200 ℃ of dryings take by weighing 5 grams and disperse to make in 30 minutes the carbon slurry with 400 milliliters of ethylene glycol sonic oscillations after 4 hours.3.9 gram chloroplatinic acid (containing 1.44 gram platinum) and 1.94 gram ruthenium trichlorides (containing 0.72 gram ruthenium) are dissolved into and are mixed with platinum ruthenium mixed solution in 50 ml deionized water, sonic oscillation is transferred to after 20 minutes in the carbon slurry, logical argon gas deoxygenation was stirred after 4 hours, NaOH/the ethylene glycol solution that adds 50 milliliter of 1 mol, continue stirring and be warming up to 185 ℃ of maintenances 4 hours after 4 hours, be cooled to 25 ℃ then, with dilute hydrochloric acid solution adjust pH to 3, stir after 3 hours, filter.Filter cake obtained the catalyst of 20%Pt-10Ru% in 8 hours 85 ℃ of following vacuum drying, and yield is 98.8%.Transmission electron microscope and X-ray diffraction experiment result show that double elements noble metal granule size is below 2.5 nanometers.
Embodiment 2:PtRu/C (60PtRu%, Pt/Ru=1) preparation of anode catalyst
Active carbon XC-72R handles with the salpeter solution of 5mol/L in advance, and 200 ℃ of dryings take by weighing 2 grams and disperse to make in 30 minutes the carbon slurry with 150 milliliters of glycol waters (ethylene glycol content is 95%) sonic oscillation after 4 hours.Measure 40 milliliters of chloroplatinic acid/ethylene glycol solutions (50 milligrams of platinum/milliliters), measure 25 milliliters of mixing of the ruthenium trichloride aqueous solution (40 milligrams of ruthenium/milliliters), sonic oscillation is added drop-wise to after 20 minutes in the carbon slurry, logical argon gas deoxygenation was stirred after 4 hours, drip 15 milliliters of the NaOH/ethylene glycol solutions of 1.5 mol, continue to stir and be warming up to 180 ℃ of maintenances 4 hours after 4 hours, be cooled to 25 ℃ then, dilute hydrochloric acid solution adjust pH to 2.5 with 1.5 mol, stir after 6 hours, filter, filtrate is as clear as crystal.110 ℃ of vacuum drying of solid obtained the catalyst of 40%Pt-20Ru% in 8 hours.Yield 93%, transmission electron microscope and X-ray diffraction experiment result show that double elements noble metal granule size is below 3.0 nanometers.
Embodiment 3:PtRu/C (90PtRu%, Pt/Ru=1) Preparation of catalysts
Active carbon XC-72R handles with the salpeter solution of 5mol/L in advance, and 200 ℃ of dryings take by weighing 1 gram and disperse to make in 30 minutes the carbon slurry with 60 milliliters of ethylene glycol sonic oscillations after 4 hours.Measure 120 milliliters of chloroplatinic acid/ethylene glycol solutions (50 milligrams of platinum/milliliters), measure 60 milliliters of mixing of ruthenium trichloride/ethylene glycol (50 milligrams of ruthenium/milliliters), sonic oscillation after 50 minutes and carbon slurry mix, logical argon gas deoxygenation was stirred after 10 hours, dripped 10 milliliters of the sodium hydrate aqueous solutions of 2.5 mol, continue to stir and be warming up to 180 ℃ of maintenances 6 hours after 5 hours, be cooled to 25 ℃ then,, stir after 5 hours with the dilute hydrochloric acid solution adjust pH to 2.5 of 1.5 mol, filter, filtrate is as clear as crystal.70 ℃ of vacuum drying of solid obtained the catalyst of 90Pt+Ru% in 8 hours, yield 86%, and transmission electron microscope and X-ray diffraction experiment result show that double elements noble metal granule size is below 5.0 nanometers.
Embodiment 4:PtRu/ CNT (30PtRu%, Pt/Ru=1) Preparation of catalysts
CNT passes through sulfuric acid treatment in advance.200 ℃ of dryings take by weighing 1 aqueous solution (ethylene glycol content the is 95%) sonic oscillation that restrains with 50 milliliters of ethylene glycol and disperse to make in 30 minutes carbon nano tube suspension after 4 hours.Measure 5.9 milliliters of chloroplatinic acid aqueous solutions (50 milligrams of platinum/milliliters), measure 23 milliliters of mixing of ethylene glycol solution (6.4 milligrams of ruthenium/milliliters) of ruthenium trichloride, sonic oscillation was added drop-wise in the carbon nano tube suspension after 20 minutes, and logical argon gas deoxygenation was stirred after 10 hours, with potassium hydroxide/ethylene glycol solution adjust pH to 10 of 1M, continue to stir and be warming up to 185 ℃ of maintenances 4 hours after 5 hours, be cooled to 25 ℃ then,, stir after 3 hours with dilute hydrochloric acid solution adjust pH to 3, filter, filtrate is as clear as crystal.70 ℃ of vacuum drying of solid obtained the catalyst of 20%Pt-10Ru% in 8 hours.Yield 95%, transmission electron microscope and X-ray diffraction experiment result show that double elements noble metal granule size is below 5.0 nanometers.
Embodiment 5:PtCo/C (20Pt%, Pt/Co=2) Preparation of catalysts
Active carbon XC-72R takes by weighing 2 grams 200 ℃ of dryings in advance and disperses to make in 30 minutes the carbon slurry with 75 milliliters of ethylene glycol sonic oscillations after 4 hours.Measure 15 milliliters of chloroplatinic acid/ethylene glycol solutions (38.5 milligrams of platinum/milliliters), measure 10.0 milliliters of mixing of cobalt nitrate aqueous solution (30 milligrams of cobalt/milliliters), sonic oscillation is transferred to after 40 minutes in the carbon slurry, and logical argon gas deoxygenation was stirred after 10 hours, with potassium hydroxide/ethylene glycol solution adjust pH to 11 of 1M, continue to stir and be warming up to 185 ℃ of maintenances 6 hours after 16 hours, be cooled to 25 ℃ then,, stir after 8 hours with dilute hydrochloric acid solution adjust pH to 3, filter, filtrate is as clear as crystal.100 ℃ of vacuum drying of solid obtained PtCo/C (20Pt%) catalyst in 8 hours.Yield 97.7%, transmission electron microscope and X-ray diffraction experiment result show that the double elements metal particle size is below 3.0 nanometers.
Embodiment 6:PtIrRu/C (20Pt%, Pt/Ir/Ru=1) Preparation of catalysts
Active carbon XC-72R takes by weighing 1.3 grams 200 ℃ of dryings in advance and disperses to make in 30 minutes the carbon slurry with 60 milliliters of ethylene glycol sonic oscillations after 4 hours.Measure 8 milliliters of chloroplatinic acid aqueous solutions (50 milligrams of platinum/milliliters), measure 10 milliliters of mixing of ruthenium trichloride/ethylene glycol (10.4 milligrams of ruthenium/milliliters), measure 10 milliliters of the chloro-iridic acid aqueous solution (20 milligrams of iridium/milliliters), mixing sonic oscillation transfers to after 30 minutes in the carbon slurry, logical argon gas deoxygenation was stirred after 6 hours, drip 15 milliliters of 1M NaOH ethylene glycol solutions, continue to stir and be warming up to 180 ℃ of maintenances 6 hours after 12 hours, be cooled to 25 ℃ then, with dilute hydrochloric acid solution adjust pH to 3.5, stir after 5 hours, filter, filtrate is as clear as crystal.90 ℃ of vacuum drying of solid obtained PtIrRu/C (20Pt%) catalyst (total metal contents in soil is 35%) in 8 hours.Yield 98%, transmission electron microscope and X-ray diffraction experiment result show that three constituent element noble metal granule sizes are below 3.0 nanometers.
Embodiment 7:PtCuFe/C (20Pt%, Pt/Cu/Fe=1) Preparation of catalysts
5 gram chloroplatinic acids are dissolved in 100 milliliters of ethylene glycol (containing 1.85 gram platinum), with 1.18 gram CuSO
4-5H
2O and 1.28 gram FeCl
3-6H
2O dissolves with 20 ml deionized water, and two kinds of solution are mixed, and sonic oscillation disperseed 120 minutes.Used carrier active carbon XC-72R 120 ℃ of dryings in carbon dioxide take by weighing 6.8 grams and disperse to make in 60 minutes the carbon slurry with 300 milliliters of ethylene glycol and 30 ml water sonic oscillations after 4 hours.The mixed solution of metal is transferred in the carbon slurry, logical argon gas deoxygenation was stirred after 10 hours, drip 50 milliliters of the NaOH/ethylene glycol solutions of 1.0 mol, continue to stir and be warming up to 170 ℃ of maintenances 4 hours after 12 hours, reduce to room temperature then,, be warming up to 80 ℃ again and stir after 1.5 hours with dilute hydrochloric acid solution adjust pH to 3.5, filter, 70 ℃ of vacuum drying obtained PtCuFe/C (20Pt%) catalyst in 8 hours.Yield 98.7%, transmission electron microscope and X-ray diffraction experiment result show that the double elements metal particle size is below 3.0 nanometers.This catalyst can be used as oxygen electrochemical reducting reaction catalyst.
Embodiment 8:NiPt/ CNT (30NiPt%, Ni/Pt=5/3) Preparation of catalysts
CNT passes through sulfuric acid treatment in advance.200 ℃ of dryings take by weighing 5 grams and disperse to make in 30 minutes carbon nano tube suspension with 140 milliliters of glycerine and 60 ml water sonic oscillations after 4 hours.3.9g chloroplatinic acid (contain 1.44 gram platinum) and 3.6g nickel nitrate (contain 0.72 and restrain nickel) are dissolved in 60 milliliters of glycerine and 40 milliliters, sonic oscillation was transferred in the carbon nano tube suspension after 50 minutes, logical argon gas deoxygenation was stirred after 12 hours, ethylene glycol solution adjust pH to 13 with 1M potassium hydroxide, continue to stir and be warming up to 175 ℃ of maintenances 5 hours after 5 hours, be cooled to 25 ℃ then, with dilute nitric acid solution adjust pH to 3.5, stir after 5 hours, filter, the hot deionized water washing, 70 ℃ of vacuum drying of solid obtained the catalyst of 30NiPt% in 8 hours.Yield 95%, transmission electron microscope and X-ray diffraction experiment result show that double elements noble metal granule size is below 6.0 nanometers.
Embodiment 9:PdCu/C (30PdCu%, preparation Pd/Cu=1.2)
Active carbon XC-72R handles with the salpeter solution of 5mol/L in advance, and 200 ℃ of dryings take by weighing 5 grams and disperse to make in 30 minutes the carbon slurry with 270 milliliters of glycerine sonic oscillations after 4 hours.2.38 gram PdCl2 (containing 1.43 gram palladiums) is dissolved in 30 milliliters of dilute hydrochloric acid solutions, add copper sulphate 2.79 grams (containing 0.71 gram copper) again, sonic oscillation is transferred to after 20 minutes in the carbon slurry, and logical argon gas deoxygenation was stirred after 10 hours, with the ethylene glycol solution adjust pH to 13 of NaOH, continue to stir and be warming up to 190 ℃ of maintenances 4 hours after 5 hours, be cooled to 25 ℃ then,, stir after 3 hours with dilute hydrochloric acid solution adjust pH to 3, filter, filtrate is as clear as crystal.70 ℃ of vacuum drying of solid obtained the catalyst of 30%PtCu/C in 8 hours, and yield is 98.8%.Transmission electron microscope and X-ray diffraction experiment result show that double elements noble metal granule size is below 3.0 nanometers.
Embodiment 10:PtRhFe/C (20Pt%, preparation Pt/Rh/Fe=10/3/7)
With 5 gram active carbon XC-72R in advance 200 ℃ of dryings be dispersed into carbon with 300 milliliters of ultrasonic concussions of ethylene glycol after 8 hours and starch.3.17 gram chloroplatinic acid (H
2PtCl
66H
2O contains 1.37 gram platinum), 0.56 gram rhodium chloride (RhCl
33H
2O contains 0.218 gram rhodium) and 2 gram ferric nitrate (Fe (NO
3)
39H
2O, contain 0.275 gram iron) be dissolved in the aqueous solution (wherein ethylene glycol content is 80%) of 150 milliliters of ethylene glycol, sonic oscillation 60 minutes, logical argon gas deoxygenation was stirred after 6 hours, drip 15 milliliters of the potassium hydroxide/ethylene glycol solutions of 1 mol, continue to stir after 8 hours and mixing with the carbon slurry and stirring and spend the night.Be warming up to 170 ℃ and kept 3 hours, be cooled to 25 ℃ then, with dilute hydrochloric acid solution adjust pH to 3, stir after 3 hours, filter, filter cake was 70 ℃ of vacuum drying 12 hours.
This catalyst is divided into several parts, and a copy of it is handled according to following program: under the argon shield, 900 ℃ kept 1 hour, were cooled to 600 ℃ then and were keeping 1 hour, reduced to room temperature and took out, and carried out TEM and XRD experiment.
The comparative example 1: (20Pt%, Pt/Rh/Fe=10/3/7) catalyst 5g active carbon XC-72R disperses with the 270ml deionized water, stirs 15 minutes according to document [8] preparation PtRhFe/C.3.17 gram chloroplatinic acid (H
2PtCl
66H
2O contains 1.37 gram platinum), 0.56 gram rhodium chloride (RhCl
33H
2O contains 0.218 gram rhodium) and 2 gram ferric nitrate (Fe (NO
3)
39H
2O, contain 0.275 gram iron) be dissolved in the 30ml deionized water, the active carbon that dropwise is added drop-wise to boiling suspended in night, stirred then 30 minutes, with the slow adjust pH to 9 of 2.5MNaOH solution, 8.1m12.5MNaOH solution mixes with 1.8ml formalin (37%), be added drop-wise to then in the above-mentioned mixed liquor, stir after 15 minutes and filter, a large amount of hot deionized water washings, 70 ℃ of vacuum drying.
This catalyst is divided into several parts, and a copy of it is handled according to following program: under the argon shield, 900 ℃ kept 1 hour, were cooled to 600 ℃ then and were keeping 1 hour, reduced to room temperature and took out, and carried out TEM and XRD experiment.
According to the prepared metallic catalyst experimental result of the present invention
| Sample | Mean particle diameter (nm) | ||
| Transmission electron microscope result (TEM) | X-ray diffraction result (XRD) | ||
| Embodiment 1, and PtRu/C (30PtRu%, Pt/Ru=1) | 1.7 | - | |
| Embodiment 2, and PtRu/C (60PtRu%, Pt/Ru=1) | 2.9 | 2.3 | |
| Embodiment 3, and PtRu/C (90PtRu%, Pt/Ru=1) | 4.5 | 2.7 | |
| Embodiment 4, and the PtRu/ CNT (30PtRu%, Pt/Ru=1) | 4.8 | 4.4 | |
| Embodiment 5, and PtCo/C (20Pt%, Pt/Co=2) | 2.7 | 2.4 | |
| Embodiment 6, and PtIrRu/C (20Pt%, Pt/Ir/Ru=1) | 3.1 | 2.7 | |
| Embodiment 7, and PtCuFe/C (20Pt%, Pt/Cu/Fe=1) | 2.9 | 2.8 | |
| Embodiment 8, and NiPt/C (30NiPt%, Ni/Pt=5/3) | 5.1 | 4.3 | |
| Embodiment 9, PdCu/C (30PdCu%, Pd/Cu=1 | ?2.6 | 2.4 | |
| Embodiment 10, and PtRhFe/C (20Pt%, Pt/Rh/Fe=10/3/7) | Before the high-temperature process | 3.0 | 2.7 |
| After the high-temperature process | 5.1 | 4.7 | |
| Comparative Examples 1, and PtRhFe/C (20Pt%, Pt/Rh/Fe=10/3/7) | Before the high-temperature process | 5.8 | 5.4 |
| After the high-temperature process | 9.4 | 9.0 | |
By the foregoing description, the present invention and background technology characteristics of comparing and being had as can be seen:
1, preparation nanometer Pt and alloy catalyst thereof in document [1], [3], needs at first are transformed into hydrosulfide with the chloride of Pt and Ru, though this process can be eliminated the influence of trace chlorine to catalytic performance more effectively, but need more operating procedure, cause certain precious metal losses easily.The present invention does not need metal precursor is done any processing, and metal precursor compound is not had special requirement yet, and operating procedure is simple and convenient.
2, it is similar that document [2] prepares the method such as the document [1] of catalyst, but do not remove the chlorion step midway, the catalyst yield is higher, but it is not very high utilizing the alloying level of two kinds of metals in the catalyst of this method preparation, cooperative interaction between the metal is not strong, when this catalyst was used as the DMFC anode catalyst, noble metal did not reach very desirable stage to the catalytic action of methyl alcohol.
3, the boron hydracid quaternary ammonium salt NR that has long carbochain is adopted in document [4], [5]
4BR
3H makes reducing agent and protective agent reduction noble metal and other transition metal precursors, prepares the narrower nano level metal colloid of particle size distribution range.This method requires the anhydrous and oxygen-free system, and typical preparation process is finished in the oxolane system.Though this method can be prepared the very little noble metal catalyst of particle diameter; but make surperficial protective agent and reducing agent owing to adopt larger molecular organics; also must in the anhydrous and oxygen-free system, prepare simultaneously; complex operation; the operating condition harshness; the Preparation of Catalyst cost is higher, and is not suitable for the batch process of catalyst.Compare with this method, the present invention does not adopt any larger molecular organics or other surfactant, need not extra reducing agent yet, and is simple to operate, can reduce cost significantly; And the catalyst granules of preparation is still very little.
4, the three constituent element catalyst that the active carbon of document [6] preparation supports have shown the ability of anti-CO preferably, but this method uses sulfur-containing compound to make reducing agent in preparation, after metallic reducing being finished and is supported on carrier, do not have timely filtration washing, but the mixture drying is disperseed washing later on again, the especially various chloride sulfide of the multiple salinity that forms in the metal reduction reaction process all together absorption deposit on the active carbon, and be not easy to remove, and the existence of these materials all causes certain influence to the performance of catalyst inevitably, reduced the utilization rate of noble metal, this process is also comparatively loaded down with trivial details.And the present invention can be once with metallic reducing and support fully on the carrier, need not to pass through again vapour phase reduction, can reduce the influence of all kinds of impurity effectively, simple to operate, time saving and energy saving.
5, document [7] is though adopt dipping method can prepare the catalyst of multicomponent, and demonstrate catalytic activity preferably, but when adopting dipping method to prepare the high slightly load type metal catalyst of loading, be unfavorable for that metal disperses, the utilization rate of metal is not high, so dipping method is not suitable for preparing the high slightly load type metal catalyst of loading.Compare with this method, the present invention can not only prepare double elements, the multicomponent group load type metal catalyst of low loading, and can also prepare the higher double elements of loading, multicomponent group load type metal catalyst.
6, compare the Pt of the present invention's preparation with document [8]
50Rh
15Fe
35The catalyst metals particle is littler, between the 1-5 nanometer, is evenly distributed, even through after 900 ℃ of high-temperature process, still be no more than 6 nanometers.And according to the Pt of the method in the document [8] preparation
50Rh
15Fe
35The catalyst metals particle about 9 nanometers, skewness.
In sum, the preparation method of a kind of loaded noble metal catalyst provided by the invention, the method is nano level take the loaded catalyst of noble metal as the basis towards high loadings, prepared loaded noble metal catalyst can be a kind of among Pt, Pd, Ru, Os, Ir, Rh, the Re etc. or several, or double elements, the multicomponent catalyst of a kind of or several compositions in a kind of in the above-mentioned noble metal or several and other transition metal. The loaded catalyst of this invention preparation has that height supports, high dispersive, using rate of metal high. The catalyst preparation process that this invention provides has characteristics simple to operate, with low cost.
1, do not adopt any surfactant or other macromolecular organic compounds in the Kaolinite Preparation of Catalyst process of the present invention, reduced the preparation cost of catalyst.
2, the catalyst noble metal of the present invention's preparation is uniformly dispersed, and particle is little, and decentralization is high, improves the metal utilization ratio.
3, owing to metal precursor is dissolved in the same solvent in advance, fully mix certain hour, then adjust pH makes it in identical Water Under solution, reduction again, thereby the catalyst of preparing, metal in conjunction with closely, interacts by force each other, and catalytic activity is high.
4, the present invention need not metal precursor is done any extra process, and metal precursor is not had specific (special) requirements yet, and operating procedure is few, and is simple to operate.
5, the needed solvent of Kaolinite Preparation of Catalyst of the present invention can reclaim, and reuses.
Claims (7)
1, the preparation method of a kind of high loadings double elements or multicomponent noble metal catalyst, its key step is as follows:
(1) mixed system of forming with the alcohol and the water of binary and/or ternary is a solvent, and wherein Chun volume content is 5-100%; 40-250 ℃ of dry a few hours, it is scatter before carrier used, make the carrier suspension of 0.01-0.03g/ml with solvent; Described carrier is active carbon or CNT;
(2) noble metal and other metallic compound are dissolved respectively with described solvent of step (1) or water, the corresponding aqueous solution or alcoholic solution or pure water mixed solution are made in sonic oscillation mixing 5-60 minute, and wherein tenor is 0.01-100mg/ml; Selected noble metal is a kind of among Pt, Pd, Ru, Os, Ir, Rh, the Re or several, and other metals are a kind of in other transition metal that comprise beyond the selected noble metal or several;
(3) by the requirement of metal atomic ratio, the solution that step (2) is prepared mixes with carrier suspension, and sonic oscillation 5-150 minute, inert gas shielding was stirred 0.5-24 hour down;
(4) at-10-30 ℃, it is the alkaline solution of 0.01-4 mol that inert gas shielding adds concentration down, and the solution that step (3) is prepared transfers to the pH value for alkaline, sonic oscillation 5-600 minute, inert gas shielding was stirred 0.5-24 hour down, kept 0.5-12 hour down in 40-250 ℃;
(5) solution with step (4) preparation is cooled to 0-50 ℃, with concentration is that to regulate pH value be acidity for the acid solution of 0.01-10 mol, stir or heat up and keep a period of time, to promote precipitation, filter hot deionized water washing, 40-200 ℃ of following vacuum drying, obtain comprising a kind of loaded catalyst of or several noble metals, its total metal content is 0.01-90%;
(6) catalyst that makes uses after 0.5-24 hour in 150-1200 ℃ of processing under reducing atmosphere or inert atmosphere.
2, preparation method according to claim 1 is characterized in that, the described solution of step (2) is regulated its pH value be alkalescence, (3) and step (5) operation then set by step.
3, preparation method according to claim 1 is characterized in that, described alcohol is dihydroxylic alcohols or the trihydroxylic alcohol of C2-C6.
4, preparation method according to claim 1 is characterized in that, described aqueous slkali is to use the solvent identical with preparing carrier suspension to add alkali to make.
According to claim 1 or 4 described preparation methods, it is characterized in that 5, described aqueous slkali is NaOH or potassium hydroxide solution.
6, preparation method according to claim 1 is characterized in that, described noble metal and other transistion metal compounds are water soluble compound.
7, preparation method according to claim 1 is characterized in that, the catalyst of step (5) preparation can directly use.
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| KR100601984B1 (en) | 2005-01-20 | 2006-07-18 | 삼성에스디아이 주식회사 | Supported catalyst and preparing method thereof |
| CN101015798B (en) * | 2007-02-16 | 2012-05-30 | 中国科学院上海微***与信息技术研究所 | Platinum-ruthenium radical nano-electrocatalyst and preparing method based on metal cluster compound path |
| CN101670286B (en) * | 2008-09-12 | 2012-03-21 | 北京大学 | Supported transition metal or transition metal alloy nanocluster catalyst and preparation method and application thereof |
| KR101118473B1 (en) * | 2009-03-27 | 2012-03-12 | (주)바이오니아 | Nanoporous films and method of manufacturing nanoporous films |
| CN104416164B (en) * | 2013-09-04 | 2017-01-04 | 中国科学院苏州纳米技术与纳米仿生研究所 | Platinum black and preparation method thereof |
| KR102287646B1 (en) * | 2018-12-31 | 2021-08-06 | 한화솔루션 주식회사 | Carbon-based noble metal-transition metal complex catalyst and preparation method thereof |
| CN114430048A (en) * | 2020-10-14 | 2022-05-03 | 中国石油化工股份有限公司 | Catalyst, preparation method thereof, membrane electrode and direct liquid fuel cell |
| CN112725828B (en) * | 2020-12-28 | 2021-11-23 | 宁波中科科创新能源科技有限公司 | IrRu-based multicomponent alloy metal precipitation catalyst and preparation method thereof |
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