CN116099566A - Preparation method of platinum doped modified cobalt-based catalyst - Google Patents
Preparation method of platinum doped modified cobalt-based catalyst Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 150000001868 cobalt Chemical class 0.000 title claims abstract description 67
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 42
- 239000003054 catalyst Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 47
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000758 substrate Substances 0.000 claims abstract description 31
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229960003638 dopamine Drugs 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 19
- 238000000137 annealing Methods 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 229910052786 argon Inorganic materials 0.000 claims abstract description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004202 carbamide Substances 0.000 claims abstract description 10
- -1 platinum ions Chemical class 0.000 claims abstract description 9
- 239000002344 surface layer Substances 0.000 claims abstract description 8
- 238000002791 soaking Methods 0.000 claims abstract description 6
- 229910001429 cobalt ion Inorganic materials 0.000 claims abstract description 4
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- 239000008367 deionised water Substances 0.000 claims description 35
- 229910021641 deionized water Inorganic materials 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 33
- 238000001035 drying Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 15
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 14
- 239000007853 buffer solution Substances 0.000 claims description 11
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- 229920001690 polydopamine Polymers 0.000 claims description 3
- 238000000224 chemical solution deposition Methods 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims 2
- 238000011068 loading method Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 31
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 7
- 239000010410 layer Substances 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 238000005342 ion exchange Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 62
- 229910052799 carbon Inorganic materials 0.000 description 60
- 239000003792 electrolyte Substances 0.000 description 37
- 239000011521 glass Substances 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 28
- 238000012360 testing method Methods 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 230000007935 neutral effect Effects 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 238000001816 cooling Methods 0.000 description 13
- 239000011259 mixed solution Substances 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000003153 chemical reaction reagent Substances 0.000 description 12
- 238000004140 cleaning Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 11
- 229920006395 saturated elastomer Polymers 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 230000010287 polarization Effects 0.000 description 7
- 238000011144 upstream manufacturing Methods 0.000 description 7
- 230000002378 acidificating effect Effects 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 238000003892 spreading Methods 0.000 description 5
- 230000007480 spreading Effects 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000010411 electrocatalyst Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229940111688 monobasic potassium phosphate Drugs 0.000 description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 description 2
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000840 electrochemical analysis 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
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UONOSZUBLNXHGW-UHFFFAOYSA-L mercury(2+);sulfite Chemical compound [Hg+2].[O-]S([O-])=O UONOSZUBLNXHGW-UHFFFAOYSA-L 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
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- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- 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
- B01J27/24—Nitrogen compounds
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
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Abstract
The invention provides a preparation method of a platinum doped modified cobalt-based catalyst. Firstly, cobalt chloride hexahydrate and urea are used as raw materials, and a layer of basic cobalt salt is grown in situ on a substrate material through a hydrothermal reaction; then coating a layer of dopamine high polymer on the surface of the basic cobalt salt to prevent the dopamine high polymer from falling off; then soaking the mixture in a chloroplatinic acid solution to promote ion exchange between platinum ions and cobalt ions, so as to obtain a platinum doped basic cobalt salt precursor with a dopamine polymer coated on the surface layer; and finally annealing the material in dicyandiamide atmosphere under the protection of argon to finally obtain the platinum doped modified cobalt-based catalytic material.
Description
Technical Field
The invention relates to preparation of high-catalytic-performance electrocatalyst, which is applied to the field of green energy storage and conversion devices represented by fuel cells, water electrolysis devices and rechargeable metal-based batteries.
Background
Continuous consumption of fossil fuels such as petroleum, coal, etc. has prompted the development of high-efficiency energy storage and conversion technologies. Rechargeable metal-air batteries, water electrolysis devices and fuel cells are receiving attention for their inherent environmental friendliness, high energy density and safety of energy conversion. Hydrogen Evolution Reaction (HER), oxygen Evolution Reaction (OER) are two important reactions of electrolyzed water; oxygen Reduction Reactions (ORR) and Oxygen Evolution Reactions (OER) are considered to be two key processes of rechargeable metal-air batteries. These electrochemical reactions are slow in kinetics and generally require the overcoming of large overpotentials, and efforts have been made to search for electrocatalysts with high catalytic activity in order to accelerate the reaction process. At present, the widely used catalyst is mainly a noble metal-based catalyst, but the noble metal-based catalyst has scarce reserves and high cost, and is not suitable for large-scale popularization and application. The development of non-noble metal-based catalysts to reduce or replace the use of noble metal-based catalysts is an effective approach to solving the current problems.
In recent years, transition metal-nitrogen-carbon (TM-N-C) materials have been widely reported in OER and ORR, which are considered as the most promising cathode materials for rechargeable metal-air batteries. In general, the ORR electrocatalytic activity of transition metals in alkaline medium is in turn Fe > Co > Ni, while the OER electrocatalytic activity thereof is in turn Ni > Co > Fe. Clearly, the Co-N-C material is a very promising bifunctional catalyst, which also benefits from its modest free energy of adsorption-dissolution for ORR and OER intermediates. And the electronic structure of the metal cobalt (Co) is closest to that of noble metal platinum (Pt), so that the catalyst is an ideal platinum-based catalyst substitute. However, the catalytic performance of the Co-N-C catalytic material is still inferior to that of a platinum-based catalyst, if a small amount of Pt can be doped into the Co-N-C catalytic material, whether the catalyst has catalytic performance superior or not inferior to that of the platinum-based catalytic material can be ensured, and the cost of the catalyst can be effectively controlled due to the small doping amount of Pt. The method has great research significance and practical value in promoting the large-scale commercial application of the electrocatalytic material.
While carbon nanotubes (NCNTs), which are nitrogen-doped carbon (NC) base materials supporting transition metals, have large specific surface area, high conductivity, porosity, corrosion resistance, and characteristics of easy chemical modification by introducing metal sites, are considered to be ideal carriers for imparting high activity and durability to electrocatalysts. If Co@NCNTs are used as a base material and a small amount of noble metal Pt is doped to obtain the platinum doped cobalt-based catalytic material, the cobalt-based catalytic material has high catalytic potential.
Disclosure of Invention
In view of this, the present invention provides a method for obtaining a platinum doped modified cobalt-based catalyst by one-step annealing, the preparation of which comprises the following steps:
the preparation method of the platinum doped modified cobalt-based catalyst comprises the following steps:
s1, dipping a basic cobalt salt substrate material coated with a dopamine high polymer in a chloroplatinic acid solution to obtain a substrate material growing with a platinum doped basic cobalt salt precursor coated with a polydopamine high polymer on the surface layer;
s2, placing the substrate material obtained in the step S1 in a tube furnace, adding dicyandiamide, and annealing under the protection of argon to obtain the platinum doped modified cobalt-based catalyst.
The preparation method of the basic cobalt salt base material coated with the dopamine high polymer comprises the following steps: dissolving cobalt chloride and urea in deionized water, and growing a needle-shaped basic cobalt salt array on a conductive substrate by using a chemical bath deposition method to obtain a substrate material growing with basic cobalt salt;
and (3) soaking the substrate material growing with the basic cobalt salt in the dopamine solution for a certain time, taking out, washing the surface of the substrate material with deionized water, and drying to obtain the uniform dopamine high polymer coated on the surface layer of the basic cobalt salt.
The load of the basic cobalt salt on the substrate material is 0.5-2 mg/cm 2 。
The concentration of the dopamine hydrochloride is 0.1-0.4 mg/L, and the soaking time of the substrate material in the dopamine hydrochloride buffer solution is 12-24 h.
Basic cobalt salt (Co (OH)) supported by platinum ions and a base material in the chloroplatinic acid solution 2 ) The molar ratio of cobalt ions is 3:100-10:100.
The cobalt-platinum ion replacement temperature is 30-80 ℃ and the replacement time is 12-24 h.
The annealing temperature is 700-900 ℃ and the annealing time is 2-3 h.
First, growing basic cobalt salt on a substrate material: firstly, dissolving cobalt chloride hexahydrate and urea with certain mass in deionized water, and magnetically stirring to obtain a uniform solution; pouring the solution into a glass test tube and placing the substrate material into the solution so that the solution submerges the substrate material; this is to allow the substrate material to be in sufficient contact with the solution, and the basic cobalt salt can be grown uniformly on the substrate material. And then putting the test tube into a constant temperature oven for hydrothermal reaction for a certain time, cooling, taking out, flushing the substrate material with water, and drying to obtain the basic cobalt salt growing on the substrate material in situ. This step serves to allow uniform growth of the basic cobalt salt on the substrate.
Second, coating of dopamine high polymer: dissolving dopamine hydrochloride in weak alkaline buffer solution with pH value of 7.5-8.5 to prepare dopamine hydrochloride buffer solution with certain concentration, soaking the substrate material growing with basic cobalt salt in the dopamine solution for a certain time, taking out, washing the surface with deionized water and drying to obtain the uniform dopamine polymer coated on the surface layer of the basic cobalt salt. In this process, the pH of the buffer solution for dissolving dopamine hydrochloride is about 7.5-8.5, because dissolution of dopamine hydrochloride in pure water makes the solution acidic, and the acidic solution dissolves basic cobalt salts. Therefore, a weakly basic buffer must be used to solubilize and neutralize dopamine hydrochloride, and only in a neutral or weakly basic environment, the basic cobalt salt is stable. The effect of wrapping a layer of dopamine high polymer is equivalent to wrapping a layer of membrane on the outer layer of basic cobalt salt, so that the basic cobalt salt can stably grow on the base fiber without falling off. And, the high polymer may provide a nitrogen source in a subsequent annealing step to form a nitrogen-doped carbon structure.
Third step, doping of platinum ions: and immersing the substrate material obtained by the steps in a chloroplatinic acid solution, and reacting for a certain time at a certain temperature to fully replace platinum ions and cobalt ions, thereby finally obtaining the substrate material growing the platinum doped basic cobalt salt precursor with the surface layer coated with the polydopamine high polymer. Most of the platinum doped catalytic materials are doped with platinum after annealing, but the platinum is doped before annealing, and the catalytic material is obtained by one-step annealing. The preparation process of the invention is simpler and more convenient, and the platinum atoms can be distributed more uniformly in the Co/Pt Co-annealing process, so that more monoatomic platinum catalytic active sites can be formed, which is very beneficial to the catalytic performance of the catalyst.
Fourth, precursor annealing: and (3) placing the Pt doped basic cobalt salt precursor, the surface layer of which is coated with the dopamine high polymer, growing on the substrate material in the center of a tube furnace, taking a certain amount of dicyandiamide, placing the dicyandiamide in the upstream of the tube furnace, annealing for a certain time at a certain temperature under the protection of argon, and cooling and taking out the dicyandiamide to obtain the platinum doped modified cobalt-based catalytic material. In this process, the whole annealing process must be performed under the protection of argon. The high annealing temperature causes that the entering of a trace amount of air can influence the normal progress of the reaction. The annealing temperature and the annealing time are the key points of the catalyst to obtain high catalytic performance, and a large number of experiments to obtain an optimal scheme are also one of the key points of the invention.
Drawings
FIG. 1 shows ORR polarization curves of samples prepared in examples 1, 2, 3 and 4, as measured in oxygen saturated (a) alkaline, (b) neutral, (c) acid electrolyte.
Fig. 2 shows HER polarization curves measured in nitrogen saturated (a) alkaline, (b) neutral, (c) acidic electrolyte for the samples prepared in example 1, example 2, example 3 and example 4.
Fig. 3 is a graph showing the HOR polarization curves of the samples prepared in example 1, example 2, example 3 and example 4 in a hydrogen saturated alkaline electrolyte.
Fig. 4 is a HER polarization curve measured in a nitrogen saturated alkaline electrolyte for the sample prepared in example 5.
Fig. 5 is a HER polarization curve measured in a nitrogen saturated alkaline electrolyte for the sample prepared in example 6.
Fig. 6 is an XRD pattern of the samples prepared in example 1, example 3 and example 4.
Fig. 7 is an SEM image of the sample prepared in example 1.
Fig. 8 is an SEM image of the sample prepared in example 3.
Fig. 9 is an SEM image of the sample prepared in example 4.
Detailed Description
Characterization conditions:
all electrochemical tests are carried out by matching CHI760E electrochemical workstation of Shanghai Chen Hua instrument Limited company with CHI760E software. And the standard three-electrode device is assembled by taking a graphite electrode as an auxiliary electrode, a replaceable platinum electrode clamp and a test sample as working electrodes, and a mercury/mercury oxide electrode (alkaline environment), a silver/silver chloride electrode (neutral environment) or a mercury/mercury sulfite electrode (acid environment) as reference electrodes for testing.
ORR performance test: the alkaline ORR tests of the examples of the invention were all performed in an oxygen saturated 0.1M potassium hydroxide solution; neutral ORR tests were all performed in an oxygen saturated dibasic potassium phosphate and monobasic potassium phosphate mixed solution (ph=7); the acidic ORR tests were all performed in an oxygen saturated 0.05M sulfuric acid solution.
HER performance test: the alkaline HER tests of the examples of the invention were all performed in a nitrogen saturated 1M potassium hydroxide solution; neutral HER tests were all performed in a nitrogen saturated dibasic potassium phosphate and monobasic potassium phosphate mixed solution (ph=7); the acidic HER tests were all performed in a nitrogen saturated 0.05M sulfuric acid solution.
HOR performance test: the alkaline HOR tests of the examples of the present invention were all performed in a hydrogen saturated 0.1M potassium hydroxide solution.
Produced by Rigaku corporation of Japan
Radiation Ultima IV type X-ray diffractometer pairXRD test of the inventive examples TEM test was performed on the inventive examples using a FEI Quanta 250 scanning electron microscope manufactured by Rigaku corporation of Japan.
Example 1
1.428g of cobalt chloride hexahydrate and 2.667g of urea were dissolved in 40mL of deionized water to obtain a hydrothermal reagent having a metal ion concentration of 0.15 mol/L. Taking an area of 10cm 2 (2.5×5cm 2 ) Washing Dongli carbon paper with absolute ethanol, placing in a mixture of water and alcohol, taking out after ultrasonic treatment for 15min, and cleaning with deionized water. The hydrothermal reagent and Dongli carbon paper (2.5X15 cm) 2 ) Transferred to glass test tubes and transferred to a hydrothermal tank, respectively, and heat treated at 90 ℃ for 2h. Cooling to room temperature, taking out, washing the surface of the carbon paper with deionized water, and drying to obtain a light pink basic cobalt salt precursor sample (the load of basic cobalt salt on the carbon paper is 1 mg/cm) 2 ). 20mg of dopamine hydrochloride was taken and dissolved in 100mL of buffer solution with ph=8.5. And hanging the prepared carbon paper with the basic cobalt salt in a dopamine solution to enable the carbon paper to be completely immersed in the solution. Setting the rotating speed to be 100r/min, reacting for 24 hours at normal temperature, and cleaning the carbon paper by using deionized water and drying after the reaction is finished. And (3) placing the carbon paper subjected to the treatment in the center of a tube furnace, placing 1g of dicyandiamide on the upstream of the tube furnace, heating to 350 ℃ from room temperature under the protection of argon at 10 ℃/min, performing constant-temperature reaction for 1h, heating to 900 ℃ at 3 ℃/min, and performing constant-temperature reaction for 2h to obtain a final sample.
A-c in FIG. 1 and Table 1 show the ORR catalytic performance of the example 1 samples in different electrolytes, their half-wave potential in alkaline electrolyte (E 1/2 ) 0.89V, E in neutral electrolyte 1/2 =0.82, E in acid electrolyte 1/2 =0.78v. A-c in fig. 2 and table 2 show HER catalytic performance of the example 1 samples in different electrolytes, which achieved 10mA cm in alkaline electrolyte 2 The overpotential required for the current density was 167mV, 10mA cm was achieved in neutral electrolyte 2 The overpotential required for the current density is 135mV, and 10mA cm of the acid electrolyte is realized 2 The overpotential required for the current density is 14mV. The implementation is shown in FIGS. 3 a-c and Table 3Example 1 the HOR catalytic performance of the sample in alkaline electrolyte has an HOR half-wave potential of 18mV. The XRD and SEM images of the sample are shown in fig. 6 and 7.
Example 2
1.428g of cobalt chloride hexahydrate and 2.667g of urea were dissolved in 40mL of deionized water to obtain a hydrothermal reagent having a metal ion concentration of 0.15 mol/L. Taking an area of 10cm 2 (2.5×5cm 2 ) Washing Dongli carbon paper with absolute ethanol, placing in a mixture of water and alcohol, taking out after ultrasonic treatment for 15min, and cleaning with deionized water. The hydrothermal reagent and Dongli carbon paper (2.5X15 cm) 2 ) Transferred to glass test tubes and transferred to a hydrothermal tank, respectively, and heat treated at 90 ℃ for 2h. Cooling to room temperature, taking out, washing the surface of the carbon paper with deionized water, and drying to obtain a light pink basic cobalt salt precursor sample (the load of basic cobalt salt on the carbon paper is 1 mg/cm) 2 ). 20mg of dopamine hydrochloride was taken and dissolved in 100mL of buffer solution with ph=8.5. And hanging the prepared carbon paper with the basic cobalt salt in a dopamine solution to enable the carbon paper to be completely immersed in the solution. Setting the rotating speed to be 100r/min, reacting for 24 hours at normal temperature, and cleaning the carbon paper by using deionized water and drying after the reaction is finished. Taking 3mL of methanol and DMF with the volume ratio of 1:1, adding 265uL of 1mol/L chloroplatinic acid isopropanol solution, and uniformly mixing (the mol ratio of cobalt to platinum is 100:3). Spreading the carbon paper in a glass culture dish, pouring the mixed solution into the glass culture dish, enabling the mixed solution to be soaked in the carbon paper, sealing the glass culture dish, placing the glass culture dish in an incubator at 60 ℃ for reaction for 24 hours, cooling, taking out the glass culture dish, washing the glass culture dish with deionized water, and drying the glass culture dish. And (3) placing the carbon paper subjected to the treatment in the center of a tube furnace, placing 1g of dicyandiamide on the upstream of the tube furnace, heating to 350 ℃ from room temperature under the protection of argon at 10 ℃/min, performing constant-temperature reaction for 1h, heating to 900 ℃ at 3 ℃/min, and performing constant-temperature reaction for 2h to obtain a final sample.
A-c in FIG. 1 and Table 1 show the ORR catalytic performance of the sample of example 2 in alkaline electrolyte with half-wave potential (E 1/2 ) 0.91V. A-c in fig. 2 and table 2 show HER catalytic performance in alkaline electrolyte of example 2 sample, achieving 10mA cm 2 The overpotential required for the current density was 167mV, 10mA was achieved in neutral electrolytecm 2 The required overpotential for the current density is 180mV. The a-c in FIG. 3 and Table 3 show the HOR catalytic performance of the example 2 sample in alkaline electrolyte with a HOR half-wave potential of 7mV.
Example 3
1.428g of cobalt chloride hexahydrate and 2.667g of urea were dissolved in 40mL of deionized water to obtain a hydrothermal reagent having a metal ion concentration of 0.15 mol/L. Taking an area of 10cm 2 (2.5×5cm 2 ) Washing Dongli carbon paper with absolute ethanol, placing in a mixture of water and alcohol, taking out after ultrasonic treatment for 15min, and cleaning with deionized water. The hydrothermal reagent and Dongli carbon paper (2.5X15 cm) 2 ) Transferred to glass test tubes and transferred to a hydrothermal tank, respectively, and heat treated at 90 ℃ for 2h. Cooling to room temperature, taking out, washing the surface of the carbon paper with deionized water, and drying to obtain a light pink basic cobalt salt precursor sample (the load of basic cobalt salt on the carbon paper is 1 mg/cm) 2 ). 20mg of dopamine hydrochloride was taken and dissolved in 100mL of buffer solution with ph=8.5. And hanging the prepared carbon paper with the basic cobalt salt in a dopamine solution to enable the carbon paper to be completely immersed in the solution. Setting the rotating speed to be 100r/min, reacting for 24 hours at normal temperature, and cleaning the carbon paper by using deionized water and drying after the reaction is finished. Taking 3mL of methanol and DMF with the volume ratio of 1:1, adding 440uL of chloroplatinic acid isopropanol solution with the volume ratio of 1mol/L, and uniformly mixing (the mol ratio of cobalt to platinum is 100:5). Spreading the carbon paper in a glass culture dish, pouring the mixed solution into the glass culture dish, enabling the mixed solution to be soaked in the carbon paper, sealing the glass culture dish, placing the glass culture dish in an incubator at 60 ℃ for reaction for 24 hours, cooling, taking out the glass culture dish, washing the glass culture dish with deionized water, and drying the glass culture dish. And (3) placing the carbon paper subjected to the treatment in the center of a tube furnace, placing 1g of dicyandiamide on the upstream of the tube furnace, heating to 350 ℃ from room temperature under the protection of argon at 10 ℃/min, performing constant-temperature reaction for 1h, heating to 900 ℃ at 3 ℃/min, and performing constant-temperature reaction for 2h to obtain a final sample.
A-c in FIG. 1 and Table 1 show the ORR catalytic performance of the example 3 samples in different electrolytes, their half-wave potential in alkaline electrolyte (E 1/2 ) 0.92V, E in neutral electrolyte 1/2 =0.89, E in acid electrolyte 1/2 =0.86V. The real results are shown in FIG. 2 a-c and Table 2Example 3 HER catalytic performance of samples in different electrolytes, which achieved 10mA cm in alkaline electrolyte 2 The overpotential required for the current density was 131mV, 10mA cm was achieved in neutral electrolyte 2 The overpotential required for the current density was 126mV, 10mA cm was achieved in the acid electrolyte 2 The overpotential required for the current density is 1mV. The a-c in FIG. 3 and Table 3 show the HOR catalytic performance of the sample of example 3 in alkaline electrolyte with a HOR half-wave potential of 6mV. The XRD and SEM images of the sample are shown in fig. 6 and 8. Table 4 shows the element content of the sample of example 3, from which the atomic ratio of platinum to cobalt is less than 5:100.
Example 4
1.428g of cobalt chloride hexahydrate and 2.667g of urea were dissolved in 40mL of deionized water to obtain a hydrothermal reagent having a metal ion concentration of 0.15 mol/L. Taking an area of 10cm 2 (2.5×5cm 2 ) Washing Dongli carbon paper with absolute ethanol, placing in a mixture of water and alcohol, taking out after ultrasonic treatment for 15min, and cleaning with deionized water. The hydrothermal reagent and Dongli carbon paper (2.5X15 cm) 2 ) Transferred to glass test tubes and transferred to a hydrothermal tank, respectively, and heat treated at 90 ℃ for 2h. Cooling to room temperature, taking out, washing the surface of the carbon paper with deionized water, and drying to obtain a light pink basic cobalt salt precursor sample (the load of basic cobalt salt on the carbon paper is 1 mg/cm) 2 ). 20mg of dopamine hydrochloride was taken and dissolved in 100mL of buffer solution with ph=8.5. And hanging the prepared carbon paper with the basic cobalt salt in a dopamine solution to enable the carbon paper to be completely immersed in the solution. Setting the rotating speed to be 100r/min, reacting for 24 hours at normal temperature, and cleaning the carbon paper by using deionized water and drying after the reaction is finished. 3mL of a 1:1 volume ratio of methanol and DMF was taken, 880uL of 1mol/L chloroplatinic acid isopropyl alcohol solution was added and mixed well (molar ratio of cobalt to platinum was 100:10). Spreading the carbon paper in a glass culture dish, pouring the mixed solution into the glass culture dish, enabling the mixed solution to be soaked in the carbon paper, sealing the glass culture dish, placing the glass culture dish in an incubator at 60 ℃ for reaction for 24 hours, cooling, taking out the glass culture dish, washing the glass culture dish with deionized water, and drying the glass culture dish. Placing the carbon paper treated by the method in the center of a tube furnace, placing 1g of dicyandiamide at the upstream of the tube furnace, heating from room temperature to 350 ℃ at 10 ℃/min under the protection of argon, and reversing at constant temperatureAfter 1h, heating to 900 ℃ at 3 ℃/min, and reacting at constant temperature for 2h to obtain the final sample.
A-c in FIG. 1 and Table 1 show the ORR catalytic performance of the example 4 samples in different electrolytes, their half-wave potential in alkaline electrolyte (E 1/2 ) 0.92V, E in neutral electrolyte 1/2 =0.89, E in acid electrolyte 1/2 =0.85V. A-c in fig. 2 and table 2 show HER catalytic performance of the example 4 samples in different electrolytes, which achieved 10mA cm in alkaline electrolyte 2 The overpotential required for the current density is 116mV, and 10mA cm of neutral electrolyte is realized 2 The overpotential required for the current density was 126mV, 10mA cm was achieved in the acid electrolyte 2 The overpotential required for the current density is 4mV. The a-c in FIG. 3 and Table 3 show the HOR catalytic performance of the sample of example 4 in alkaline electrolyte with a HOR half-wave potential of 6mV. The XRD and SEM images of the sample are shown in fig. 6 and 9.
Example 5
1.428g of cobalt chloride hexahydrate and 2.667g of urea were dissolved in 40mL of deionized water to obtain a hydrothermal reagent having a metal ion concentration of 0.15 mol/L. Taking an area of 10cm 2 (2.5×5cm 2 ) Washing Dongli carbon paper with absolute ethanol, placing in a mixture of water and alcohol, taking out after ultrasonic treatment for 15min, and cleaning with deionized water. The hydrothermal reagent and Dongli carbon paper (2.5X15 cm) 2 ) Transferred to glass test tubes and transferred to a hydrothermal tank, respectively, and heat treated at 90 ℃ for 2h. Cooling to room temperature, taking out, washing the surface of the carbon paper with deionized water, and drying to obtain a light pink basic cobalt salt precursor sample (the load of basic cobalt salt on the carbon paper is 1 mg/cm) 2 ). 20mg of dopamine hydrochloride was taken and dissolved in 100mL of buffer solution with ph=8.5. And hanging the prepared carbon paper with the basic cobalt salt in a dopamine solution to enable the carbon paper to be completely immersed in the solution. Setting the rotating speed to be 100r/min, reacting for 24 hours at normal temperature, and cleaning the carbon paper by using deionized water and drying after the reaction is finished. Taking 3mL of methanol and DMF with the volume ratio of 1:1, adding 440uL of chloroplatinic acid isopropanol solution with the volume ratio of 1mol/L, and uniformly mixing (the mol ratio of cobalt to platinum is 100:5). Spreading the carbon paper in a glass culture dish, and pouringAdding the mixed solution and enabling the mixed solution to be soaked in carbon paper, sealing, placing the mixed solution in a constant temperature box at 60 ℃ for reaction for 24 hours, cooling, taking out, washing with deionized water, and drying. And (3) placing the carbon paper subjected to the treatment in the center of a tube furnace, placing 1g of dicyandiamide on the upstream of the tube furnace, heating to 350 ℃ from room temperature under the protection of argon at 10 ℃/min, performing constant-temperature reaction for 1h, heating to 700 ℃ at 3 ℃/min, and performing constant-temperature reaction for 2h to obtain a final sample.
FIG. 4 is a plot of HER polarization measured in alkaline electrolyte for a sample of example 5, implementing 10mA cm 2 The required overpotential for the current density was 66mV.
Example 6
1.428g of cobalt chloride hexahydrate and 2.667g of urea were dissolved in 40mL of deionized water to obtain a hydrothermal reagent having a metal ion concentration of 0.15 mol/L. Taking an area of 10cm 2 (2.5×5cm 2 ) Washing Dongli carbon paper with absolute ethanol, placing in a mixture of water and alcohol, taking out after ultrasonic treatment for 15min, and cleaning with deionized water. The hydrothermal reagent and Dongli carbon paper (2.5X15 cm) 2 ) Transferred to glass test tubes and transferred to a hydrothermal tank, respectively, and heat treated at 90 ℃ for 2h. Cooling to room temperature, taking out, washing the surface of the carbon paper with deionized water, and drying to obtain a light pink basic cobalt salt precursor sample (the load of basic cobalt salt on the carbon paper is 1 mg/cm) 2 ). 20mg of dopamine hydrochloride was taken and dissolved in 100mL of buffer solution with ph=8.5. And hanging the prepared carbon paper with the basic cobalt salt in a dopamine solution to enable the carbon paper to be completely immersed in the solution. Setting the rotating speed to be 100r/min, reacting for 24 hours at normal temperature, and cleaning the carbon paper by using deionized water and drying after the reaction is finished. Taking 3mL of methanol and DMF with the volume ratio of 1:1, adding 440uL of chloroplatinic acid isopropanol solution with the volume ratio of 1mol/L, and uniformly mixing (the mol ratio of cobalt to platinum is 100:5). Spreading the carbon paper in a glass culture dish, pouring the mixed solution into the glass culture dish, enabling the mixed solution to be soaked in the carbon paper, sealing the glass culture dish, placing the glass culture dish in an incubator at 60 ℃ for reaction for 24 hours, cooling, taking out the glass culture dish, washing the glass culture dish with deionized water, and drying the glass culture dish. Placing the carbon paper treated by the method in the center of a tube furnace, placing 1g of dicyandiamide at the upstream of the tube furnace, heating from room temperature to 350 ℃ at 10 ℃/min under the protection of argon, and keeping the temperature constantAfter reacting for 1h, heating to 800 ℃ at 3 ℃/min, and reacting at constant temperature for 2h to obtain a final sample.
FIG. 5 is a plot of HER polarization measured in alkaline electrolyte for a sample of example 6, implementing 10mA cm 2 The required overpotential for the current density is 60mV.
Table 1: ORR catalytic performance data comparison of samples of different examples in alkaline, neutral and acidic systems
Table 2: comparison of HER catalytic performance data for samples of different examples in basic, neutral and acidic systems
Table 3: HOR catalytic performance data comparison of samples of different examples in alkaline systems
Table 4: example three sample element content table
Claims (7)
1. The preparation method of the platinum doped modified cobalt-based catalyst is characterized by comprising the following steps:
s1, dipping a basic cobalt salt substrate material coated with a dopamine high polymer in a chloroplatinic acid solution to obtain a substrate material growing with a platinum doped basic cobalt salt precursor coated with a polydopamine high polymer on the surface layer;
s2, placing the substrate material obtained in the step S1 in a tube furnace, adding dicyandiamide, and annealing under the protection of argon to obtain the platinum doped modified cobalt-based catalyst.
2. The method for preparing the platinum doped modified cobalt-based catalyst according to claim 1, wherein the method for preparing the basic cobalt salt base material coated with the dopamine high polymer comprises the following steps: dissolving cobalt chloride and urea in deionized water, and growing a needle-shaped basic cobalt salt array on a conductive substrate by using a chemical bath deposition method to obtain a substrate material growing with basic cobalt salt;
and (3) soaking the substrate material growing with the basic cobalt salt in the dopamine solution for a certain time, taking out, washing the surface of the substrate material with deionized water, and drying to obtain the uniform dopamine high polymer coated on the surface layer of the basic cobalt salt.
3. The method for preparing a platinum doped modified cobalt-based catalyst according to claim 2, wherein the basic cobalt salt loading amount on the substrate material is 0.5-2 mg/cm 2 。
4. The preparation method of the platinum doped modified cobalt-based catalyst according to claim 2, wherein the concentration of the dopamine hydrochloride is 0.1-0.4 mg/L, and the soaking time of the substrate material in the dopamine hydrochloride buffer solution is 12-24 h.
5. The method for preparing a platinum doped modified cobalt-based catalyst according to claim 1, wherein the basic cobalt salt (Co (OH) supported by platinum ions and a base material in the chloroplatinic acid solution 2 ) The molar ratio of cobalt ions is 3:100-10:100.
6. The method for preparing a platinum doped modified cobalt-based catalyst according to claim 1, wherein the substitution temperature of cobalt and platinum ions is 30-80 ℃ and the substitution time is 12-24 h.
7. The method for preparing a platinum doped modified cobalt-based catalyst according to claim 1, wherein the annealing temperature is 700-900 ℃ and the annealing time is 2-3 h.
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