CN115772662A - Preparation method of porous palladium membrane - Google Patents
Preparation method of porous palladium membrane Download PDFInfo
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- CN115772662A CN115772662A CN202211487448.1A CN202211487448A CN115772662A CN 115772662 A CN115772662 A CN 115772662A CN 202211487448 A CN202211487448 A CN 202211487448A CN 115772662 A CN115772662 A CN 115772662A
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- palladium
- tantalum substrate
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- silver powder
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 221
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 110
- 239000012528 membrane Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 62
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 48
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 48
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000007747 plating Methods 0.000 claims abstract description 28
- 239000000126 substance Substances 0.000 claims abstract description 27
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 22
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000000137 annealing Methods 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 13
- 239000002002 slurry Substances 0.000 claims abstract description 10
- 230000003213 activating effect Effects 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 8
- 238000002791 soaking Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 150000003481 tantalum Chemical class 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 10
- 238000005498 polishing Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- LXAHHHIGZXPRKQ-UHFFFAOYSA-N 5-fluoro-2-methylpyridine Chemical compound CC1=CC=C(F)C=N1 LXAHHHIGZXPRKQ-UHFFFAOYSA-N 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 12
- 230000002776 aggregation Effects 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 9
- 238000005054 agglomeration Methods 0.000 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000446 fuel Substances 0.000 abstract description 4
- 238000007581 slurry coating method Methods 0.000 abstract description 3
- 229910001252 Pd alloy Inorganic materials 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 abstract 1
- 229910052709 silver Inorganic materials 0.000 description 15
- 239000004332 silver Substances 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000012190 activator Substances 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052774 Proactinium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemically Coating (AREA)
Abstract
The invention discloses a preparation method of a porous palladium membrane, which comprises the following steps: 1. treating the tantalum substrate; 2. coating an activating agent on the surface of the tantalum substrate to carry out vacuum heat treatment; 3. soaking in hydrazine hydrate solution for treatment; 4. putting the palladium alloy into a chemical palladium plating solution and adding a hydrazine hydrate solution to carry out chemical palladium plating; 5. preparing silver powder slurry; 6. and performing vacuum annealing treatment after coating the silver powder slurry to form a porous palladium film in the tantalum matrix. The method carries out chemical plating, silver powder slurry coating and annealing heat treatment on the tantalum substrate, and obtains the porous palladium membrane on the surface of the tantalum substrate by using the silver powder as a pore-forming agent, so that the porous palladium membrane has a high pore structure, the surface area of the porous palladium membrane is effectively increased, the occurrence of palladium particle agglomeration is avoided, the performance of the porous palladium membrane is ensured, and the method has higher practical value in the fields of fuel cells, hydrogen energy key materials and the like.
Description
Technical Field
The invention belongs to the technical field of hydrogen separation membrane materials and metal composite membranes, and particularly relates to a preparation method of a porous palladium membrane.
Background
The metal palladium related material is widely applied to the fields of hydrogen isotope storage and separation, catalysis, sensing and the like. The supported palladium catalytic material has excellent electrochemical catalytic oxidation performance of ethanol, methanol and the like and excellent methane catalytic combustion performance, so that the catalyst is widely applied to the field of alcohol fuel cells. However, the existing research shows that the supported palladium catalytic material has many defects, such as instability in the engineering application process, aggregation and growth of nanoparticles, and sharp performance reduction of the supported palladium catalytic material. Unlike palladium sheets, sponge palladium powder and supported palladium catalytic materials, porous palladium has a high pore structure and can avoid the occurrence of agglomeration.
Therefore, it is the focus of current research to develop a novel porous palladium material and a preparation method thereof to meet the requirements of electrochemical catalytic oxidation performance of ethanol, methanol and the like in specific fields.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a method for preparing a porous palladium membrane, aiming at the defects of the prior art. The method comprises the steps of carrying out chemical plating, silver powder slurry coating and annealing heat treatment on a tantalum substrate, and obtaining the porous palladium membrane on the surface of the tantalum substrate by using silver powder as a pore-forming agent, so that the porous palladium membrane has a high pore structure, the surface area of the porous palladium membrane is effectively increased, the occurrence of the agglomeration phenomenon of palladium particles is avoided, and the problem of rapid reduction of the performance of the palladium membrane caused by agglomeration is solved.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a method for preparing a porous palladium membrane is characterized by comprising the following steps:
firstly, grinding a tantalum substrate by using 280#, 600# and 1000# abrasive paper in sequence, then polishing by using mixed acid liquor, cleaning by using deionized water, and drying by using nitrogen to obtain a treated tantalum substrate;
step two, dissolving palladium chloride into absolute ethyl alcohol to obtain an activating agent, then coating the activating agent on the surface of the treated tantalum substrate obtained in the step one, and carrying out vacuum heat treatment to obtain an activated tantalum substrate;
step three, soaking the activated tantalum substrate obtained in the step two in 1mol/L hydrazine hydrate solution for treatment for 15min +/-1 min;
step four, placing the activated tantalum substrate treated in the step three in a chemical palladium plating solution, adding a hydrazine hydrate solution, then performing chemical palladium plating to form a palladium film on the tantalum substrate, and obtaining the tantalum substrate with the palladium film; the chemical palladium plating solution comprises the following components: 5g/L of palladium chloride, 380mL/L of ammonia water, 45g/L of EDTA disodium, and the balance of water, wherein the mass concentration of the hydrazine hydrate solution is 0.8%, and the addition amount of the hydrazine hydrate solution in the chemical palladium plating solution is 10mL/L;
dispersing the spherical silver powder into a mixed solution consisting of absolute ethyl alcohol and water to obtain silver powder slurry;
and step six, coating the silver powder slurry obtained in the step five on the surface of the tantalum substrate with the palladium membrane obtained in the step four, and then carrying out vacuum annealing treatment to form a porous palladium membrane in the tantalum substrate.
The method comprises the steps of grinding, polishing, cleaning and drying the surface of a tantalum substrate, activating, carrying out chemical plating on the tantalum substrate to form a palladium film, coating silver powder slurry on the surface of the tantalum substrate with the palladium film, doping the surface of the tantalum substrate with the palladium film, using the characteristic that silver is alloyed with palladium at a lower temperature to diffuse silver in the palladium film through the alloying process in the vacuum annealing treatment process to form a silver and silver-rich area, combining the vacuum annealing treatment process to carry out a gas-phase dealloying process, using the difference of saturated vapor pressures of palladium and silver, particularly the vacuum volatilization characteristic of silver, to volatilize silver in the silver and silver-rich area, and forming a porous structure by self-assembly of other components, so that the palladium film is converted into the porous palladium film, wherein the porous palladium film has a high-pore structure, the agglomeration phenomenon is avoided, and the problem of rapid performance reduction of the palladium film caused by the aggregation and growth of palladium particles in the application process is solved; meanwhile, partial silver atoms enter a palladium lattice gap to cause the change of a palladium electronic structure, so that the catalytic activity and the hydrogen embrittlement resistance of the porous palladium membrane are improved.
The preparation method of the porous palladium membrane is characterized in that in the step one, the mixed acid solution comprises 40 mass percent of HF and 68 mass percent of HNO 3 Prepared according to the volume ratio of 1 to 3, and the polishing time is 30s.
The preparation method of the porous palladium membrane is characterized in that the vacuum degree of the vacuum heat treatment in the step two is 3.0 multiplied by 10 -3 Pa～9.0×10 -2 Pa, temperature of 600 +/-10 ℃ and time of 30 +/-1 min.
The preparation method of the porous palladium membrane is characterized in that the chemical palladium plating in the step four is carried out at the temperature of 50 +/-10 ℃ for 50 +/-5 min.
The preparation method of the porous palladium membrane is characterized in that the granularity of the spherical silver powder in the fifth step is 1-6 mu m, and D90 is less than 5.6 mu m; the volume ratio of the absolute ethyl alcohol to the water in the mixed solution is 0.05-0.1. By limiting the granularity and D90 of the spherical silver powder, on one hand, the spherical structure of the spherical silver powder is utilized to obtain the porous palladium membrane with relatively consistent pore structure, on the other hand, the granularity of the spherical silver powder is controlled, so that the situation that the spherical silver powder is too thick to cause no pore formation or too large pore size and the situation that the spherical silver powder is too thin to cause too small pore size cannot be applied is avoided, and the pore diameter of the porous palladium membrane is adjusted to ensure the application performance of the porous palladium membrane.
The preparation method of the porous palladium membrane is characterized in that the vacuum degree of the vacuum annealing treatment in the sixth step is 3.0 multiplied by 10 -3 Pa～9.0×10 -2 Pa, temperature of 500 +/-10 ℃ and time of 4h. According to the invention, by controlling the technological parameters of vacuum annealing treatment, alloying of silver powder and the palladium membrane is realized firstly, and then volatilization of silver is realized due to different saturated vapor pressures of palladium and silver, so that the porous palladium membrane is obtained, and the problems that the palladium and silver cannot be alloyed at too low temperature, the porous palladium membrane cannot be obtained, and the porous palladium membrane has too large pore diameter and the application performance is reduced due to too high temperature are solved.
Compared with the prior art, the invention has the following advantages:
1. the method carries out chemical plating, silver powder slurry coating and annealing heat treatment on the tantalum substrate, and obtains the porous palladium membrane on the surface of the tantalum substrate by using the silver powder as a pore-forming agent, so that the porous palladium membrane has a high pore structure, the surface area of the porous palladium membrane is effectively increased, the occurrence of the agglomeration phenomenon of palladium particles is avoided, the problem of rapid reduction of the performance of the porous palladium membrane caused by agglomeration is solved, and the application of the palladium membrane in the fields of alcohol fuel cells and the like is expanded.
2. The invention adopts superfine spherical silver powder as a pore-forming agent, the silver powder and the palladium membrane are firstly alloyed through vacuum heat treatment, and then silver and silver-rich components are selectively removed by utilizing the different saturated vapor pressures of palladium and silver, so as to obtain the porous palladium membrane with the pore diameter of 100 nm-300 nm, and the porous palladium membrane can play a doping role, thereby improving the catalytic activity and hydrogen embrittlement resistance of the porous palladium membrane, and has higher practical value in the fields of fuel cells, hydrogen energy key materials and the like.
3. The preparation method has the advantages of simple preparation process, easy operation, low cost, environmental friendliness and suitability for large-scale industrial production.
The technical solution of the present invention is further described in detail by examples below.
Detailed Description
Example 1
The embodiment comprises the following steps:
step one, sequentially adopting 280#, 600# and 1000# sandpaper to polish a tantalum substrate with the diameter of 20mm multiplied by 0.1mm (the diameter is multiplied by the thickness), then adopting mixed acid liquid to polish, and then cleaning with deionized water and drying with nitrogen to obtain the treated tantalum substrate; the mixed acid solution consists of HF with the mass fraction of 40% and HNO with the mass fraction of 68% 3 The polishing agent is prepared according to the volume ratio of 1;
step two, dissolving 0.04g of palladium chloride into 50mL of absolute ethyl alcohol to obtain an activator, coating the activator on the surface of the treated tantalum substrate obtained in the step one, and performing vacuum heat treatment to obtain an activated tantalum substrate; the vacuum degree of the vacuum heat treatment is 8.0 x 10 -3 Pa, the temperature is 600 +/-10 ℃, and the time is 30min;
step three, soaking the activated tantalum substrate obtained in the step two in a hydrazine hydrate solution of 1mol/L for treatment for 15min;
step four, placing the activated tantalum substrate treated in the step three in a chemical palladium plating solution, adding a hydrazine hydrate solution, then performing chemical palladium plating for 50min at 50 +/-10 ℃ to form a palladium film on the tantalum substrate, and obtaining the tantalum substrate with the palladium film; the chemical palladium plating solution comprises the following components: 5g/L of palladium chloride, 380mL/L of ammonia water, 45g/L of EDTA disodium, and the balance of water, wherein the mass concentration of the hydrazine hydrate solution is 0.8%, and the addition amount of the hydrazine hydrate solution in the chemical palladium plating solution is 10mL/L;
step five, dispersing spherical silver powder with the particle size of 1-6 microns and the D90 of less than 5.6 microns into a mixed solution consisting of absolute ethyl alcohol and water according to the volume ratio of 0.075;
step six, coating the silver powder slurry obtained in the step five on the surface of the tantalum substrate with the palladium film obtained in the step four, and then performing vacuum annealing treatment to form a porous palladium film in the tantalum substrate; the vacuum degree of the vacuum annealing treatment is 8.0 multiplied by 10 -3 Pa, the temperature is 500 +/-10 ℃ and the time is 4h.
Example 2
The embodiment comprises the following steps:
firstly, sequentially grinding a tantalum substrate with the diameter of 20mm multiplied by 0.1mm (the diameter multiplied by the thickness) by using 280#, 600# and 1000# abrasive paper, then polishing by using mixed acid liquor, cleaning by using deionized water and drying by using nitrogen to obtain the treated tantalum substrate; the mixed acid solution consists of HF with the mass fraction of 40% and HNO with the mass fraction of 68% 3 The polishing solution is prepared according to the volume ratio of 1;
step two, dissolving 0.04g of palladium chloride into 50mL of absolute ethyl alcohol to obtain an activating agent, then coating the activating agent on the surface of the treated tantalum substrate obtained in the step one, and performing vacuum heat treatment to obtain an activated tantalum substrate; the vacuum degree of the vacuum heat treatment is 9.0 x 10 -2 Pa, at the temperature of 600 +/-10 ℃ for 29min;
step three, soaking the activated tantalum substrate obtained in the step two in a hydrazine hydrate solution of 1mol/L for treatment for 14min;
step four, placing the activated tantalum substrate treated in the step three in a chemical palladium plating solution, adding a hydrazine hydrate solution, then performing chemical palladium plating for 45min at 50 +/-10 ℃ to form a palladium film on the tantalum substrate, and obtaining the tantalum substrate with the palladium film; the chemical palladium plating solution comprises the following components: 5g/L of palladium chloride, 380mL/L of ammonia water, 45g/L of EDTA disodium, and the balance of water, wherein the mass concentration of the hydrazine hydrate solution is 0.8%, and the addition amount of the hydrazine hydrate solution in the chemical palladium plating solution is 10mL/L;
step five, dispersing spherical silver powder with the particle size of 1-6 microns and the D90 of less than 5.6 microns into a mixed solution consisting of absolute ethyl alcohol and water according to the volume ratio of 0.05;
step six, coating the silver powder slurry obtained in the step five on the surface of the tantalum substrate with the palladium film obtained in the step four, and then performing vacuum annealing treatment to form a porous palladium film in the tantalum substrate; the vacuum degree of the vacuum annealing treatment is 9.0 multiplied by 10 -2 Pa, the temperature is 500 +/-10 ℃ and the time is 4h.
Example 3
The embodiment comprises the following steps:
step one, sequentially adopting 280#, 600# and 1000# sandpaper to polish a tantalum substrate with the diameter of 20mm multiplied by 0.1mm (the diameter is multiplied by the thickness), then adopting mixed acid liquid to polish, and then cleaning with deionized water and drying with nitrogen to obtain the treated tantalum substrate; the mixed acid solution consists of HF with the mass fraction of 40% and HNO with the mass fraction of 68% 3 The polishing agent is prepared according to the volume ratio of 1;
step two, dissolving 0.04g of palladium chloride into 50mL of absolute ethyl alcohol to obtain an activator, coating the activator on the surface of the treated tantalum substrate obtained in the step one, and performing vacuum heat treatment to obtain an activated tantalum substrate; the vacuum degree of the vacuum heat treatment is 3.0 × 10 -3 Pa, the temperature is 600 +/-10 ℃, and the time is 31min;
step three, soaking the activated tantalum substrate obtained in the step two in a hydrazine hydrate solution of 1mol/L for treatment for 16min;
step four, placing the activated tantalum substrate treated in the step three in a chemical palladium plating solution, adding a hydrazine hydrate solution, then performing chemical palladium plating for 55min at 50 +/-10 ℃ to form a palladium film on the tantalum substrate, and obtaining the tantalum substrate with the palladium film; the chemical palladium plating solution comprises the following components: 5g/L of palladium chloride, 380mL/L of ammonia water, 45g/L of EDTA disodium, and the balance of water, wherein the mass concentration of the hydrazine hydrate solution is 0.8%, and the addition amount of the hydrazine hydrate solution in the chemical palladium plating solution is 10mL/L;
step five, dispersing spherical silver powder with the particle size of 1-6 microns and the D90 of less than 5.6 microns into a mixed solution consisting of absolute ethyl alcohol and water according to the volume ratio of 0.1;
step six, coating the silver powder slurry obtained in the step five on the surface of the tantalum substrate with the palladium film obtained in the step four, and then performing vacuum annealing treatment to form a porous palladium film in the tantalum substrate; the vacuum degree of the vacuum annealing treatment is 3.0 multiplied by 10 -3 Pa, the temperature is 500 +/-10 ℃ and the time is 4h.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (6)
1. A method for preparing a porous palladium membrane is characterized by comprising the following steps:
firstly, grinding a tantalum substrate by using 280#, 600# and 1000# abrasive paper in sequence, then polishing by using mixed acid liquor, cleaning by using deionized water, and drying by using nitrogen to obtain a treated tantalum substrate;
step two, dissolving palladium chloride into absolute ethyl alcohol to obtain an activating agent, then coating the activating agent on the surface of the treated tantalum substrate obtained in the step one, and performing vacuum heat treatment to obtain an activated tantalum substrate;
step three, soaking the activated tantalum substrate obtained in the step two in 1mol/L hydrazine hydrate solution for treatment for 15min +/-1 min;
step four, placing the activated tantalum substrate treated in the step three into a chemical palladium plating solution, adding a hydrazine hydrate solution, then performing chemical palladium plating to form a palladium film on the tantalum substrate, and obtaining the tantalum substrate with the palladium film; the chemical palladium plating solution comprises the following components: 5g/L of palladium chloride, 380mL/L of ammonia water, 45g/L of EDTA disodium, and the balance of water, wherein the mass concentration of the hydrazine hydrate solution is 0.8%, and the addition amount of the hydrazine hydrate solution in the chemical palladium plating solution is 10mL/L;
dispersing the spherical silver powder into a mixed solution consisting of absolute ethyl alcohol and water to obtain silver powder slurry;
and step six, coating the silver powder slurry obtained in the step five on the surface of the tantalum substrate with the palladium membrane obtained in the step four, and then carrying out vacuum annealing treatment to form a porous palladium membrane in the tantalum substrate.
2. The method as claimed in claim 1, wherein the acid mixture in step one comprises 40 wt% of HF and 68 wt% of HNO 3 The polishing solution is prepared according to the volume ratio of 1.
3. The method as claimed in claim 1, wherein the degree of vacuum of the vacuum heat treatment in step two is 3.0 x 10 -3 Pa～9.0×10 -2 Pa, the temperature is 600 +/-10 ℃, and the time is 30min +/-1 min.
4. The method for preparing a porous palladium membrane according to claim 1, wherein the electroless palladium plating is performed at 50 ℃ ± 10 ℃ for 50min ± 5min in step four.
5. The method according to claim 1, wherein the spherical silver powder in step five has a particle size of 1 μm to 6 μm and a D90 of less than 5.6 μm; the volume ratio of the absolute ethyl alcohol to the water in the mixed solution is 0.05-0.1.
6. The method as claimed in claim 1, wherein the vacuum degree of the vacuum annealing treatment in the sixth step is 3.0 x 10 -3 Pa～9.0×10 -2 Pa, the temperature is 500 +/-10 ℃ and the time is 4h.
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