CN101775595A - Chemical composition plating method for preparing supported platinum bimetallic alloy composite material - Google Patents
Chemical composition plating method for preparing supported platinum bimetallic alloy composite material Download PDFInfo
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- CN101775595A CN101775595A CN 201010125055 CN201010125055A CN101775595A CN 101775595 A CN101775595 A CN 101775595A CN 201010125055 CN201010125055 CN 201010125055 CN 201010125055 A CN201010125055 A CN 201010125055A CN 101775595 A CN101775595 A CN 101775595A
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Abstract
The invention relates to a chemical composition plating method for preparing a supported platinum bimetallic alloy composite material, which belongs to the technical field of the preparation of the bimetallic alloy material. A chemical platinum plating layer prepared by using the single platinum chemical planting method has bad performance and higher cost. For improving the performance of the single platinum planting layer and reducing the usage of the noble platinum, the invention provides the chemical composition plating method for depositing a platinum bimetallic alloy, which comprises three steps of pretreatment of a matrix, activation of the matrix, chemical composition plating and heat treatment after planting. After being subjected to pretreatment and activation, inorganic oxides, composite oxides and a carbon carrier or a molecular sieve matrix are added into platinum-rhenium or platinum-iridium bimetallic chemical plating solution to carry out bimetallic chemical composition planting, and the obtained sample is subjected to heat treatment to obtain the supported platinum bimetallic alloy composite material. The platinum bimetallic alloy composite material prepared by the method has the characteristics of low cost, sintering resistance and excellent catalytic performance.
Description
Technical field
The present invention relates to a kind of chemically composited electroplating method for preparing the supported platinum bimetallic alloy matrix material, belong to the bimetallic alloy technical field of material.
Background technology
Electroless plating (Electroless plating) (generally includes H by reductive agent suitable in the solution
2PO
2 -, N
2H
4And BH
4 -Deng) make metal ion under the self-catalysis of matrix surface, reduce the metal deposition process that carries out.Up to now, the history in existing more than 50 year of the development of electroless plating.The forties in 20th century, the A.Brenner of National Bureau of Standards has developed the chemical nickel-plating plating solution that can work and has carried out relevant scientific research with G.Riddell, and they are considered to the real founder of electroless plating technology.Early stage electroless plating research mainly concentrates on the electroless plating of nickel and alloy thereof.Through 50 years of development, industrial production is also studied and be applied to gradually to metal such as electroless copper, palladium, cobalt and alloy technology.Nowadays, electroless plating technology has been widely used in the enterprising row metal deposition of metal or non-metallic material, to obtain functional materials with property (chemical property, catalytic performance, magnetic property, electrical property and mechanical property).The loading type NiB amorphous alloy catalyst that for example adopts chemical plating method to obtain has excellent Catalytic Hydrogenation Properties; The palladium catalyst that adopts chemical plating method to obtain shows good exhaust purification catalytic performance.
On the document report more be non-noble metal electroless depositions such as nickel, copper, cobalt, and less, and mainly be the electroless plating of monometallic platinum about the electroless plating research of metal platinum about the research report of precious metal especially metal platinum electroless plating.Bimetal load or be deposited on matrix or matrix material that carrier surface forms is compared with monometallic, often shows more excellent performance.Be better than Ni-B and Co-B catalyzer on the Ni-Co-B catalyst catalytic performance that obtains as chemical plating method; Pt-Re/Al
2O
3Success substitutes Pt/Al
2O
3Becoming the petroleum reforming catalyzer is to show that bimetallic catalyst is better than the example of single-metal reforming catalyst.Need to prove, the load of platinum bimetallic or deposition, traditional method is exactly the method for dipping-hydrogen reduction, and there is complicated process of preparation in this method, the shortcoming that cost is higher.
Summary of the invention
The objective of the invention is deficiency and defective, in order to improve the performance of platinum monometallic coating, reduce the consumption of noble metal platinum simultaneously, the invention provides a kind of chemically composited electroplating method for preparing the supported platinum bimetallic alloy matrix material at the prior art existence.
Technical scheme of the present invention is as follows:
A kind of chemically composited electroplating method for preparing the supported platinum bimetallic alloy matrix material is characterized in that it comprises the steps:
1) substrate pretreated: with matrix thermal treatment under 80～500 ℃ of conditions, heat treatment time at least 1 hour; Then, adopt the method for dipping, the matrix after the thermal treatment is soaked platinum or iridium sensitizing solution, dry under room temperature to 200 ℃ condition, promptly obtain activating precursor, wherein sensitization accounts for 0.1～5.0% of substrate quality with platinum or iridium; Described matrix is inorganic oxide, composite oxides, carbon support or molecular sieve;
2) activation of matrix: the activation precursor that step (1) is obtained joins KBH
4, NaBH
4Or reduce in the solution of hydrazine hydrate reduction agent, reductive agent is 1: 1～20: 1 with activating the mol ratio that activates with precious metal in the precursor, and the recovery time is 5～60 minutes, with the activation precursor after the deionized water wash reduction, until washings is neutral, the matrix after promptly obtaining activating;
3) Ni-P and plating postheat treatment: with step 2) matrix after the gained activation is placed directly in and carries out electroless plating in the platinum bimetallic alloy chemical plating fluid, the control plating temperature is 35 to 95 ℃, the electroless plating time is 10～120 minutes, product is extremely neutral with deionized water wash, thermal treatment under 60～900 ℃ of conditions, at least 1 hour time, thereby obtain the platinum bimetallic alloy matrix material of load, wherein, by accounting for 1～50% of substrate quality after the thermal treatment with the chemically composited total platinum quality that plates on the substrate pretreated dipping, the mass ratio of iridium or rhenium is 1: 0.01～1: 50 in total platinum content and its alloy.
In the technique scheme, described platinum of step 1) or iridium sensitizing solution are that Platinic chloride, ammonium chloroplatinate, Platinic chloride are received, the aqueous solution of potassium platinichloride, platinum nitrate, chloro-iridic acid, ammonium iridichloride, sodium iridichloride or chloro-iridic acid, or are dissolved in formed solution in acetone, ethanol, acetone water or the ethanol water.Described inorganic oxide adopts Al
2O
3, TiO
2, SiO
2, ZrO
2Or CeO
2, described composite oxides comprise TiO
2-Al
2O
3, ZrO
2-Al
2O
3, CeO
2-Al
2O
3, SiO
2-Al
2O
3, TiO
2-SiO
2Or CeO
2-ZrO
2Described carbon support is carbon nanotube, activated carbon or carbon fiber.
Platinum bimetallic alloy chemical plating fluid of the present invention composed as follows:
Platinum based compound 0.1～5.0g/L
Sodium phosphate dibasic Na
2HPO
412H
2O 20～300g/L
Secondary ammonium phosphate (NH
4)
2HPO
41.5～40g/L
Oxammonium hydrochloride NH
2OHHCl 0.5～20g/L
Hydrazine hydrate H
4N
2H
2O 1.0～100ml/L
The compound amount of iridium or rhenium is according to treating total platinum content and iridium in the alloyage
Or the rhenium mass ratio was determined in 1: 0.01～1: 50
35～95 ℃ of bath temperatures
Platinum based compound of the present invention is meant that Platinic chloride, ammonium chloroplatinate, Platinic chloride receive or potassium platinichloride; The compound of described iridium or rhenium is meant chloro-iridic acid, ammonium iridichloride, sodium iridichloride, potassium hexachloroiridate, perrhenic acid, ammonium perrhenate, potassium perrhenate or perrhenic acid sodium.
The present invention compared with prior art has the following advantages and the high-lighting effect:
The platinum bimetallic alloy matrix material that adopts the present invention to obtain has low, the anti-sintering of cost, catalytic performance excellent characteristics; And the present invention compares with traditional load type platinum bimetallic alloy composite material preparation process, and easy to operate, step is simple, the preparation good reproducibility.
Embodiment
A kind of chemically composited electroplating method for preparing the supported platinum bimetallic alloy matrix material provided by the invention, its concrete processing step is as follows:
1) substrate pretreated: with matrix thermal treatment under 80～500 ℃ of conditions, heat treatment time at least 1 hour; Then, adopt the method for dipping, the matrix after the thermal treatment is soaked platinum or iridium sensitizing solution, dry under room temperature to 200 ℃ condition, promptly obtain activating precursor, wherein sensitization accounts for 0.1～5.0% of substrate quality with platinum or iridium; Described matrix is that inorganic oxide (comprises Al
2O
3, TiO
2, SiO
2, ZrO
2Or CeO
2), composite oxides (comprise TiO
2-Al
2O
3, ZrO
2-Al
2O
3, CeO
2-Al
2O
3, SiO
2-Al
2O
3, TiO
2-SiO
2Or CeO
2-ZrO
2), carbon support (adopting carbon nanotube, activated carbon or carbon fiber) or molecular sieve.Described platinum or iridium sensitizing solution are that Platinic chloride, ammonium chloroplatinate, Platinic chloride are received, the aqueous solution of potassium platinichloride, platinum nitrate, chloro-iridic acid, ammonium iridichloride, sodium iridichloride or chloro-iridic acid, or are dissolved in formed solution in acetone, ethanol, acetone water or the ethanol water.
2) activation of matrix: the activation precursor that step 1) is obtained joins KBH
4, NaBH
4Or reduce in the solution of hydrazine hydrate reduction agent, reductive agent is 1: 1～20: 1 with activating the mol ratio that activates with precious metal in the precursor, and the recovery time is 5～60 minutes, with the activation precursor after the deionized water wash reduction, until washings is neutral, the matrix after promptly obtaining activating;
3) Ni-P and plating postheat treatment: with step 2) matrix after the gained activation is placed directly in and carries out electroless plating in the platinum bimetallic alloy chemical plating fluid, the control plating temperature is 35 to 95 ℃, the electroless plating time is 10～120 minutes, product is extremely neutral with deionized water wash, thermal treatment under 60～900 ℃ of conditions, at least 1 hour time, thus the platinum bimetallic alloy matrix material of load obtained.Wherein, by accounting for 1～50% of substrate quality after the thermal treatment with the chemically composited total platinum content that plates on the substrate pretreated dipping, the mass ratio of iridium or rhenium is 1: 0.01～1: 50 in total platinum content and its alloy.Described platinum bimetallic alloy is meant platinoiridita or platinum rhenium bimetallic alloy.
Described platinum bimetallic alloy chemical plating fluid composed as follows:
Platinum based compound 0.1～5.0g/L
Sodium phosphate dibasic Na
2HPO
412H
2O 20～300g/L
Secondary ammonium phosphate (NH
4)
2HPO
41.5～40g/L
Oxammonium hydrochloride NH
2OHHCl 0.5～20g/L
Hydrazine hydrate H
4N
2H
2O 1.0～100ml/L
The compound amount of iridium or rhenium is according to treating total platinum content and iridium in the alloyage
Or the rhenium mass ratio was determined in 1: 0.01～1: 50
Bath temperature 35～95C
Platinum based compound in the above-mentioned platinum bimetallic alloy chemical plating fluid is meant that Platinic chloride, ammonium chloroplatinate, Platinic chloride receive or potassium platinichloride; The compound of described iridium or rhenium is meant chloro-iridic acid, ammonium iridichloride, sodium iridichloride, potassium hexachloroiridate, perrhenic acid, ammonium perrhenate, potassium perrhenate or perrhenic acid sodium.
Describe the present invention in detail below by embodiment.
Embodiment 1～8
Embodiment 1 preparation platinoiridita double metallic composite material 5%Pt-1%Ir/ activated carbon
With activated carbon thermal treatment under 120 ℃ of conditions, heat treatment time 4 hours; Then, adopt the method for dipping, the matrix after the thermal treatment is soaked platinum sensitizing solution-chloroplatinic acid aqueous solution, dry under 120 ℃ of conditions, promptly obtain activating precursor, wherein sensitization accounts for 1% of activated carbon quality with platinum; The activation precursor that obtains is joined KBH
4Reduce in the solution, reductive agent is 20: 1 with activating the mol ratio that activates with precious metal in the precursor, and the recovery time is 5 minutes, with the activation precursor after the deionized water wash reduction, is neutral until washings, the matrix after promptly obtaining activating; Matrix after the gained activation is placed directly in the platinoiridita bimetallic alloy chemical plating fluid carries out electroless plating, plating bath is formed referring to table 1, the control plating temperature is 45 ℃, the electroless plating time is 60 minutes, product is extremely neutral with deionized water wash, thermal treatment is 4 hours under 120 ℃ of conditions, thereby obtains activated carbon loaded platinoiridita bimetallic alloy matrix material.Wherein, by accounting for 5% of substrate quality after the thermal treatment with the chemically composited total platinum content that plates on the substrate pretreated dipping, the mass ratio of iridium is 1: 0.2 in total platinum content and its alloy.
Embodiment 2 preparation platinoiridita double metallic composite material 1%Pt-50%Ir/Al
2O
3
With Al
2O
3Thermal treatment under 450 ℃ of conditions, heat treatment time 2 hours; Then, adopt the method for dipping, the matrix after the thermal treatment is soaked iridium sensitizing solution-chloro-iridic acid aqueous solution, dry under 200 ℃ of conditions, promptly obtain activating precursor, wherein sensitization accounts for Al with iridium
2O
35% of quality; The activation precursor that obtains is joined NaBH
4Reduce in the solution, reductive agent is 10: 1 with activating the mol ratio that activates with precious metal in the precursor, and the recovery time is 60 minutes, with the activation precursor after the deionized water wash reduction, is neutral until washings, the matrix after promptly obtaining activating; Matrix after the gained activation is placed directly in the platinoiridita bimetallic alloy chemical plating fluid carries out electroless plating, plating bath is formed referring to table 1, and controlling plating temperature is 85 ℃, the electroless plating time is 120 minutes, to neutral, thermal treatment is 2 hours under 450 ℃ of conditions, thereby obtains Al with deionized water wash for product
2O
3The platinoiridita bimetallic alloy matrix material of load.Wherein, total platinum content accounts for 1% of substrate quality after the thermal treatment, and the mass ratio of iridium is 1: 50 in total platinum content and its alloy.
Embodiment 3 preparation platinum rhenium double metallic composite material 10%Pt-0.1%Re/CeO
2-ZrO
2
With CeO
2-ZrO
2Thermal treatment under 500 ℃ of conditions, heat treatment time 2 hours; Then, adopt the method for dipping, the matrix after the thermal treatment is soaked the ethanolic soln of platinum sensitizing solution-Platinic chloride, drying promptly obtains activating precursor at ambient temperature, and wherein sensitization accounts for CeO with platinum
2-ZrO
21% of quality; The activation precursor that obtains joined in the hydrazine hydrate solution reduce, reductive agent is 20: 1 with activating the mol ratio that activates with precious metal in the precursor, and the recovery time is 30 minutes, with the activation precursor after the deionized water wash reduction, until washings is neutral, the matrix after promptly obtaining activating; Matrix after the gained activation is placed directly in the platinoiridita bimetallic alloy chemical plating fluid carries out electroless plating, plating bath is formed referring to table 1, and controlling plating temperature is 95 ℃, the electroless plating time is 10 minutes, to neutral, thermal treatment is 5 hours under 900 ℃ of conditions, thereby obtains CeO with deionized water wash for product
2-ZrO
2The platinum rhenium bimetallic alloy matrix material of load.Wherein, by accounting for 10% of substrate quality after the thermal treatment with the chemically composited total platinum content that plates on the substrate pretreated dipping, the mass ratio of rhenium is 1: 0.01 in total platinum content and its alloy.
Embodiment 4 preparation platinum rhenium double metallic composite material 20%Pt-1%Re/ carbonaceous molecular sieves
With carbonaceous molecular sieve thermal treatment under 200 ℃ of conditions, heat treatment time 1 hour; Then, adopt the method for dipping, the matrix after the thermal treatment is soaked the aqueous solution of platinum sensitizing solution-platinum nitrate, drying promptly obtains activating precursor under 120 ℃ of conditions, and wherein sensitization accounts for 3% of carbonaceous molecular sieve quality with platinum; The activation precursor that obtains is joined NaBH
4Reduce in the solution, reductive agent is 15: 1 with activating the mol ratio that activates with precious metal in the precursor, and the recovery time is 40 minutes, with the activation precursor after the deionized water wash reduction, is neutral until washings, the matrix after promptly obtaining activating; Matrix after the gained activation is placed directly in the platinoiridita bimetallic alloy chemical plating fluid carries out electroless plating, plating bath is formed referring to table 1, the control plating temperature is 80 ℃, the electroless plating time is 90 minutes, product is extremely neutral with deionized water wash, thermal treatment is 12 hours under 60 ℃ of conditions, thereby obtains the platinum rhenium bimetallic alloy matrix material of carbonaceous molecular sieve load.Wherein, by accounting for 20% of substrate quality after the thermal treatment with the chemically composited total platinum content that plates on the substrate pretreated dipping, the mass ratio of rhenium is 1: 0.05 in total platinum content and its alloy.
Embodiment 5 preparation platinum rhenium double metallic composite material 10%Pt-10%Re/ carbon nanotubes
With carbon nanotube thermal treatment under 80 ℃ of conditions, heat treatment time 2 hours; Then, adopt the method for dipping, the matrix after the thermal treatment is soaked the acetone soln of platinum sensitizing solution-Platinic chloride, drying promptly obtains activating precursor at ambient temperature, and wherein sensitization accounts for 0.5% of carbon nanotube quality with platinum; The activation precursor that obtains is joined KBH
4Reduce in the solution, reductive agent is 10: 1 with activating the mol ratio that activates with precious metal in the precursor, and the recovery time is 20 minutes, with the activation precursor after the deionized water wash reduction, is neutral until washings, the matrix after promptly obtaining activating; Matrix after the gained activation is placed directly in the platinum rhenium bimetallic alloy chemical plating fluid carries out electroless plating, plating bath is formed referring to table 1, the control plating temperature is 55 ℃, the electroless plating time is 60 minutes, product is extremely neutral with deionized water wash, thermal treatment is 12 hours under 500 ℃ of conditions, thereby obtains carbon nanotube loaded platinum rhenium bimetallic alloy matrix material.Wherein, by accounting for 10% of substrate quality after the thermal treatment with the chemically composited total platinum content that plates on the substrate pretreated dipping, the mass ratio of rhenium is 1: 1 in total platinum content and its alloy.
Embodiment 6 preparation platinum rhenium double metallic composite material 2%Pt-10%Re/SiO
2
With SiO
2Thermal treatment under 400 ℃ of conditions, heat treatment time 2 hours; Then, adopt the method for dipping, the matrix after the thermal treatment is soaked the aqueous acetone solution of platinum sensitizing solution-Platinic chloride, drying promptly obtains activating precursor under 100 ℃ of conditions, and wherein sensitization accounts for SiO with platinum
20.1% of quality; The activation precursor that obtains joined in the hydrazine hydrate solution reduce, reductive agent is 5: 1 with activating the mol ratio that activates with precious metal in the precursor, and the recovery time is 30 minutes, with the activation precursor after the deionized water wash reduction, until washings is neutral, the matrix after promptly obtaining activating; Matrix after the gained activation is placed directly in the platinum rhenium bimetallic alloy chemical plating fluid carries out electroless plating, plating bath is formed referring to table 1, and controlling plating temperature is 65 ℃, the electroless plating time is 80 minutes, to neutral, thermal treatment is 2 hours under 800 ℃ of conditions, thereby obtains SiO with deionized water wash for product
2The platinum rhenium bimetallic alloy matrix material of load.Wherein, by accounting for 2% of substrate quality after the thermal treatment with the chemically composited total platinum content that plates on the substrate pretreated dipping, the mass ratio of rhenium is 1: 5 in total platinum content and its alloy.
Embodiment 7 preparation platinoiridita double metallic composite material 25%Pt-25%Ir/TiO
2-Al
2O
3
With TiO
2-Al
2O
3Thermal treatment under 350 ℃ of conditions, heat treatment time 2 hours; Then, adopt the method for dipping, the matrix after the thermal treatment is soaked the aqueous solution of iridium sensitizing solution-potassium hexachloroiridate, drying promptly obtains activating precursor under 120 ℃ of conditions, and wherein sensitization accounts for TiO with iridium
2-Al
2O
30.1% of quality; The activation precursor that obtains joined in the KBH4 solution reduce, reductive agent is 15: 1 with activating the mol ratio that activates with precious metal in the precursor, and the recovery time is 30 minutes, with the activation precursor after the deionized water wash reduction, until washings is neutral, the matrix after promptly obtaining activating; Matrix after the gained activation is placed directly in the platinoiridita bimetallic alloy chemical plating fluid carries out electroless plating, plating bath is formed referring to table 1, and controlling plating temperature is 50 ℃, the electroless plating time is 90 minutes, to neutral, thermal treatment is 8 hours under 500 ℃ of conditions, thereby obtains TiO with deionized water wash for product
2-Al
2O
3The platinoiridita bimetallic alloy matrix material of load.Wherein, total platinum content accounts for 25% of substrate quality after the thermal treatment, and the mass ratio of iridium is 1: 1 in total platinum content and its alloy.
Embodiment 8 preparation platinoiridita double metallic composite material 50%Pt-1%Ir/HZSM-5 molecular sieves
With the thermal treatment under 200 ℃ of conditions of HZSM-5 molecular sieve, heat treatment time 2 hours; Then, adopt the method for dipping, the matrix after the thermal treatment is soaked the aqueous acetone solution of platinum sensitizing solution-Platinic chloride, drying promptly obtains activating precursor under 120 ℃ of conditions, and wherein sensitization accounts for 5% of HZSM-5 molecular sieve quality with platinum; The activation precursor that obtains is joined NaBH
4Reduce in the solution, reductive agent is 1: 1 with activating the mol ratio that activates with precious metal in the precursor, and the recovery time is 60 minutes, with the activation precursor after the deionized water wash reduction, is neutral until washings, the matrix after promptly obtaining activating; Matrix after the gained activation is placed directly in the platinoiridita bimetallic alloy chemical plating fluid carries out electroless plating, plating bath is formed referring to table 1, the control plating temperature is 75 ℃, the electroless plating time is 90 minutes, product is extremely neutral with deionized water wash, thermal treatment is 8 hours under 450 ℃ of conditions, thereby obtains the molecular sieve carried platinoiridita bimetallic alloy matrix material of HZSM-5.Wherein, by accounting for 50% of substrate quality after the thermal treatment with the chemically composited total platinum content that plates on the substrate pretreated dipping, the mass ratio of iridium is 1: 0.02 in total platinum content and its alloy.
The corresponding plating bath of table 1 embodiment is formed
The practicality explanation
It is low that the platinum bimetallic alloy matrix material that adopts the present invention to obtain has a cost, anti-sintering, the catalytic performance excellent characteristics, for the industrial applicibility of gained matrix material of the present invention is described, and the superior performance of comparing with traditional loading type monometallic platinum or iridium material, the present invention estimates the catalytic performance of gained matrix material, the activated carbon loaded platinoiridita double metallic composite material 5%Pt-1%Ir/AC (activated carbon) that catalyst system therefor obtains for embodiment 1, the comparative catalyst is a method electroless deposition platinum that adopts embodiment 1 or 5%Pt/AC and the 1%Ir/AC that iridium obtains respectively, probe reaction is that hydrogen iodide decomposes the reaction that generates iodine and hydrogen, test condition and result are as follows: hydrogen iodide decomposes catalytic performance test to carry out on the self-assembly fixed-bed reactor, quartz reactor internal diameter 14mm, hydroiodic acid HI (7.1mol/L, chemical reagents corporation of traditional Chinese medicines group) flow is 1.0ml/min, catalyst levels 0.1g, granules of catalyst 40～60 orders, temperature of reaction is selected 400 ℃, utilizes H in the hydroiodic acid HI of standard solution of sodium hydroxide drop reaction front and back
+Concentration is calculated the transformation efficiency of reaction.Analytical results is listed in table 2.
Table 25%Pt-1%Ir/AC, the HI degrading activity contrast of 5%Pt/AC and 1%Ir/AC
As can be seen from Table 2, according to the prepared platinoiridita double metallic composite material 5%Pt-1%Ir/AC of the present invention in the hydrogen iodide cartalytic decomposition effect, the catalytic activity that shows demonstrates good prospects for application far above correlated monometallic material 5%Pt/AC and 1%Ir/AC.
Claims (5)
1. a chemically composited electroplating method for preparing the supported platinum bimetallic alloy matrix material is characterized in that it comprises the steps:
1) substrate pretreated: with matrix thermal treatment under 80～500 ℃ of conditions, heat treatment time at least 1 hour; Then, adopt the method for dipping, the matrix after the thermal treatment is soaked platinum or iridium sensitizing solution, dry under room temperature to 200 ℃ condition, promptly obtain activating precursor, wherein sensitization accounts for 0.1～5.0% of substrate quality with platinum or iridium; Described matrix is inorganic oxide, composite oxides, carbon support or molecular sieve;
2) activation of matrix: the activation precursor that step (1) is obtained joins KBH
4, NaBH
4Or reduce in the solution of hydrazine hydrate reduction agent, reductive agent is 1: 1～20: 1 with activating the mol ratio that activates with precious metal in the precursor, and the recovery time is 5～60 minutes, with the activation precursor after the deionized water wash reduction, until washings is neutral, the matrix after promptly obtaining activating;
3) Ni-P and plating postheat treatment: with step 2) matrix after the gained activation is placed directly in and carries out electroless plating in the platinum bimetallic alloy chemical plating fluid, the control plating temperature is 35 to 95 ℃, the electroless plating time is 10～120 minutes, product is extremely neutral with deionized water wash, thermal treatment under 60～900 ℃ of conditions, at least 1 hour time, thereby obtain the platinum bimetallic alloy matrix material of load, wherein, by accounting for 1～50% of substrate quality after the thermal treatment with the chemically composited total platinum quality that plates on the substrate pretreated dipping, the mass ratio of iridium or rhenium is 1: 0.01～1: 50 in total platinum content and its alloy; Described platinum bimetallic alloy is meant platinoiridita or platinum rhenium bimetallic alloy.
2. the chemically composited electroplating method of preparation supported platinum bimetallic alloy matrix material as claimed in claim 1, it is characterized in that: described platinum of step 1) or iridium sensitizing solution are that Platinic chloride, ammonium chloroplatinate, Platinic chloride are received, the aqueous solution of potassium platinichloride, platinum nitrate, chloro-iridic acid, ammonium iridichloride, sodium iridichloride or chloro-iridic acid, or are dissolved in formed solution in acetone, ethanol, acetone water or the ethanol water.
3. the chemically composited electroplating method of preparation supported platinum bimetallic alloy matrix material as claimed in claim 1 is characterized in that: the described inorganic oxide of step 1) adopts Al
2O
3, TiO
2, SiO
2, ZrO
2Or CeO
2, described composite oxides comprise TiO
2-Al
2O
3, ZrO
2-Al
2O
3, CeO
2-Al
2O
3, SiO
2-Al
2O
3, TiO
2-SiO
2Or CeO
2-ZrO
2Described carbon support is carbon nanotube, activated carbon or carbon fiber.
4. the chemically composited electroplating method of preparation supported platinum bimetallic alloy matrix material as claimed in claim 1 is characterized in that: the described platinum bimetallic alloy chemical plating fluid of step 3) composed as follows:
Platinum based compound 0.1～5.0g/L
Sodium phosphate dibasic Na
2HPO
412H
2O 20～300g/L
Secondary ammonium phosphate (NH
4)
2HPO
41.5～40g/L
Oxammonium hydrochloride NH
2OHHCl 0.5～20g/L
Hydrazine hydrate H
4N
2H
2O 1.0～100ml/L
The compound amount of iridium or rhenium is according to treating total platinum content and iridium in the alloyage
Or the rhenium mass ratio was determined in 1: 0.01～1: 50
35～95 ℃ of bath temperatures
5. the chemically composited electroplating method of preparation supported platinum bimetallic alloy matrix material as claimed in claim 4 is characterized in that: described platinum based compound is meant that Platinic chloride, ammonium chloroplatinate, Platinic chloride receive or potassium platinichloride; The compound of described iridium or rhenium is meant chloro-iridic acid, ammonium iridichloride, sodium iridichloride, potassium hexachloroiridate, perrhenic acid, ammonium perrhenate, potassium perrhenate or perrhenic acid sodium.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104593753A (en) * | 2015-02-11 | 2015-05-06 | 苏州捷迪纳米科技有限公司 | Method for metalizing surfaces of carbon nanotubes |
| CN106622232A (en) * | 2016-12-26 | 2017-05-10 | 北京神雾环境能源科技集团股份有限公司 | Denitration catalyst and preparation method thereof |
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| CN1388218A (en) * | 2001-05-30 | 2003-01-01 | 中国石油化工股份有限公司 | Reforming Pt-Re catalyst and its prepn |
| CN1393513A (en) * | 2001-06-29 | 2003-01-29 | 中国石油化工股份有限公司 | Bimetal reforming catalyst and its preparing process |
| CN101138721A (en) * | 2007-09-07 | 2008-03-12 | 清华大学 | Process for preparation of catalysts for catalytic decomposition of hydrogen iodide |
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2010
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1388218A (en) * | 2001-05-30 | 2003-01-01 | 中国石油化工股份有限公司 | Reforming Pt-Re catalyst and its prepn |
| CN1393513A (en) * | 2001-06-29 | 2003-01-29 | 中国石油化工股份有限公司 | Bimetal reforming catalyst and its preparing process |
| CN101138721A (en) * | 2007-09-07 | 2008-03-12 | 清华大学 | Process for preparation of catalysts for catalytic decomposition of hydrogen iodide |
Non-Patent Citations (1)
| Title |
|---|
| 《化学工程师》 20041231 马宁等 担载型铂基催化剂制备方法的研究 51-52 1-5 , 第12期 2 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104593753A (en) * | 2015-02-11 | 2015-05-06 | 苏州捷迪纳米科技有限公司 | Method for metalizing surfaces of carbon nanotubes |
| CN106622232A (en) * | 2016-12-26 | 2017-05-10 | 北京神雾环境能源科技集团股份有限公司 | Denitration catalyst and preparation method thereof |
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| CN101775595B (en) | 2011-11-30 |
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