CN112517001B - Preparation method of platinum black catalyst and platinum black catalyst - Google Patents
Preparation method of platinum black catalyst and platinum black catalyst Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000002245 particle Substances 0.000 claims abstract description 25
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 16
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910003446 platinum oxide Inorganic materials 0.000 claims abstract description 14
- NFOHLBHARAZXFQ-UHFFFAOYSA-L platinum(2+);dihydroxide Chemical compound O[Pt]O NFOHLBHARAZXFQ-UHFFFAOYSA-L 0.000 claims abstract description 14
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 13
- 150000002367 halogens Chemical class 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 11
- -1 silver ions Chemical class 0.000 claims abstract description 11
- 239000002244 precipitate Substances 0.000 claims abstract description 8
- 229910052709 silver Inorganic materials 0.000 claims abstract description 6
- 239000004332 silver Substances 0.000 claims abstract description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 5
- 239000006174 pH buffer Substances 0.000 claims abstract description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000012528 membrane Substances 0.000 claims description 11
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- 238000009792 diffusion process Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002923 metal particle Substances 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 25
- 230000000694 effects Effects 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 239000003446 ligand Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000000872 buffer Substances 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000013110 organic ligand Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000006179 pH buffering agent Substances 0.000 description 1
- AAIMUHANAAXZIF-UHFFFAOYSA-L platinum(2+);sulfite Chemical compound [Pt+2].[O-]S([O-])=O AAIMUHANAAXZIF-UHFFFAOYSA-L 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B01J35/33—
-
- B01J35/40—
-
- B01J35/613—
-
- 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
Abstract
The invention provides a preparation method of a platinum black catalyst and the platinum black catalyst. The method for preparing the platinum black catalyst comprises the following steps: dissolving a halogen-containing platinum precursor in strong acid, reacting the precursor with silver ions, and removing precipitates to obtain a reaction solution; adjusting the pH of the reaction liquid to 3 to 4 in the presence of a pH buffer to form platinum hydroxide and/or platinum oxide; and reducing the platinum hydroxide and/or the platinum oxide to obtain a platinum black catalyst. The obtained platinum black catalyst has extremely small particle size and thus has high catalytic activity. The platinum black catalyst can obtain good performance when being applied to electrochemical application.
Description
Technical Field
The invention relates to the field of electrochemical catalysts, in particular to a preparation method of a platinum black catalyst and the platinum black catalyst obtained by the preparation method.
Background
Platinum black catalysts are catalysts for electrochemical applications, such as for fuel cells and electrolyzers, especially in those applications where an ion exchange membrane is used as the separation medium or electrolyte.
An early preparation of platinum black catalysts was carried out by first synthesizing H using a platinum sulfite complex as a precursor, as described in US3992512 and US4059541 3 Pt(SO 3 ) 2 OH, then reacts with hydrogen peroxide to produce a colloid, which can be adsorbed on carbon or left in solution and finally reduced (e.g. with N) 2 H 2 Or hydrogen) into platinum particles. The method needs to control the pH continuously in the synthesis process, and the obtained platinum particles are generally large and are unevenly distributed on the carbon carrier, and sulfur is not easy to be removed completely, so that the method has negative effects on the performance of the catalyst.
The other path is S 2 O 3 2- Reduction of chloroplatinic acid H 2 PtCl 6 In the case of a carbon support, the colloidal platinum particles formed are adsorbed on the carbon support, but this adsorption is complicated and difficult to reproduce, and is particularly difficult to achieve when the platinum loading is high. Therefore, the reaction is very slow, large particles are easily formed, the total area of the particles is small, the particles are not uniformly distributed on the carbon carrier, and the performance is poor.
In patent US 439292927, a platinum precursor is added to a sodium carbonate solution to precipitate a metal hydroxide, which is finally reduced. However, the intermediate metal hydroxides do not have a fixed composition and are generally not reproducible and are not formed uniformly in solution, with the result that the final catalyst particles are very non-uniform and have poor properties.
The complex is synthesized by combining the complex with a reducing agent in the process for preparing the platinum catalyst. Chloroplatinic acid (H) as in patent US8012905B2 2 PtCl 6 ) Is a platinum precursor, ethylene glycol is a ligand (ligand) and is also a reducing agent, and at the temperature of 140 ℃, the platinum particles are protected by ethylene glycol after being formed so as to prevent the platinum particles from being aggregated to form large particles. This patent also uses ethanol/water as a solvent to react with the reducing agent polyvinylpyrrolidone at 90 ℃ to give a slightly inferior catalyst. However, the ethylene glycol and PVP remaining in the catalyst in this method also affect its performance. In the Catalysis Letters, volume 129, pages1-6 (2009) by Jeong Y.park et al, several nitrogen and sulfur ligands are used to prevent platinum particles from aggregating into large particles. The precursor is K 2 PtCl 4 The reducing agent is NaBH 4 And is carried out in 50 ℃ aqueous solution. The platinum particles thus obtained are large (12 nm) and the ligand is difficult to remove, using uv light, which is difficult to do in mass production.
Therefore, the platinum black catalyst prepared in the prior art has the disadvantages of large particle size, difficult removal of impurities contained therein, and the like.
Disclosure of Invention
The invention provides a preparation method of a platinum black catalyst and the platinum black catalyst obtained by the preparation method. The preparation method has simple steps and easily obtained raw materials, and is beneficial to industrial production. The obtained platinum black catalyst has extremely small particle size and thus has high catalytic activity.
The platinum black catalyst can obtain good performance when being applied to electrochemical application. For example, the platinum black catalyst of the present invention can obtain excellent specific mass activity and specific area activity when used in a gas diffusion electrode, a catalyst-coated membrane or a membrane electrode.
The present invention provides a method for preparing a platinum black catalyst, which comprises:
dissolving a halogen-containing platinum precursor in strong acid, reacting the strong acid with silver ions, and removing precipitates to obtain a reaction solution;
adjusting the pH of the reaction liquid to 3 to 4 in the presence of a pH buffer to form platinum hydroxide and/or platinum oxide; and
the platinum hydroxide and/or the platinum oxide is reduced to obtain a platinum black catalyst.
In one embodiment, the halogen-containing platinum precursor is selected from H 2 PtCl 6 、Na 2 PtCl 6 、Na 2 PtCl 4 、K 2 PtCl 4 、Na 2 PtBr 6 And Na 2 PtI 6 Or a hydrate thereof.
In one embodiment, the pH of the reaction solution is adjusted at a temperature of 35 to 95 ℃, preferably 60 to 90 ℃, to form platinum hydroxide and/or platinum oxide. At this reaction temperature, the reaction can be rapidly and completely carried out.
In one embodiment, the pH buffering agent is one or more of acetic acid, propionic acid, butyric acid, and phosphoric acid.
In one embodiment, the strong acid is selected from HClO 4 、HBrO 4 、HNO 3 、CF 3 One or more of COOH, toluene sulfonic acid, triflic acid, HCl and HBr.
In one embodiment, by N 2 H 2 、NaBH 4 、NaH 2 PO 2 A reducing agent selected from one or more of HCHO and oxalic acid to reduce the platinum hydroxide and/or platinum oxide.
In one embodiment, the platinum hydroxide and/or platinum oxide is reduced by hydrogen or a hydrogen-containing gas mixture at a temperature of 100 to 600 ℃.
In one embodiment, by NaOH, KOH, na 2 CO 3 、K 2 CO 3 And NH 4 One or more of OH is used to adjust the pH of the reaction solution.
In another aspect, the present invention also provides a platinum black catalyst obtained by the above method of the present invention, wherein the platinum metal particles in the platinum black catalyst have a particle size of 3.9 to 5.5nm.
In still another aspect, the present invention also provides a gas diffusion electrode, catalyst-coated membrane (CCM) or membrane electrode comprising the platinum black catalyst of the present invention described above. The gas diffusion electrode, catalyst-coated membrane or membrane electrode can obtain good performance due to the inclusion of the above highly active platinum black catalyst.
Compared with the prior art, the scheme of the invention has the following advantages:
1. the method for preparing the platinum black catalyst has simple steps, easily obtained raw materials, no impurity introduced in the reaction process and convenient post-treatment.
2. The platinum black catalyst of the present invention has a very small particle size and thus has a very high catalytic activity.
3. The gas diffusion electrode, the membrane electrode, the catalyst-coated membrane and the like using the platinum black catalyst have excellent electrochemical activity, and the specific surface area of the electrochemical activity is 30-60 m 2 Per g, preferably from 45 to 55m 2 /g。
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a method for preparing a platinum black catalyst, which comprises the following steps: dissolving a halogen-containing platinum precursor in strong acid, reacting the precursor with silver ions, and removing precipitates to obtain a reaction solution; adjusting the pH of the reaction liquid to 3 to 4 in the presence of a pH buffer to form platinum hydroxide and/or platinum oxide; and reducing the platinum hydroxide and/or the platinum oxide to obtain a platinum black catalyst.
The invention directly uses a halogen-containing platinum precursor as a raw material, wherein halogen is used as a complexing ligand, strong acid is firstly added to adjust the pH of the solution to be acidic or weakly acidic, such as pH1-2, and then silver ions are added to remove chloride ions, and then hydration ions of platinum are obtained. The inventors have surprisingly found that: in the presence of a strong acid and silver ions, the halogen ions are removed from the halogen-containing platinum precursor and a precipitate is formed. When platinum ions are not complexed with a halogen strong ligand (ligand), the platinum ions slowly form a less soluble hydroxide or oxide in neutral or slightly acidic aqueous solutions. If small-sized platinum black catalyst particles are to be formed, it is necessary to control the pH so as to slowly vary within a certain range, which can be achieved by adding a buffer. The inventors have surprisingly found that the pH can be controlled to change slowly by two factors: the platinum precursor is first protected by the halogen strong ligand, and after the halogen ligand is removed, the pH of the solution is slowly increased to promote the generation of hydroxide or oxide.
The preparation method of the invention avoids using organic ligands such as polyethylene glycol, and the like, because the organic ligands can be removed at high temperature, and the process needs a large amount of heat energy, and the carbon carrier or the catalyst is easy to be burnt under the condition of the carbon carrier. In addition, because organic ligands are not used, water can be directly used as a reaction solvent in the method, and the method is favorable for the recovery of waste liquid after reaction and environmental protection.
Examples
I. Preparation of platinum black catalyst
Preparation example 1
117.93 g of Na 2 PtCl 4 ·xH 2 O (Pt = 42.4%) was dissolved in 835mL of deionized water, 165mL of perchloric acid (11.6 mol/L) was added, and the mixture was stirred well. 178.5 grams of silver nitrate was dissolved in 1050mL of deionized water to prepare a 1mol/L silver nitrate solution. Under continuous stirring, the silver nitrate solution is added dropwise to Na to which perchloric acid has been added over 40 minutes 2 PtCl 4 ·xH 2 O in solution. After stirring for another 30 minutes, the silver chloride precipitate was filtered, and the precipitate was washed with 500mL of deionized water three times, and the filtrates were combined to obtain a reaction solution.
The reaction solution was placed in a large beaker, and 31.25g of acetic acid (99.9%) as a buffer was added. NaOH was added in a proportion of 20% per minute at a rate of 10 mL/min until the pH was between 3 and 4 (about 410-470 g) with uniform stirring. After the addition, stirring was carried out for a further 30 minutes, heating was started from room temperature, brought to 90 ℃ after one hour and reacted for one hour at 90 ℃. The heating and stirring were then stopped, and after allowing the slurry precipitate to cool, it was filtered and washed with deionized water. The collected catalyst block was dried at 115 ℃ and crushed, then heat treated at 200 ℃ under hydrogen, and reduced to obtain a platinum black catalyst having a particle size of 3.5-5.5nm as measured by a laser particle sizer.
Preparation example 2
The procedure for obtaining a reaction solution was the same as in example 1. The reaction solution was placed in a large beaker, and 31.25g of acetic acid (99.9%) as a buffer was added. To the obtained reaction solution was added 20% NaOH, the pH was adjusted to 3 to 4, and the mixture was stirred for another 30 minutes, heated from room temperature to 90 ℃ after one hour, and reacted at 90 ℃ for one hour. Then, 234mL of formaldehyde as a reducing agent was slowly added to the reaction solution over one hour. After the addition was complete, stirring was continued for an additional hour, then heating and stirring were stopped, and after allowing the slurry to settle and cool, it was filtered and washed with deionized water. The collected catalyst cake was dried at 115 ℃ and crushed to obtain a platinum black catalyst having a particle size of 3.5-5.5nm as measured by a laser particle sizer.
Preparation example 3
The procedure was as in preparation 1, but the content was determined by 177mL68% HNO 3 165mL of 70% HClO 4 。
Preparation example 4
The procedure was the same as in preparation 1, but propionic acid was used as buffer instead of acetic acid.
Preparation example 5
The procedure was the same as in preparation example 1, except that the reaction temperature was 60 ℃.
Testing of catalyst Performance
The method for preparing the slurry and the electrode comprises the following steps: after the platinum black catalyst obtained in the above preparation example was sufficiently homogenized in a water-alcohol mixed solvent, a fixed amount of the catalyst dispersion was applied to a carbon amorphous rotary electrode (Pine Research, usa) by a pipette, and after the catalyst dispersion was dried, a thin film deposited on the electrode was obtained, and the platinum black catalyst was generally coated in an amount of 16 μ g per square centimeter of the electrode.
The method of rotating the disk electrode: in order to research the distribution of the current density on the surface of the electrode, a rotating disc electrode method is adopted for testing. The procedure of this method can be found in T.Schmidt et al, J.electrochem.Soc.,146 (1999), p1296 and H.A.Gasteiger et al, applied Catalysis, B2005, 56, p9-35.
According to the analysis conclusion of the latter document, the rotating electrode is in HClO 4 In the electrolyte, the current measured at 0.9V can correspond well to the current observed in the MEA test. The method comprises the following specific steps: placing the electrode prepared by the above steps in 0.1moles/L HClO 4 The voltage in the solution was swept (100 mv/s) between 0.05V and 0.95V (relative to RHE) to remove the negatively acting chemicals introduced during the preparation of the catalyst coating. The electrochemical active area (ECSA) is calculated from a hydrogen adsorption current in a Cyclic Voltammetry (CV) graph (50 mv/s). The oxygen reduction activity was measured at 0.1moles/L HClO saturated with oxygen 4 In the middle, the electrode was swept from 0.3V to 0.95V at 1600RPM (1600 RPM) to measure the activity of reducing oxygen, expressed as specific mass activity (a/mg Pt, MA), 0.9V (relative to RHE), and during the test, factors due to the oxygen diffusion rate were corrected using the standard method conventional in the art, i.e. the limiting current plateau through low voltage corresponds to the oxygen diffusion rate correction. The specific area activity is obtained by the specific mass activity and an ECSA calculation method.
ECSA calculation method 1:
in the above formula, SH is a peak area; v is the sweeping speed; mC.cm -2 Represents millicoulombs per square centimeter; m Pt Is the mass of platinum in g.
The results of the rotating disk electrode testing are listed in table one. A commercial platinum black catalyst was used as a standard for comparison.
TABLE-comparison of Performance data for Membrane electrodes made with different catalyst types
As shown in Table I, the specific activity by mass and the specific activity by area of the platinum black catalyst prepared by the present invention are higher than those of the commercial platinum black catalyst, and these advantages can be explained by the superiority of the preparation method of the present invention.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (8)
1. A method of preparing a platinum black catalyst, comprising:
dissolving a halogen-containing platinum precursor in a strong acid, reacting the precursor with silver ions, and removing precipitates to obtain a reaction solution, wherein the strong acid is selected from HClO 4 、HBrO 4 、HNO 3 One or more of HCl and HBr;
adjusting the pH of the reaction solution to 3 to 4 in the presence of a pH buffer to form platinum hydroxide and/or platinum oxide, the pH buffer being one or more of acetic acid, propionic acid, butyric acid and phosphoric acid; and
reducing the platinum hydroxide and/or the platinum oxide to obtain a platinum black catalyst in which the platinum metal particles have a particle diameter of 3.9 to 5.5nm.
2. The method of claim 1, wherein the halogen-containing platinum precursor is selected from H 2 PtCl 6 、Na 2 PtCl 6 、Na 2 PtCl 4 、K 2 PtCl 4 、Na 2 PtBr 6 Or Na 2 PtI 6 。
3. The method according to claim 1 or 2, characterized in that the pH of the reaction liquid is adjusted at a temperature of 35 to 95 ℃ to form platinum hydroxide and/or platinum oxide.
4. The method of claim 1 or 2, wherein N is passed 2 H 2 、NaBH 4 、NaH 2 PO 2 A reducing agent selected from one or more of HCHO and oxalic acid to reduce the platinum hydroxide and/or platinum oxide.
5. The method according to claim 1, characterized in that the platinum hydroxide and/or platinum oxide is reduced by hydrogen or a hydrogen-containing gas mixture at a temperature of 100 ℃ to 600 ℃.
6. The method of claim 1, wherein the reaction is carried out by NaOH, KOH, na 2 CO 3 、K 2 CO 3 And NH 4 And one or more of OH is used for adjusting the pH of the reaction liquid.
7. A platinum black catalyst obtained by the method of any one of claims 1 to 6, wherein the platinum metal particles in the platinum black catalyst have a particle size of 3.9nm to 5.5nm.
8. A gas diffusion electrode, catalyst-coated membrane or membrane electrode comprising the platinum black catalyst as claimed in claim 7.
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