CN1226086C - Solid supported noble metal catalyst and its preparing method - Google Patents
Solid supported noble metal catalyst and its preparing method Download PDFInfo
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- CN1226086C CN1226086C CN 01144123 CN01144123A CN1226086C CN 1226086 C CN1226086 C CN 1226086C CN 01144123 CN01144123 CN 01144123 CN 01144123 A CN01144123 A CN 01144123A CN 1226086 C CN1226086 C CN 1226086C
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Abstract
The present invention relates to a noble metal catalyst in a loading type. An active component is one element of Ru, Rh, Pd, Os, Ir, Pt, Au, Ag, Cu or Ni; a carrier is one element of active carbon, graphite carbon, nanometer charcoal pipes, Al2O3, SiO2, molecular sieves, MgO or TiO2, wherein the content of the active component is from 0.1 to 90%, and the metal grain diameter of the catalyst is form 0.5 to 6 nm. The present invention has the preparation processes that the active component, alkali metals or hydroxides thereof or carbonate and the carrier are respectively dispersed in a solvent and are proportionally mixed; the solution is heated; nitric acid, sulfuric acid, hydrochloric acid, oxalic acid or acetic acid is added as precipitants; the solution is dried. The catalyst is used as a fuel cell catalyst, and the performance of the catalyst is superior to that of the cell with the same commercial catalyst. The method has the advantages of environmental protection, simple and short process, little time consumption, high yield, and reduction of the production cost of the catalyst.
Description
Technical field
The present invention relates to a kind of supported metal catalyst and this Preparation of catalysts method.
Background technology
Solid supported noble metal catalyst has been widely used and has made electrode catalyst of fuel cell, the oxidation reaction catalyst of hydrogenation, dehydrogenation reaction and minority.Because the costing an arm and a leg of platinum, scarcity of resources.So must take suitable preparation method and process conditions to reduce the platinum particle size, increase the decentralization of platinum on charcoal, improve activity of such catalysts and utilization rate, especially for the solid supported noble metal catalyst of high carrying capacity.
In the last few years, domestic and international many researchers had attempted several different methods and had prepared solid supported noble metal catalyst:
Document [1] (Henry G Petrow, US 3992331) has been introduced a kind of method for preparing the active carbon supported platinum catalyst of high degree of dispersion.This method is prepared into sulfurous acid platinum sodium (Na with chloroplatinic acid earlier
6[Pt (SO
3)
4]), then by ion-exchange, sodium ion in the sulfurous acid platinum sodium is exchanged into hydrogen ion, in air, heat and boil, discharge unnecessary sulfite ion, the last dry at a certain temperature black colloid that makes platinum, this colloid can be distributed in water or other solvents once more, thereby is easy to support on all kinds of carriers.Utilize this method can make the platinum catalyst of 1.5-2.5 nanometer, this method is owing to utilize inferior sulfate radical that chloride ions displace is fallen simultaneously, therefore, can avoid trace chlorine in the catalyst to cause the reduction of catalytic activity effectively.The weak point of this method is the preparation cost height, the technological process complexity, and process is wayward.
Document [2] (M.Watanabe, J.Electroanal.Chem.229 (1987) 395) in prepare catalyst method be first platinic sodium chloride to be made sulfurous acid platinum sodium, but what be different from document [1] is that this method is not separated sulfurous acid platinum sodium separately, but directly add excessive hydrogen peroxide with its oxidation Decomposition, form a kind of stable platinum oxide colloid, in this colloid, drip the compound of ruthenium such as ruthenium trichloride etc. then, decompose unnecessary hydrogen peroxide rapidly, the oxide junction of ruthenium-oxide of Sheng Chenging and platinum is synthesized platinum ru oxide cluster simultaneously, adjusting by pH, they are deposited on the carrier such as active carbon, platinum wherein is 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 its surperficial metal cluster.
The method for preparing catalyst in the document [3] (A.K.Shukla, J.Appl.Electrochem.29 (1999) 129) is at first respectively the chloride of platinum and ruthenium all to be transformed into the sulfurous acid complex compound, i.e. sulfurous acid platinum sodium and sulfurous acid ruthenium sodium (Na
6[Ru (SO
3)]
4), and it is separated, then with its mixing, resolve into the mixed oxide colloid with hydrogen peroxide oxidation, support again on the active carbon, perhaps as in the document [2] earlier with hydrogen peroxide with sulfurous acid platinum sodium oxidation Decomposition, add sulfurous acid ruthenium sodium branch then and take off unnecessary hydrogen peroxide, simultaneously sulfurous acid ruthenium sodium is transformed into ruthenium-oxide, and the modulation by pH makes two kinds of oxide co-precipitations to active carbon, adds formic acid at last or feeds hydrogen reducing and make.
Above-mentioned two kinds of methods are not to adopt to make the method that metallic colloid disperses again earlier and make, but earlier with behind the high hydrogen peroxide oxidation sulfurous acid platinum sodium of cost again with hydrogen or irritating formic acid reduction-oxidation platinum, not only technological process complexity, cost is higher, also causes environmental pollution to a certain extent.
Document [4] (H.B nnemann, Angew.Chem.Int.Ed.Engl.30 (1991) 1312) and document [5] (H.B nnemann, US 5641723) adopt NR
4BR
3H is reducing metal salt in oxolane (THF), has prepared the very narrow nano level metal colloid of particle size distribution range of multiple quaternary amine protection.Wherein the preparation of Rh colloid is carried out as follows: the RhCl of 2.79 grams
3Be dissolved in 500 milliliters of oxolanes, join 100 milliliters 0.4mol/LN (C
8H
17)
4BEt
3The H tetrahydrofuran solution, after the dissolving fully, fed stirring of inert gas 15 hours under the room temperature, at 40 ℃, drying makes the Rh colloid under the 10-3 millibar, the Rh colloid that will make then slowly adds in the active carbon of the titaniferous that is scattered in oxolane after being dissolved in oxolane, makes titaniferous 0.2wt% at last, contains the catalyst of Rh 10wt%.
Above-mentioned two kinds of methods are operated under the anhydrous and oxygen-free condition, use a large amount of toxic organic solvent, and produce a large amount of by-product waste materials, are not eco-friendly technical process.
Document [6] (H.E.Van Dam, J.Catal., 131 (1991) 335) has been introduced the formaldehyde reducing process and has been prepared the charcoal platinum catalyst.Chloroplatinic acid aqueous solution is added by in pretreated NoritROX 0.8 active carbon of diverse ways, slowly stir under the room temperature, flood 5 days to adsorption equilibrium, elimination solution, hydrothermal treatment consists in 95 ℃ of closed containers, add the formaldehyde reduction at last and make platiniferous 5wt% charcoal platinum catalyst, its decentralization is about 60%.This method weak point is to need to use formaldehyde to make reducing agent, and formaldehyde is very big to human body harm.
Summary of the invention
The object of the present invention is to provide a kind of supported metal catalyst, this catalyst particle size is little and be evenly distributed, and has good decentralization.
Another purpose of the present invention is to provide a kind of method for preparing solid supported noble metal catalyst, and this method is with low cost, environmental friendliness, and technological process is simple, and process is easy to control.
For achieving the above object, a kind of solid supported noble metal catalyst active constituent provided by the invention is Ru, Rh, Pd, Os, Ir, Pt, Au, Ag, Cu or Ni, and carrier is active carbon, graphite charcoal, nano carbon tube, Al
2O
3, SiO
2, molecular sieve, MgO or TiO
2, the metal particle diameter of this catalyst is 0.5-6nm.Wherein the content of active constituent is 5-90%, is recommended as 10-60%.
A kind of method for preparing solid supported noble metal catalyst provided by the invention, its preparation process is as follows:
(1) hydroxide of active constituent, alkali metal or alkaline-earth metal or carbonate and carrier are scattered in respectively in the solvent, the concentration of its three kinds of solution is respectively:
Precious metal salt solution concentration is 0.1-100mg/ml;
The hydroxide of alkali metal or alkaline-earth metal or carbonate solution concentration are 0.1-10mol/L;
Carrier suspension concentration 0.1-1000g/L;
(2) again these three kinds of solution are pressed 1: 0.01-1: the 0.5-3 volume ratio is mixed, and the pH of solution is 6-14;
(3) solution of heating steps (2) preparation keeps 60-250 ℃ of temperature, time 15-600 minute;
(4) adding concentration in above-mentioned mixed solution is that nitric acid, sulfuric acid, hydrochloric acid, oxalic acid or the acetic acid of 0.1-10mol/L is made setting accelerator, and making mixed solution system pH is 1-8, stirs 30 minutes, and filtration is washed till no Cl repeatedly with deionized water
-, oven dry maintains the temperature at 40-200 ℃, retention time 30-1800 minute;
Described active constituent is a kind of in the nitrate, halide of Ru, Rh, Pd, Os, Ir, Pt, Au, Ag, Cu, Ni,
Described dispersant is C
2-C
8A kind of or mixed solution in monohydric alcohol, dihydroxylic alcohols, the trihydroxylic alcohol or mix the solvent of forming with water.
Above-mentioned steps (1) and step (2) are carried out according to the following steps:
Active constituent is dissolved in the dispersant;
Hydroxide or carbonate solution with alkali metal or alkaline-earth metal transfer to 6-14 with its pH, add carrier;
And then carry out step (3) and (4).
The present invention has following effect:
1, changes the composition of solvent in the dispersion, under the situation of not using any surfactant, make charcoal supported noble metal catalyst particle diameter than high loadings little to 0.5-6nm and be evenly distributed, improved the utilization rate of noble metal.
2, adopt gentle and eco-friendly reducing agent reduction precious metal ion, avoided reducing agent commonly used to use the harmful effect that environment is caused.
3, by processing, strengthened the interaction between metal and the carrier, avoided the growth of the particle diameter in the catalyst use the activated carbon surface carrier.
4, by changing the composition of solvent in the dispersion, impel the more weak carrier of hydrophily to obtain good infiltration.
5, use this method to prepare solid supported noble metal catalyst, technology is simple, and flow process is short, and consuming time few, rate of recovery height has reduced the Catalyst Production cost greatly.
6, the catalyst that makes with this method is used as fuel-cell catalyst, and performance is better than using the battery of homotype commercial catalyst.
Description of drawings
Also in conjunction with the accompanying drawings the present invention is described further description below by embodiment, wherein:
Fig. 1 is a platinum containing amount 20wt% charcoal supported platinum catalyst transmission electron microscope picture of the present invention;
Fig. 2 is a platinum containing amount 40wt% charcoal supported platinum catalyst transmission electron microscope picture of the present invention;
Fig. 3 contains ruthenium amount 10wt% charcoal supported ruthenium catalyst transmission electron microscope picture for the present invention;
Fig. 4 is a platinum containing amount 10wt% nano carbon tube platinum catalyst transmission electron microscope picture of the present invention.
The specific embodiment
Embodiment 1: 1 gram chloroplatinic acid hexahydrate is dissolved in the mixed solvent of 100 milliliter ethanol, 300 milliliter ethylene glycol and 100 ml waters composition, stirs, add the 0.25mol/L NaOH aqueous solution 50 milliliters; under protective atmosphere, be heated to 250 ℃; kept 30 minutes, and added and to be scattered in Black Pearls charcoal 3.4 grams in the water, reduce to room temperature after; add setting accelerator; stirred 30 minutes, and filtered, washing; 80 ℃ of dryings 6 hours, platinum containing amount is 10% charcoal platinum catalyst 3.8 grams.
Embodiment 2: the ruthenium trichloride trihydrate of 1 gram is dissolved in the mixed solvent of 100 milliliter ethanol, 300 milliliter ethylene glycol and 100 ml waters composition, stirs, add the 0.25mol/LNaOH aqueous solution 50 milliliters again; under protective atmosphere, be heated to 180 ℃ then; kept 30 minutes, and added XC-72R charcoal 3.4 grams be scattered in the water, reduce to room temperature after; add setting accelerator; stirred 30 minutes, and filtered, washing; 80 ℃ of dryings 6 hours must contain the ruthenium amount and are 10% charcoal and carry ruthenium catalyst 3.7 grams.
Embodiment 3: the rhodium chloride trihydrate of 1 gram is dissolved in the mixed solvent of 250 milliliter ethylene glycol and 250 ml waters composition, stirs, add the 0.25mol/L NaOH aqueous solution 25 milliliters; under protective atmosphere, be heated to 120 ℃ then; kept 30 minutes, and added palm shell charcoal 3.6 grams be scattered in the water, reduce to room temperature after; add setting accelerator; stirred 30 minutes, and filtered, washing; 80 ℃ of dryings 6 hours, the rhodium-containing amount is that 10% charcoal carries rhodium catalyst 3.9 grams.
Embodiment 4: the palladium chloride of 1 gram is dissolved in the mixed solvent of 100 milliliter glycerine, 300 milliliter ethylene glycol and 100 ml waters composition, stirs, add the 0.25mol/L NaOH aqueous solution 10 milliliters; under protective atmosphere, be heated to 200 ℃; kept 30 minutes, and added almond charcoal 5.6 grams be scattered in the water, reduce to room temperature after; add setting accelerator; stirred 30 minutes, and filtered, washing; 80 ℃ of dryings 6 hours must contain the palladium amount and be 10% carbon-carried palladium catalyst 5.9 grams.
Embodiment 5: the chloro-iridic acid of 1 gram is dissolved in the mixed solvent of 100 milliliters of glycerine and 900 ml waters composition; stir; add 1mol/L NaOH ethylene glycol solution 20 milliliters, add the ZSM-5 molecular sieve of 370 grams, under protective atmosphere, be heated to 60 ℃; stir down and kept 10 hours; after reducing to room temperature, filter washing; 120 ℃ of dryings 6 hours must contain the iridium amount and be Ir catalyst 363.1 grams that 0.1% ZSM-5 supports.
Embodiment 6: the osmium tetroxide of 0.5 gram is dissolved in the mixed solvent of 50 milliliters of glycerine and 450 ml waters composition; stir; add 1mol/L NaOH ethylene glycol solution 20 milliliters, add the NACF of 7.1 grams, under protective atmosphere, be heated to 80 ℃; stir down and kept 10 hours; after reducing to room temperature, filter washing; 120 ℃ of dryings 6 hours must contain the osmium amount and be osmium catalyst 7.2 grams that 0.1% NACF supports.
Embodiment 7: the gold chloride of 1 gram is dissolved in the mixed solvent of 100 milliliters of tert-butyl alcohols and 400 ml waters composition; stir, add the 0.5mol/LNaOH aqueous solution 5 milliliters, add the titanium dioxide (anatase) of 9.1 grams; under protective atmosphere; be heated to 250 ℃ and kept 30 minutes, then drop to 120 ℃ and kept 3 hours, reduce to room temperature after; filter; washing, 120 ℃ of dryings 6 hours, TiO 2 carrying Au catalyst 9.1 grams of gold content 5%.
Embodiment 8: in the silver nitrate aqueous solution of 20 milliliters of 0.5mol/L; the isooctanol that adds 5 milliliters stirs, and adds the 0.25mol/LNaOH aqueous solution 1 milliliter; the silica that adds 12.4 grams; under protective atmosphere, be heated to 250 ℃ and kept 15 minutes, the news prompt drop is to room temperature; filter; washing, 120 ℃ of dryings 6 hours, the silica of silver content 8% carries silver catalyst 12.3 grams.
Embodiment 9: in the copper nitrate aqueous solution of 50 milliliters of 1mol/L, add 30 milliliters isopropyl alcohol, stir; add the 0.25mol/LNaOH aqueous solution 2 milliliters; the magnesia that adds 23.3 grams under protective atmosphere, is heated to 250 ℃ and kept 30 minutes; then dropping to 120 ℃ kept 3 hours; after reducing to room temperature, filter washing; 120 ℃ of dryings 6 hours, copper-loaded catalyst 26.0 grams of magnesia of copper content 12%.
Embodiment 10: in the nickel nitrate aqueous solution of 50 milliliters of 1mol/L, add 20 milliliters glycerine, stir, add the 0.25mol/L NaOH aqueous solution 2 milliliters, add the γ-Al of 21.5 grams
2O
3, under protective atmosphere, be heated to 250 ℃ and kept 30 minutes, then drop to 120 ℃ and kept 3 hours, reduce to room temperature after, filter, washing, 120 ℃ of dryings 6 hours, carrying alumina Raney nickel 23.9 grams of nickel content 12%.
Embodiment 11: according to the preparation method of example 1, as carrier, the chloroplatinic acid hexahydrate of 2 grams is made raw material with Norit ROX0.8 charcoal 3.0 grams, makes charcoal platinum catalyst 3.7 grams of platinum containing amount 20wt%.
Embodiment 12: according to the preparation method of example 1, make carrier with almond charcoal 3.0 gram, the metal platinum of 2 grams are dissolved in chloroazotic acid and make chloroplatinic acid and make raw material, make platinum containing amount 40wt% charcoal platinum catalyst 4.9 grams.
Embodiment 13: according to the preparation method of example 1, make carrier with graphite charcoal 2.0 gram, the metal platinum of 3 grams are dissolved in chloroazotic acid and make chloroplatinic acid and make raw material, make platinum containing amount 60wt% charcoal platinum catalyst 4.9 grams.
Embodiment 14: according to the preparation method of example 1, make carrier with oil glue charcoal 0.5 gram, the metal platinum of 4.5 grams are dissolved in chloroazotic acid and make chloroplatinic acid and make raw material, make platinum containing amount 90% charcoal platinum catalyst 4.9 grams.
Embodiment 15: according to the preparation method of example 1, make carrier for 180 milligrams with nano carbon tube, 54 milligrams of chloroplatinic acid six hydrates make 195 milligrams of platinum containing amount 10wt% nano carbon tube platinum catalysts as raw material.
Claims (5)
1, a kind of solid supported noble metal catalyst, active constituent are any one of Ru, Rh, Pd, Os, Ir, Pt, Au, Ag, Cu or Ni, and carrier is active carbon, graphite charcoal, nano carbon tube, Al
2O
3, SiO
2, molecular sieve, MgO or TiO
2Any one, wherein the content of active constituent is 5-90%, it is characterized in that, the metal particle diameter of this catalyst is 0.5-6nm.
2, solid supported noble metal catalyst as claimed in claim 1 is characterized in that, the content of active constituent is 10-60%.
3, a kind of method for preparing the described solid supported noble metal catalyst of claim 1, its preparation process is as follows:
(1) hydroxide of active constituent, alkali metal or alkaline-earth metal or carbonate and carrier are scattered in respectively in the solvent, the concentration of its three kinds of solution is respectively:
Precious metal salt solution concentration is 0.1-100mg/ml;
The hydroxide of alkali metal or alkaline-earth metal or carbonate solution concentration are 0.1-10mol/L;
Carrier suspension concentration 0.1-1000g/L;
(2) with these three kinds of solution by 1: 0.01-1: the 0.5-3 volume ratio is mixed, and to make pH be 6-14;
(3) solution of heating steps (2) preparation keeps 60-250 ℃ of temperature, time 15-600 minute;
(4) adding concentration is that setting accelerator is made in the acid of 0.1-10mol/L, and making mixed solution system pH is 1-8, stirs 30 minutes, and filtration is washed till no Cl repeatedly with deionized water
-, oven dry maintains the temperature at 40-200 ℃, retention time 30-1800 minute;
Described dispersant is C
2-C
8A kind of or mixed solution in monohydric alcohol, dihydroxylic alcohols, the trihydroxylic alcohol or mix the solvent of forming with water.
4, preparation method as claimed in claim 3 is characterized in that, carry out according to the following steps step (1) and (2):
Active constituent is dissolved in the dispersant;
Hydroxide or carbonate solution with alkali metal or alkaline-earth metal transfer to 6-14 with its pH, add carrier;
And then carry out step (3) and (4).
5, preparation method as claimed in claim 3 is characterized in that, described acid is nitric acid, sulfuric acid, hydrochloric acid, oxalic acid or acetic acid.
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