WO2022120687A1 - Phosphorus-activated platinum-based catalyst, preparation method therefor, and application thereof - Google Patents
Phosphorus-activated platinum-based catalyst, preparation method therefor, and application thereof Download PDFInfo
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- WO2022120687A1 WO2022120687A1 PCT/CN2020/135149 CN2020135149W WO2022120687A1 WO 2022120687 A1 WO2022120687 A1 WO 2022120687A1 CN 2020135149 W CN2020135149 W CN 2020135149W WO 2022120687 A1 WO2022120687 A1 WO 2022120687A1
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- platinum
- phosphorus
- based catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- 239000011574 phosphorus Substances 0.000 title claims abstract description 60
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 60
- -1 Phosphorus-activated platinum Chemical class 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 134
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 54
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011259 mixed solution Substances 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 238000010992 reflux Methods 0.000 claims abstract description 16
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 150000003057 platinum Chemical class 0.000 claims abstract description 9
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 7
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- 239000012265 solid product Substances 0.000 claims abstract description 6
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 239000012266 salt solution Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 37
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 36
- 239000006229 carbon black Substances 0.000 claims description 30
- 239000002131 composite material Substances 0.000 claims description 22
- 239000002585 base Substances 0.000 claims description 15
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 14
- 229910052700 potassium Inorganic materials 0.000 claims description 14
- 239000011591 potassium Substances 0.000 claims description 14
- 239000002105 nanoparticle Substances 0.000 claims description 10
- 239000004210 ether based solvent Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 7
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000005456 alcohol based solvent Substances 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- 239000003945 anionic surfactant Substances 0.000 claims description 4
- 239000003093 cationic surfactant Substances 0.000 claims description 4
- 239000003759 ester based solvent Substances 0.000 claims description 4
- 239000005453 ketone based solvent Substances 0.000 claims description 4
- 239000002736 nonionic surfactant Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- QTAGQHZOLRFCBU-UHFFFAOYSA-N (R)-Oxypeucedanin Chemical compound CC1(C)OC1COC1=C(C=CO2)C2=CC2=C1C=CC(=O)O2 QTAGQHZOLRFCBU-UHFFFAOYSA-N 0.000 claims description 2
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000003570 air Substances 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 229910000102 alkali metal hydride Inorganic materials 0.000 claims description 2
- 150000008046 alkali metal hydrides Chemical class 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- FOSZYDNAURUMOT-UHFFFAOYSA-J azane;platinum(4+);tetrachloride Chemical compound N.N.N.N.[Cl-].[Cl-].[Cl-].[Cl-].[Pt+4] FOSZYDNAURUMOT-UHFFFAOYSA-J 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 2
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 claims description 2
- 229920000428 triblock copolymer Polymers 0.000 claims description 2
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 229910019142 PO4 Inorganic materials 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 1
- 239000010452 phosphate Substances 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 73
- 229960004756 ethanol Drugs 0.000 description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000002135 nanosheet Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000007787 solid Substances 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 description 5
- 239000012279 sodium borohydride Substances 0.000 description 5
- 239000000446 fuel Substances 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- LTEOHQLUJPPHMP-UHFFFAOYSA-N C(C)O.[P] Chemical compound C(C)O.[P] LTEOHQLUJPPHMP-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 238000003411 electrode reaction Methods 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical class ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
Images
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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/089—Alloys
-
- 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
Definitions
- the invention belongs to the technical field of catalytic materials, and particularly relates to a phosphorus-activated platinum-based catalyst and a preparation method and application thereof.
- Electrochemical energy storage and conversion systems such as direct methanol fuel cells
- electrochemical reactions are involved in all electrochemical systems, and the slow electrode reaction kinetics is one of the important reasons that limit its commercial application.
- electrocatalysts with high activity and stability are often required.
- platinum group metal nanocrystals play an important role in the methanol oxidation reaction (MOR) of direct methanol fuel cell anodes due to their unique high activity and high stability, and they are still irreplaceable.
- MOR methanol oxidation reaction
- platinum group metal nanomaterials are rare metal materials with very low element abundance in the earth's crust.
- my country's platinum group metal reserves only account for 0.48% of the global reserves. They rely heavily on imports and have high application costs. Methanol fuel cells are widely used commercially. Therefore, it is of great significance to develop a platinum-based catalyst with low cost and high catalytic activity.
- the purpose of the present invention is to provide a phosphorus-activated platinum-based catalyst and a preparation method and application thereof.
- the present invention provides a preparation method of a phosphorus-activated platinum-based catalyst, comprising the following steps:
- Phosphating of platinum-based catalyst add the platinum-based catalyst and phosphorus source prepared in 1) into the second solvent, and then reflux at 30-180 ° C for 5-12 hours under the protection of the atmosphere, and the obtained after refluxing is completed.
- the solid product is the phosphorus-activated platinum-based catalyst.
- the platinum-based catalyst described in step 1) is a platinum/carbon carrier composite catalyst, that is, a platinum nanoparticle layer is prepared on the surface of the carbon carrier.
- the average particle size of the platinum nanoparticles is 0.5-20 nm.
- the carbon carrier described in step 1) includes at least one of carbon black, graphite, graphene, carbon fiber, carbon nanotube, activated carbon, and carbon molecular sieve;
- the first solvent described in step 1) includes at least one of alcohol-based solvents, ether-based solvents, alcohol-ether-based solvents, ketone-based solvents, ester-based solvents, and amide-based solvents;
- the reducing agent in step 1) includes at least one of alkali metal hydride, alkali metal borohydride, and aldehyde solution.
- the surfactant described in step 1) includes at least one of nonionic surfactant, anionic surfactant, and cationic surfactant;
- the nonionic surfactant comprises at least one of polyvinylpyrrolidone, polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer;
- the anionic surfactant comprises sodium dodecylbenzenesulfonate
- the cationic surfactant comprises cetyltrimethylammonium bromide.
- the concentration of the platinum salt solution in step 1) is 0.08-0.12 mol/L;
- the platinum salt includes potassium tetrachloroplatinate, potassium chloroplatinate, tetraammine platinum nitrate, sodium chloroplatinite, dinitrosodiammine platinum, tetraammine platinum chloride, platinum tetrachloride , at least one of potassium chloroplatinite, platinum acetylacetonate, sodium hexachloroplatinate, platinum dichloride and potassium tetranitroplatinate.
- step 1) the mass ratio of carbon carrier, first solvent, deionized water, surfactant, platinum salt, and reducing agent is 1:(1 ⁇ 500):(1 ⁇ 500):(0.05 ⁇ 10): (0.05 to 10): (0.001 to 10).
- the phosphorus source described in step 2) includes at least one of black phosphorus, red phosphorus, orange phosphorus, purple phosphorus, white phosphorus, trioctylphosphine, and phosphorus oxide;
- the atmosphere described in step 2) is at least one of air, nitrogen, argon, and hydrogen.
- the second solvent in step 2) includes at least one of water, alcohol-based solvent, ether-based solvent, alcohol-ether-based solvent, ketone-based solvent, ester-based solvent, and amide-based solvent.
- the mass ratio of the platinum-based catalyst, the phosphorus source, and the second solvent is 1:(0.001-10):(1-100).
- the present invention provides a phosphorus-activated platinum-based catalyst prepared by the above-mentioned preparation method.
- the present invention provides an application of the above-mentioned phosphorus-activated platinum-based catalyst in electrocatalytic oxygen reduction.
- the present invention achieves the purpose of regulating the electronic structure state of the surface of the platinum nano-particles through the high adsorption energy of the phosphorus element and the platinum element, and the phosphorus element and the platinum element rapidly form a platinum-phosphorus bond;
- the invention can realize the alloying of phosphorus element on the surface of metal platinum at low temperature and low pressure or even under normal temperature and normal pressure, so as to achieve the effect of regulating the electronic structure of the metal platinum surface. ;
- the preparation method of the phosphorus-activated platinum-based catalyst of the invention is simple, the cost is low, and the catalytic activity is high.
- Fig. 1 is the TEM image of the phosphorus-activated platinum-based catalyst prepared in Example 1;
- Fig. 2 is the XPS comparison diagram of the platinum-based catalyst prepared in Example 1 and the phosphorus-activated platinum-based catalyst;
- FIG. 3 is a comparison diagram of electrocatalytic oxygen reduction performance of the platinum-based catalyst prepared in Example 1 and the phosphorus-activated platinum-based catalyst.
- the raw materials used in the examples can be obtained from conventional commercial channels unless otherwise specified.
- the potassium tetrachloroplatinate solution mentioned in the examples refers to an aqueous potassium tetrachloroplatinate solution.
- the structure of the prepared phosphorus-activated platinum-based catalyst was characterized by transmission electron microscopy, and the results are shown in Figure 1. It can be seen from Figure 1 that the phosphorus-activated platinum-based particles are uniformly distributed on the carbon black surface.
- the prepared platinum-based catalyst and phosphorus-activated platinum-based catalyst were characterized by X-ray photoelectron spectrometer. The results are shown in Figure 2. By comparing with the platinum-based catalyst without phosphating, it was found that the platinum-based catalyst after phosphating The X-ray photoelectron spectroscopy (XPS) of the base catalyst shows a new Pt 4f front at 72.8°, which also indicates the formation of platinum-phosphorus bonds.
- XPS X-ray photoelectron spectroscopy
- Electrochemical oxygen reduction performance testing of phosphorus-activated platinum-based catalysts Electrochemical measurements were performed at 30°C using a three-electrode system with a rotating disk electrode (RDE, 0.196 cm 2 ) connected to an electrochemical workstation. Pt foil and Ag/AgCl electrodes were used for the counter and reference electrodes, respectively.
- the catalyst platinum-based catalyst or phosphorus-activated platinum-based catalyst
- a homogeneous ink with a platinum element concentration of 0.16 mg mL -1 in the solution was prepared. 12.5 ⁇ L of the homogeneous ink was then added dropwise and spin-dried onto the pre-cleaned glassy carbon RDE.
- CV20 cycle scans were performed at a rate of 500 mV s ⁇ 1 in nitrogen-saturated HClO 4 (0.1 M).
Abstract
The present invention discloses a phosphorus-activated platinum-based catalyst, a preparation method therefor, and an application thereof. The preparation method comprises the following steps: 1) synthesis of a platinum-based catalyst: adding a first solvent, deionized water, a surfactant, and a platinum salt solution into a carbon carrier, and uniformly stirring at room temperature to obtain a base mixed solution; and then rapidly adding a reducing agent into the base mixed solution, and stirring at room temperature for 0.5-24 h (not including 24 h), a solid product obtained after stirring ends being the platinum-based catalyst; and 2) phosphating of the platinum-based catalyst: adding the platinum-based catalyst prepared in 1) and a phosphate source into a second solvent, and then refluxing at 30-180°C for 5-12 under the atmosphere protection, a solid product obtained after refluxing ends being the phosphorus-activated platinum-based catalyst. The preparation method for the phosphorus-activated platinum-based catalyst of the present invention is simple, low in costs, and high in catalytic activity.
Description
本发明属于催化材料技术领域，具体涉及一种磷活化铂基催化剂及其制备方法和应用。The invention belongs to the technical field of catalytic materials, and particularly relates to a phosphorus-activated platinum-based catalyst and a preparation method and application thereof.
发展新一代环境友好型的绿色能源体系逐渐受到世界各国的广泛关注。电化学能源存储与转换***(例如直接甲醇燃料电池等)被视为有希望解决能源与环境问题的候选者。然而，在电化学***中均涉及电化学反应，而缓慢的电极反应动力学是限制其商业化应用的重要原因之一。为了加快电极反应动力学速率，常常需要高活性及稳定性的电催化剂。目前，铂族金属纳米晶以其独特的高活性、高稳定性在直接甲醇燃料电池阳极甲醇氧化反应(Methanol oxidation reaction，MOR)具有至关重要的地位，目前仍不可替代。然而，铂族金属纳米材料属于稀有金属材料，在地壳中的元素丰度很低，特别是我国铂族金属储量仅占全球储量的0.48％，大量依赖进口，具有较高的应用成本，限制了甲醇燃料电池广泛商业化应用。因此，开发一种成本低廉、高催化活性的铂基催化剂具有重要意义。The development of a new generation of environmentally friendly green energy systems has gradually attracted widespread attention from all over the world. Electrochemical energy storage and conversion systems, such as direct methanol fuel cells, are regarded as promising candidates for solving energy and environmental problems. However, electrochemical reactions are involved in all electrochemical systems, and the slow electrode reaction kinetics is one of the important reasons that limit its commercial application. In order to accelerate the kinetic rate of the electrode reaction, electrocatalysts with high activity and stability are often required. At present, platinum group metal nanocrystals play an important role in the methanol oxidation reaction (MOR) of direct methanol fuel cell anodes due to their unique high activity and high stability, and they are still irreplaceable. However, platinum group metal nanomaterials are rare metal materials with very low element abundance in the earth's crust. In particular, my country's platinum group metal reserves only account for 0.48% of the global reserves. They rely heavily on imports and have high application costs. Methanol fuel cells are widely used commercially. Therefore, it is of great significance to develop a platinum-based catalyst with low cost and high catalytic activity.
发明内容SUMMARY OF THE INVENTION
为了解决上述背景技术中所提出的问题，本发明的目的在于提供一种磷活化铂基催化剂及其制备方法和应用。In order to solve the problems raised in the above background technology, the purpose of the present invention is to provide a phosphorus-activated platinum-based catalyst and a preparation method and application thereof.
为了达到上述目的，本发明所采用的技术方案为：一方面，本发明提供了一种磷活化铂基催化剂的制备方法，包括以下步骤：In order to achieve the above purpose, the technical scheme adopted in the present invention is: on the one hand, the present invention provides a preparation method of a phosphorus-activated platinum-based catalyst, comprising the following steps:
1)铂基催化剂的合成：在碳载体中加入第一溶剂、去离子水、表面活性剂和铂盐溶液，并在常温下搅拌均匀得到基底混合液；随后将还原剂快速加入到所述基底混合液中，并在常温下搅拌0.5-24h(不包含24h)，搅拌结束后得到的固体产物为所述铂基催化剂；1) Synthesis of platinum-based catalyst: add the first solvent, deionized water, surfactant and platinum salt solution to the carbon support, and stir evenly at room temperature to obtain a base mixed solution; then quickly add a reducing agent to the base In the mixed solution, and stirred at normal temperature for 0.5-24h (excluding 24h), the solid product obtained after stirring is the platinum-based catalyst;
2)铂基催化剂的磷化：在第二溶剂中加入1)中制备得到的铂基催化剂和磷源，然后在气氛保护下，30-180℃下回流5-12小时，回流结束后得到的固体产物为所述磷活化铂基催化剂。2) Phosphating of platinum-based catalyst: add the platinum-based catalyst and phosphorus source prepared in 1) into the second solvent, and then reflux at 30-180 ° C for 5-12 hours under the protection of the atmosphere, and the obtained after refluxing is completed. The solid product is the phosphorus-activated platinum-based catalyst.
进一步地，步骤1)中所述的铂基催化剂为铂/碳载体复合催化剂，即在碳载体表面制得铂纳米粒子层。Further, the platinum-based catalyst described in step 1) is a platinum/carbon carrier composite catalyst, that is, a platinum nanoparticle layer is prepared on the surface of the carbon carrier.
进一步地，所述铂纳米粒子的平均粒径为0.5～20nm。Further, the average particle size of the platinum nanoparticles is 0.5-20 nm.
进一步地，步骤1)中所述的碳载体包括炭黑、石墨、石墨烯、碳纤维、碳纳米管、活 性炭、碳分子筛中的至少一种；Further, the carbon carrier described in step 1) includes at least one of carbon black, graphite, graphene, carbon fiber, carbon nanotube, activated carbon, and carbon molecular sieve;
优选地，步骤1)中所述的第一溶剂包括醇类溶剂、醚类溶剂、醇醚类溶剂、酮类溶剂、酯类溶剂、酰胺类溶剂中的至少一种；Preferably, the first solvent described in step 1) includes at least one of alcohol-based solvents, ether-based solvents, alcohol-ether-based solvents, ketone-based solvents, ester-based solvents, and amide-based solvents;
优选地，步骤1)中所述的还原剂包括碱金属氢化物、碱金属硼氢化物、醛溶液中的至少一种。Preferably, the reducing agent in step 1) includes at least one of alkali metal hydride, alkali metal borohydride, and aldehyde solution.
进一步地，步骤1)中所述的表面活性剂包括非离子表面活性剂、阴离子表面活性剂、阳离子表面活性剂中的至少一种；Further, the surfactant described in step 1) includes at least one of nonionic surfactant, anionic surfactant, and cationic surfactant;
优选地，所述非离子表面活性剂包括聚乙烯吡咯烷酮、聚氧乙烯-聚氧丙烯-聚氧乙烯三嵌段共聚物中的至少一种；Preferably, the nonionic surfactant comprises at least one of polyvinylpyrrolidone, polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer;
优选地，所述阴离子表面活性剂包括十二烷基苯磺酸钠；Preferably, the anionic surfactant comprises sodium dodecylbenzenesulfonate;
优选地，所述阳离子表面活性剂包括十六烷基三甲基溴化铵。Preferably, the cationic surfactant comprises cetyltrimethylammonium bromide.
进一步地，步骤1)中所述铂盐溶液的浓度为0.08～0.12mol/L；Further, the concentration of the platinum salt solution in step 1) is 0.08-0.12 mol/L;
优选地，所述铂盐包括四氯铂酸钾、氯铂酸钾、四氨合硝酸铂、氯亚铂酸钠、二亚硝基二氨铂、四氨合氯化铂、四氯化铂、氯亚铂酸钾、乙酰丙酮铂、六氯代铂酸钠、二氯化铂、四硝基铂酸钾中的至少一种。Preferably, the platinum salt includes potassium tetrachloroplatinate, potassium chloroplatinate, tetraammine platinum nitrate, sodium chloroplatinite, dinitrosodiammine platinum, tetraammine platinum chloride, platinum tetrachloride , at least one of potassium chloroplatinite, platinum acetylacetonate, sodium hexachloroplatinate, platinum dichloride and potassium tetranitroplatinate.
进一步地，步骤1)中所述碳载体、第一溶剂、去离子水、表面活性剂、铂盐、还原剂的质量比为1：(1～500)：(1～500)：(0.05～10)：(0.05～10)：(0.001～10)。Further, in step 1), the mass ratio of carbon carrier, first solvent, deionized water, surfactant, platinum salt, and reducing agent is 1:(1～500):(1～500):(0.05～ 10): (0.05 to 10): (0.001 to 10).
进一步地，步骤2)中所述的磷源包括黑磷、红磷、橙磷、紫磷、白磷、三辛基膦、氧化磷中的至少一种；Further, the phosphorus source described in step 2) includes at least one of black phosphorus, red phosphorus, orange phosphorus, purple phosphorus, white phosphorus, trioctylphosphine, and phosphorus oxide;
优选地，步骤2)中所述的气氛为空气、氮气、氩气、氢气中的至少一种。Preferably, the atmosphere described in step 2) is at least one of air, nitrogen, argon, and hydrogen.
优选地，步骤2)中所述的第二溶剂包括水、醇类溶剂、醚类溶剂、醇醚类溶剂、酮类溶剂、酯类溶剂、酰胺类溶剂中的至少一种。Preferably, the second solvent in step 2) includes at least one of water, alcohol-based solvent, ether-based solvent, alcohol-ether-based solvent, ketone-based solvent, ester-based solvent, and amide-based solvent.
进一步地，所述铂基催化剂、磷源、第二溶剂的质量比为1：(0.001～10)：(1～100)。Further, the mass ratio of the platinum-based catalyst, the phosphorus source, and the second solvent is 1:(0.001-10):(1-100).
另一方面，本发明提供了一种磷活化铂基催化剂，由上述所述的制备方法制备得到。On the other hand, the present invention provides a phosphorus-activated platinum-based catalyst prepared by the above-mentioned preparation method.
再一方面，本发明提供了一种上述所述的磷活化铂基催化剂在电催化氧还原中的应用。In yet another aspect, the present invention provides an application of the above-mentioned phosphorus-activated platinum-based catalyst in electrocatalytic oxygen reduction.
进一步地，上述所述的磷活化铂基催化剂在直接甲醇燃料电池阳极甲醇氧化反应中的应用。Further, the application of the above-mentioned phosphorus-activated platinum-based catalyst in the anode methanol oxidation reaction of direct methanol fuel cells.
本发明的有益效果为：本发明通过磷元素与铂元素的高吸附能，磷元素与铂元素快速形成铂磷键，达到调控铂纳米颗粒表面电子结构状态的目的；The beneficial effects of the present invention are as follows: the present invention achieves the purpose of regulating the electronic structure state of the surface of the platinum nano-particles through the high adsorption energy of the phosphorus element and the platinum element, and the phosphorus element and the platinum element rapidly form a platinum-phosphorus bond;
本发明可在低温低压甚至常温常压下实现磷元素在金属铂表面合金化，达到调控金属铂 表面电子结构的作用，通过调控铂基催化剂表面电子结构以达到促进反应吸附平衡，从而提升催化活性；The invention can realize the alloying of phosphorus element on the surface of metal platinum at low temperature and low pressure or even under normal temperature and normal pressure, so as to achieve the effect of regulating the electronic structure of the metal platinum surface. ;
本发明磷活化铂基催化剂的制备方法简单，成本低廉，催化活性高。The preparation method of the phosphorus-activated platinum-based catalyst of the invention is simple, the cost is low, and the catalytic activity is high.
图1是实施例1制备得到的磷活化铂基催化剂的TEM图；Fig. 1 is the TEM image of the phosphorus-activated platinum-based catalyst prepared in Example 1;
图2是实施例1制备得到的铂基催化剂与磷活化铂基催化剂的XPS对比图；Fig. 2 is the XPS comparison diagram of the platinum-based catalyst prepared in Example 1 and the phosphorus-activated platinum-based catalyst;
图3是实施例1制备得到的铂基催化剂与磷活化铂基催化剂电催化氧还原性能对比图。FIG. 3 is a comparison diagram of electrocatalytic oxygen reduction performance of the platinum-based catalyst prepared in Example 1 and the phosphorus-activated platinum-based catalyst.
为了更好地理解本发明的内容，下面结合具体实施方法对本发明内容作进一步说明，但本发明的保护内容不局限以下实施例。实施例中所用的原料如无特殊说明，均可从常规商业途径得到。实施例中提及的四氯铂酸钾溶液指四氯铂酸钾水溶液。In order to better understand the content of the present invention, the content of the present invention will be further described below in conjunction with specific implementation methods, but the protection content of the present invention is not limited to the following examples. The raw materials used in the examples can be obtained from conventional commercial channels unless otherwise specified. The potassium tetrachloroplatinate solution mentioned in the examples refers to an aqueous potassium tetrachloroplatinate solution.
实施例1Example 1
1)铂基催化剂的合成：在50mg炭黑中加入5mL无水乙醇、12.5mL去离子水、50mg十二烷基苯磺酸钠与0.4mL 0.1mol/L四氯铂酸钾溶液并在常温下搅拌均匀，得到基底混合液；随后将0.01g硼氢化钠快速加入到上述基底混合液中。将上述混合溶液置于常温中搅拌0.5小时。搅拌结束后，分离出反应体系中的固体并使用无水乙醇洗涤多次，然后烘干，即在炭黑表面制得铂纳米粒子层，得到铂/炭黑复合催化剂；1) Synthesis of platinum-based catalyst: 5mL of absolute ethanol, 12.5mL of deionized water, 50mg of sodium dodecylbenzenesulfonate and 0.4mL of 0.1mol/L potassium tetrachloroplatinate solution were added to 50mg of carbon black. The mixture was stirred evenly at the bottom to obtain a base mixed solution; then 0.01 g of sodium borohydride was quickly added to the above base mixed solution. The above mixed solution was stirred at room temperature for 0.5 hour. After the stirring, the solid in the reaction system is separated and washed with absolute ethanol for several times, and then dried, that is, a platinum nanoparticle layer is prepared on the surface of the carbon black to obtain a platinum/carbon black composite catalyst;
2)磷活化铂基催化剂的合成：将1)中制备得到的铂/碳黑复合催化剂分散在乙醇中得到铂浓度为0.5mg/mL的铂/碳黑复合催化剂乙醇溶液。将黑磷纳米片分散在乙醇溶液中得到黑磷纳米片的浓度为0.1mg/mL的黑磷纳米片乙醇溶液。取1mL铂/碳黑复合催化剂乙醇溶液加入到0.3mL黑磷纳米片乙醇溶液中，70℃回流3h，回流结束，体系自然冷却降至室温后，分离出反应体系中的固体并使用无水乙醇洗涤多次，得到磷活化铂基催化剂，然后分散在无水乙醇中备用。2) Synthesis of phosphorus-activated platinum-based catalyst: The platinum/carbon black composite catalyst prepared in 1) was dispersed in ethanol to obtain a platinum/carbon black composite catalyst ethanol solution with a platinum concentration of 0.5 mg/mL. Disperse the black phosphorus nanosheets in an ethanol solution to obtain a black phosphorus nanosheet ethanol solution with a concentration of 0.1 mg/mL of the black phosphorus nanosheets. Add 1 mL of platinum/carbon black composite catalyst ethanol solution to 0.3 mL of black phosphorus nanosheet ethanol solution, reflux at 70 °C for 3 h, the reflux is over, after the system is naturally cooled to room temperature, the solid in the reaction system is separated and anhydrous ethanol is used. After washing for several times, a phosphorus-activated platinum-based catalyst is obtained, which is then dispersed in anhydrous ethanol for use.
以透射电镜对制备得到的磷活化铂基催化剂的结构进行表征，结果如图1所示。从图1可以看出，磷活化铂基颗粒均匀分布于炭黑表面。The structure of the prepared phosphorus-activated platinum-based catalyst was characterized by transmission electron microscopy, and the results are shown in Figure 1. It can be seen from Figure 1 that the phosphorus-activated platinum-based particles are uniformly distributed on the carbon black surface.
以X射线光电子能谱仪对制备得到的铂基催化剂、磷活化铂基催化剂进行表征，结果如图2所示，通过与未经磷化的铂基催化剂进行比较，发现经过磷化后的铂基催化剂其X射线光电子能谱(XPS)在72.8°出现新的Pt 4f锋，同样说明了铂磷键的形成。The prepared platinum-based catalyst and phosphorus-activated platinum-based catalyst were characterized by X-ray photoelectron spectrometer. The results are shown in Figure 2. By comparing with the platinum-based catalyst without phosphating, it was found that the platinum-based catalyst after phosphating The X-ray photoelectron spectroscopy (XPS) of the base catalyst shows a new Pt 4f front at 72.8°, which also indicates the formation of platinum-phosphorus bonds.
磷活化铂基催化剂的电化学氧还原性能测试：电化学测量是在30℃下使用三电极***，并将转盘电极(RDE，0.196cm
2)连接到电化学工作站。对电极和参比电极分别使用Pt箔和Ag/AgCl电极。在超声处理下，将催化剂(铂基催化剂或磷活化铂基催化剂)分散在水、异丙醇和5％Nafion的混合物(水、异丙醇、5％Nafion的体积比为4:1:0.02)中1小时，制得溶液中铂元素浓度为0.16mg mL
-1的均质油墨。然后滴加12.5μL均质油墨并旋转干燥到预清洁的玻璃碳RDE上。在电化学测量之前，在氮气饱和的HClO
4(0.1M)中以500mV s
-1的速率进行CV20个循环扫描。之后，在10mV s
-1的扫描速率和1600rpm的旋转速度下，在氧气饱和的HClO
4(0.1M)中测量了催化剂的ORR极化曲线。铂基催化剂与磷活化铂基催化剂电催化氧还原性能的测试结果如图3所示，通过与铂基催化剂电化学氧还原同等条件下性能的比较，经过简单的磷化后我们发现所形成的磷活化后催化剂的催化活性明显超越未经磷活化铂基催化剂。
Electrochemical oxygen reduction performance testing of phosphorus-activated platinum-based catalysts: Electrochemical measurements were performed at 30°C using a three-electrode system with a rotating disk electrode (RDE, 0.196 cm 2 ) connected to an electrochemical workstation. Pt foil and Ag/AgCl electrodes were used for the counter and reference electrodes, respectively. Under sonication, the catalyst (platinum-based catalyst or phosphorus-activated platinum-based catalyst) was dispersed in a mixture of water, isopropanol and 5% Nafion (volume ratio of water, isopropanol, 5% Nafion was 4:1:0.02) For 1 hour, a homogeneous ink with a platinum element concentration of 0.16 mg mL -1 in the solution was prepared. 12.5 μL of the homogeneous ink was then added dropwise and spin-dried onto the pre-cleaned glassy carbon RDE. Before electrochemical measurements, CV20 cycle scans were performed at a rate of 500 mV s −1 in nitrogen-saturated HClO 4 (0.1 M). Afterwards, the ORR polarization curves of the catalysts were measured in oxygen-saturated HClO 4 (0.1 M) at a scan rate of 10 mV s −1 and a rotation speed of 1600 rpm. The test results of the electrocatalytic oxygen reduction performance of platinum-based catalysts and phosphorus-activated platinum-based catalysts are shown in Figure 3. By comparing the performance of platinum-based catalysts under the same conditions for electrochemical oxygen reduction, we found that after simple phosphating, the resulting The catalytic activity of the catalysts activated by phosphorus is significantly higher than that of the platinum-based catalysts without phosphorus activation.
实施例2Example 2
1)铂基催化剂的合成：在50mg炭黑中加入5mL无水乙醇、12.5mL去离子水、50mg十二烷基苯磺酸钠与1mL 0.1mol/L四氯铂酸钾溶液并在常温下搅拌均匀，得到基底混合液；随后将0.01g硼氢化钠快速加入到上述基底混合液中。将上述混合溶液置于常温中搅拌0.5小时。搅拌结束后，分离出反应体系中的固体并使用无水乙醇洗涤多次，然后烘干，即在炭黑表面制得铂纳米粒子层，得到铂/炭黑复合催化剂；1) Synthesis of platinum-based catalyst: 5mL of absolute ethanol, 12.5mL of deionized water, 50mg of sodium dodecylbenzenesulfonate and 1mL of 0.1mol/L potassium tetrachloroplatinate solution were added to 50mg of carbon black, and the solution was heated at room temperature. Stir well to obtain a base mixed solution; then 0.01 g of sodium borohydride is quickly added to the above base mixed solution. The above mixed solution was stirred at room temperature for 0.5 hour. After the stirring, the solid in the reaction system is separated and washed with absolute ethanol for several times, and then dried, that is, a platinum nanoparticle layer is prepared on the surface of the carbon black to obtain a platinum/carbon black composite catalyst;
2)磷活化铂基催化剂的合成：将1)中制备得到的铂/碳黑复合催化剂分散在乙醇中得到铂浓度为0.5mg/mL的铂/碳黑复合催化剂乙醇溶液。将黑磷纳米片分散在乙醇溶液中得到黑磷纳米片的浓度为0.1mg/mL的黑磷纳米片乙醇溶液。取1mL铂/碳黑复合催化剂乙醇溶液加入到0.3mL黑磷纳米片乙醇溶液中，70℃回流3h，回流结束，体系自然冷却降至室温后，分离出反应体系中的固体并使用无水乙醇洗涤多次，得到磷活化铂基催化剂，然后分散在无水乙醇中备用。2) Synthesis of phosphorus-activated platinum-based catalyst: The platinum/carbon black composite catalyst prepared in 1) was dispersed in ethanol to obtain a platinum/carbon black composite catalyst ethanol solution with a platinum concentration of 0.5 mg/mL. Disperse the black phosphorus nanosheets in an ethanol solution to obtain a black phosphorus nanosheet ethanol solution with a concentration of 0.1 mg/mL of the black phosphorus nanosheets. Add 1 mL of platinum/carbon black composite catalyst ethanol solution to 0.3 mL of black phosphorus nanosheet ethanol solution, reflux at 70 °C for 3 h, the reflux is over, after the system is naturally cooled to room temperature, the solid in the reaction system is separated and anhydrous ethanol is used. After washing for several times, a phosphorus-activated platinum-based catalyst is obtained, which is then dispersed in anhydrous ethanol for use.
实施例3Example 3
1)铂基催化剂的合成：在50mg石墨片中加入10mL异丙醇、12.5mL去离子水、50mg十二烷基苯磺酸钠与0.4mL 0.1mol/L四氯铂酸钾溶液并在常温下搅拌均匀，得到基底混合液；随后将0.01g硼氢化钠快速加入到上述基底混合液中。将上述混合溶液置于常温中搅拌0.5小时。搅拌结束后，分离出反应体系中的固体并使用无水乙醇洗涤多次，然后烘干，即在石墨 片表面制得铂纳米粒子层，得到铂/石墨片复合催化剂；1) Synthesis of platinum-based catalyst: 10 mL of isopropanol, 12.5 mL of deionized water, 50 mg of sodium dodecyl benzene sulfonate and 0.4 mL of 0.1 mol/L potassium tetrachloroplatinate solution were added to 50 mg of graphite flakes. The mixture was stirred evenly at the bottom to obtain a base mixed solution; then 0.01 g of sodium borohydride was quickly added to the above base mixed solution. The above mixed solution was stirred at room temperature for 0.5 hour. After stirring, separate the solid in the reaction system and use dehydrated alcohol to wash multiple times, then oven dry, i.e. make platinum nanoparticle layer on graphite sheet surface, obtain platinum/graphite sheet composite catalyst;
2)磷活化铂基催化剂的合成：将1)中制备得到的铂/碳黑复合催化剂分散在乙醇中得到铂浓度为0.5mg/mL的铂/碳黑复合催化剂乙醇溶液。将黑磷纳米片分散在乙醇溶液中得到黑磷纳米片的浓度为0.1mg/mL的黑磷纳米片乙醇溶液。取1mL铂/碳黑复合催化剂乙醇溶液加入到0.3mL黑磷纳米片乙醇溶液中，70℃回流3h，回流结束，体系自然冷却降至室温后，分离出反应体系中的固体并使用无水乙醇洗涤多次，得到磷活化铂基催化剂，然后分散在无水乙醇中备用。2) Synthesis of phosphorus-activated platinum-based catalyst: The platinum/carbon black composite catalyst prepared in 1) was dispersed in ethanol to obtain a platinum/carbon black composite catalyst ethanol solution with a platinum concentration of 0.5 mg/mL. Disperse the black phosphorus nanosheets in an ethanol solution to obtain a black phosphorus nanosheet ethanol solution with a concentration of 0.1 mg/mL of the black phosphorus nanosheets. Add 1 mL of platinum/carbon black composite catalyst ethanol solution to 0.3 mL of black phosphorus nanosheet ethanol solution, reflux at 70 °C for 3 h, the reflux is over, after the system is naturally cooled to room temperature, the solid in the reaction system is separated and anhydrous ethanol is used. After washing for several times, a phosphorus-activated platinum-based catalyst is obtained, which is then dispersed in anhydrous ethanol for use.
实施例4Example 4
1)铂基催化剂的合成：在50mg炭黑中加入5mL无水乙醇、12.5mL去离子水、50mg十二烷基苯磺酸钠与0.4mL 0.1mol/L四氯铂酸钾溶液并在常温下搅拌均匀，得到基底混合液；随后将0.01g硼氢化钠快速加入到上述基底混合液中。将上述混合溶液置于常温中搅拌0.5小时。搅拌结束后，分离出反应体系中的固体并使用无水乙醇洗涤多次，然后烘干，即在炭黑表面制得铂纳米粒子层，得到铂/炭黑复合催化剂；1) Synthesis of platinum-based catalyst: 5mL of absolute ethanol, 12.5mL of deionized water, 50mg of sodium dodecylbenzenesulfonate and 0.4mL of 0.1mol/L potassium tetrachloroplatinate solution were added to 50mg of carbon black. The mixture was stirred evenly at the bottom to obtain a base mixed solution; then 0.01 g of sodium borohydride was quickly added to the above base mixed solution. The above mixed solution was stirred at room temperature for 0.5 hour. After the stirring, the solid in the reaction system is separated and washed with absolute ethanol for several times, and then dried, that is, a platinum nanoparticle layer is prepared on the surface of the carbon black to obtain a platinum/carbon black composite catalyst;
2)磷活化铂基催化剂的合成：将1)中制备得到的铂/碳黑复合催化剂分散在乙醇中得到铂浓度为0.5mg/mL的铂/碳黑复合催化剂乙醇溶液。将红磷分散在乙醇溶液中得到红磷的浓度为0.2mg/mL的红磷乙醇溶液。取1mL铂/碳黑复合催化剂乙醇溶液加入到0.3mL红磷乙醇溶液中，150℃回流6h，回流结束，体系自然冷却降至室温后，分离出反应体系中的固体并使用无水乙醇洗涤多次，得到磷活化铂基催化剂，然后分散在无水乙醇中备用。2) Synthesis of phosphorus-activated platinum-based catalyst: The platinum/carbon black composite catalyst prepared in 1) was dispersed in ethanol to obtain a platinum/carbon black composite catalyst ethanol solution with a platinum concentration of 0.5 mg/mL. Disperse the red phosphorus in the ethanol solution to obtain a red phosphorus ethanol solution with a red phosphorus concentration of 0.2 mg/mL. Add 1 mL of platinum/carbon black composite catalyst ethanol solution to 0.3 mL of red phosphorus ethanol solution, reflux at 150 °C for 6 h, the reflux is over, after the system is naturally cooled to room temperature, the solid in the reaction system is separated and washed with anhydrous ethanol. secondly, a phosphorus-activated platinum-based catalyst is obtained, which is then dispersed in anhydrous ethanol for use.
实施例5Example 5
1)铂基催化剂的合成：在50mg炭黑中加入5mL无水乙醇、12.5mL去离子水、50mg十二烷基苯磺酸钠与0.4mL 0.1mol/L四氯铂酸钾溶液并在常温下搅拌均匀，得到基底混合液；随后将0.01g硼氢化钠快速加入到上述基底混合液中。将上述混合溶液置于常温中搅拌0.5小时。搅拌结束后，分离出反应体系中的固体并使用无水乙醇洗涤多次，然后烘干，即在炭黑表面制得铂纳米粒子层，得到铂/炭黑复合催化剂；1) Synthesis of platinum-based catalyst: 5mL of absolute ethanol, 12.5mL of deionized water, 50mg of sodium dodecylbenzenesulfonate and 0.4mL of 0.1mol/L potassium tetrachloroplatinate solution were added to 50mg of carbon black. The mixture was stirred evenly at the bottom to obtain a base mixed solution; then 0.01 g of sodium borohydride was quickly added to the above base mixed solution. The above mixed solution was stirred at room temperature for 0.5 hour. After the stirring, the solid in the reaction system is separated and washed with absolute ethanol for several times, and then dried, that is, a platinum nanoparticle layer is prepared on the surface of the carbon black to obtain a platinum/carbon black composite catalyst;
2)磷活化铂基催化剂的合成：将1)中制备得到的铂/碳黑复合催化剂分散在乙醇中得到铂浓度为0.5mg/mL的铂/碳黑复合催化剂乙醇溶液。将橙磷分散在乙醇溶液中得到橙磷的浓度为0.05mg/mL的橙磷乙醇溶液。取1mL铂/碳黑复合催化剂乙醇溶液加入到0.3mL橙磷乙醇溶液中，180℃回流6h，回流结束，体系自然冷却降至室温后，分离出反应体系中的固体 并使用无水乙醇洗涤多次，得到磷活化铂基催化剂，然后分散在无水乙醇中备用。2) Synthesis of phosphorus-activated platinum-based catalyst: The platinum/carbon black composite catalyst prepared in 1) was dispersed in ethanol to obtain a platinum/carbon black composite catalyst ethanol solution with a platinum concentration of 0.5 mg/mL. The orange phosphorus was dispersed in the ethanol solution to obtain an orange phosphorus ethanol solution with an orange phosphorus concentration of 0.05 mg/mL. Add 1 mL of platinum/carbon black composite catalyst ethanol solution to 0.3 mL of orange phosphorus ethanol solution, reflux at 180 °C for 6 h, the reflux is over, after the system is naturally cooled to room temperature, the solid in the reaction system is separated and washed with anhydrous ethanol. secondly, a phosphorus-activated platinum-based catalyst is obtained, which is then dispersed in anhydrous ethanol for use.
以上所述仅为本发明的具体实施方式，不是全部的实施方式，本领域普通技术人员通过阅读本发明说明书而对本发明技术方案采取的任何等效的变换，均为本发明的权利要求所涵盖。The above descriptions are only specific embodiments of the present invention, not all of the embodiments. Any equivalent transformations to the technical solutions of the present invention that are taken by those of ordinary skill in the art by reading the description of the present invention are covered by the claims of the present invention. .
Claims (10)
- 一种磷活化铂基催化剂的制备方法，其特征在于，包括以下步骤：A kind of preparation method of phosphorus-activated platinum-based catalyst, is characterized in that, comprises the following steps:1)铂基催化剂的合成：在碳载体中加入第一溶剂、去离子水、表面活性剂和铂盐溶液，并在常温下搅拌均匀得到基底混合液；随后将还原剂快速加入到所述基底混合液中，并在常温下搅拌0.5-24h(不包含24h)，搅拌结束后得到的固体产物为所述铂基催化剂；1) Synthesis of platinum-based catalyst: add the first solvent, deionized water, surfactant and platinum salt solution to the carbon support, and stir evenly at room temperature to obtain a base mixed solution; then quickly add a reducing agent to the base In the mixed solution, and stirred at normal temperature for 0.5-24h (excluding 24h), the solid product obtained after stirring is the platinum-based catalyst;2)铂基催化剂的磷化：在第二溶剂中加入1)中制备得到的铂基催化剂和磷源，然后在气氛保护下，30-180℃下回流5-12小时，回流结束后得到的固体产物为所述磷活化铂基催化剂。2) Phosphating of platinum-based catalyst: add the platinum-based catalyst and phosphorus source prepared in 1) into the second solvent, and then reflux at 30-180 ° C for 5-12 hours under the protection of the atmosphere, and the obtained after refluxing is completed. The solid product is the phosphorus-activated platinum-based catalyst.
- 根据权利要求1所述的磷活化铂基催化剂的制备方法，其特征在于，步骤1)中所述的铂基催化剂为铂/碳载体复合催化剂，即在碳载体表面制得铂纳米粒子层；The method for preparing a phosphorus-activated platinum-based catalyst according to claim 1, wherein the platinum-based catalyst described in step 1) is a platinum/carbon carrier composite catalyst, that is, a platinum nanoparticle layer is prepared on the surface of the carbon carrier;优选地，所述铂纳米粒子的平均粒径为0.5～20nm。Preferably, the average particle size of the platinum nanoparticles is 0.5-20 nm.
- 根据权利要求1所述的磷活化铂基催化剂的制备方法，其特征在于，步骤1)中所述的碳载体包括炭黑、石墨、石墨烯、碳纤维、碳纳米管、活性炭、碳分子筛中的至少一种；The preparation method of phosphorus-activated platinum-based catalyst according to claim 1, wherein the carbon carrier described in step 1) comprises carbon black, graphite, graphene, carbon fiber, carbon nanotube, activated carbon, and carbon molecular sieve. at least one;优选地，步骤1)中所述的第一溶剂包括醇类溶剂、醚类溶剂、醇醚类溶剂、酮类溶剂、酯类溶剂、酰胺类溶剂中的至少一种；Preferably, the first solvent described in step 1) includes at least one of alcohol-based solvents, ether-based solvents, alcohol-ether-based solvents, ketone-based solvents, ester-based solvents, and amide-based solvents;优选地，步骤1)中所述的还原剂包括碱金属氢化物、碱金属硼氢化物、醛溶液中的至少一种。Preferably, the reducing agent in step 1) includes at least one of alkali metal hydride, alkali metal borohydride, and aldehyde solution.
- 根据权利要求1所述的磷活化铂基催化剂的制备方法，其特征在于，步骤1)中所述的表面活性剂包括非离子表面活性剂、阴离子表面活性剂、阳离子表面活性剂中的至少一种；The method for preparing a phosphorus-activated platinum-based catalyst according to claim 1, wherein the surfactant described in step 1) comprises at least one of a nonionic surfactant, an anionic surfactant, and a cationic surfactant kind;优选地，所述非离子表面活性剂包括聚乙烯吡咯烷酮、聚氧乙烯-聚氧丙烯-聚氧乙烯三嵌段共聚物中的至少一种；Preferably, the nonionic surfactant comprises at least one of polyvinylpyrrolidone, polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer;优选地，所述阴离子表面活性剂包括十二烷基苯磺酸钠；Preferably, the anionic surfactant comprises sodium dodecylbenzenesulfonate;优选地，所述阳离子表面活性剂包括十六烷基三甲基溴化铵。Preferably, the cationic surfactant comprises cetyltrimethylammonium bromide.
- 根据权利要求1所述的磷活化铂基催化剂的制备方法，其特征在于，步骤1)中所述铂盐溶液的浓度为0.08～0.12mol/L；The method for preparing a phosphorus-activated platinum-based catalyst according to claim 1, wherein the concentration of the platinum salt solution in step 1) is 0.08-0.12 mol/L;优选地，所述铂盐包括氯铂酸钾、四氨合硝酸铂、氯亚铂酸钠、二亚硝基二氨铂、四氨合氯化铂、四氯化铂、氯亚铂酸钾、乙酰丙酮铂、六氯代铂酸钠、二氯化铂、四硝基铂酸钾中的至少一种。Preferably, the platinum salt includes potassium chloroplatinate, tetraammine platinum nitrate, sodium chloroplatinite, dinitrosodiammine platinum, tetraammine platinum chloride, platinum tetrachloride, potassium chloroplatinite , at least one of platinum acetylacetonate, sodium hexachloroplatinate, platinum dichloride and potassium tetranitroplatinate.
- 根据权利要求1所述的磷活化铂基催化剂的制备方法，其特征在于，步骤1)中所述碳载体、第一溶剂、去离子水、表面活性剂、铂盐、还原剂的质量比为1：(1～500)：(1～500)：(0.05～10)：(0.05～10)：(0.001～10)。The method for preparing a phosphorus-activated platinum-based catalyst according to claim 1, wherein the mass ratio of the carbon carrier, the first solvent, deionized water, surfactant, platinum salt, and reducing agent in step 1) is: 1: (1 to 500): (1 to 500): (0.05 to 10): (0.05 to 10): (0.001 to 10).
- 根据权利要求1所述的磷活化铂基催化剂的制备方法，其特征在于，步骤2)中所述的磷源包括黑磷、红磷、橙磷、紫磷、白磷、三辛基膦、氧化磷中的至少一种；The method for preparing a phosphorus-activated platinum-based catalyst according to claim 1, wherein the phosphorus source in step 2) comprises black phosphorus, red phosphorus, orange phosphorus, purple phosphorus, white phosphorus, trioctylphosphine, oxidized at least one of phosphorus;优选地，步骤2)中所述的气氛为空气、氮气、氩气、氢气中的至少一种；Preferably, the atmosphere described in step 2) is at least one of air, nitrogen, argon, and hydrogen;优选地，步骤2)中所述的第二溶剂包括水、醇类溶剂、醚类溶剂、醇醚类溶剂、酮类溶剂、酯类溶剂、酰胺类溶剂中的至少一种。Preferably, the second solvent in step 2) includes at least one of water, alcohol-based solvent, ether-based solvent, alcohol-ether-based solvent, ketone-based solvent, ester-based solvent, and amide-based solvent.
- 根据权利要求1所述的磷活化铂基催化剂的制备方法，其特征在于，所述铂基催化剂、磷源、第二溶剂的质量比为1：(0.001～10)：(1～100)。The method for preparing a phosphorus-activated platinum-based catalyst according to claim 1, wherein the mass ratio of the platinum-based catalyst, the phosphorus source, and the second solvent is 1:(0.001-10):(1-100).
- 一种磷活化铂基催化剂，其特征在于，由权利要求1-8任一项所述的制备方法制备得到。A phosphorus-activated platinum-based catalyst is characterized in that, it is prepared by the preparation method described in any one of claims 1-8.
- 权利要求9所述的磷活化铂基催化剂在电催化氧还原中的应用。Application of the phosphorus-activated platinum-based catalyst of claim 9 in electrocatalytic oxygen reduction.
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