CN112968181A - Preparation method of carbon-coated titanium dioxide nanoflower carrier and application of carbon-coated titanium dioxide nanoflower carrier to carrying platinum or platinum alloy nanocatalyst - Google Patents
Preparation method of carbon-coated titanium dioxide nanoflower carrier and application of carbon-coated titanium dioxide nanoflower carrier to carrying platinum or platinum alloy nanocatalyst Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 41
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000002057 nanoflower Substances 0.000 title claims abstract description 30
- 229910001260 Pt alloy Inorganic materials 0.000 title claims abstract description 12
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000011943 nanocatalyst Substances 0.000 title abstract description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 31
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229960003638 dopamine Drugs 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 239000000446 fuel Substances 0.000 claims abstract description 11
- 229960000583 acetic acid Drugs 0.000 claims abstract description 10
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 10
- 229920001690 polydopamine Polymers 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 238000006722 reduction reaction Methods 0.000 claims abstract description 6
- 239000000376 reactant Substances 0.000 claims abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract 3
- 239000000243 solution Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 16
- 239000002105 nanoparticle Substances 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 10
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000007983 Tris buffer Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims 2
- 239000007789 gas Substances 0.000 claims 2
- 239000007853 buffer solution Substances 0.000 claims 1
- FYFFGSSZFBZTAH-UHFFFAOYSA-N methylaminomethanetriol Chemical compound CNC(O)(O)O FYFFGSSZFBZTAH-UHFFFAOYSA-N 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 33
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 abstract description 8
- 239000002131 composite material Substances 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 25
- 239000000047 product Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 15
- 238000005406 washing Methods 0.000 description 15
- 238000001035 drying Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000084 colloidal system Substances 0.000 description 12
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- 239000000725 suspension Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000010411 electrocatalyst Substances 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000000527 sonication Methods 0.000 description 4
- 102000020897 Formins Human genes 0.000 description 3
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- 150000007522 mineralic acids Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- -1 transition metal salt Chemical class 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910021650 platinized titanium dioxide Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention provides a preparation method for preparing a carbon-coated titanium dioxide nanoflower composite carrier and application of a platinum and platinum alloy supported nanocatalyst thereof, wherein glacial acetic acid and n-butyl titanate are subjected to hydrothermal reaction to generate flower-shaped TiO2Roasting the precursor in air to obtain three-dimensional TiO2Flower-shaped, then Dopamine (DA) is polymerized in situ into poly-dopamine and coated on TiO2And carrying out heat treatment on the surface of the nanoflower in an inert atmosphere to obtain the carbon-coated titanium dioxide nanoflower. The carbon-coated titanium dioxide nanoflower obtained by the method disclosed by the invention is high in conductivity and good in stability, the three-dimensional structure is favorable for the transmission of reactants, and the preparation method is simple in preparation process and easy to amplify and produce. The carbon-coated titanium oxide nanoflower composite carrier has excellent catalytic activity and stability for the oxygen reduction reaction of the fuel cell after carrying platinum or platinum alloy active components.
Description
Technical Field
The invention relates to a preparation method of a carbon-coated titanium dioxide nanoflower carrier and application of a platinum or platinum alloy supported nano catalyst thereof, in particular to a preparation method of a high-stability and high-conductivity oxygen reduction reaction catalyst carrier and a catalyst, belonging to the technical field of inorganic materials.
Background
The fuel cell is a reaction device for directly converting chemical energy of fuel into electric energy, and has the characteristics of high specific energy, high energy conversion rate, environmental friendliness and the like. The performance and cost of the electrocatalyst, which is used as a key material of the fuel cell, become key factors influencing the practical value of the device. Therefore, the development of an electrocatalyst having high activity and stability is of great importance for the practical use of fuel cell technology.
Currently, metallic Pt is widely used in fuel cells due to its high electrocatalytic activity. In order to improve the utilization rate of Pt, the practical electrocatalyst is formed by loading highly dispersed Pt nano particles on the surface of a conductive carrier such as high specific surface active carbon. The commercial Pt/C catalyst takes active carbon as a carrier, but the active carbon has low graphitization degree, so the catalyst is easy to corrode under the actual working conditions of strong acid and high potential of a fuel cell. The problem of solving the stability of the catalyst carrier of the fuel cell is a precondition for the practical use of the fuel cell.
TiO2Has excellent stability and acid corrosion resistance, and is widely researched as a non-carbon carrier. However, TiO2As a semiconductor, it has low conductivity, poor conductivity as an electrocatalyst support, and large electron transport resistance, which affects battery discharge performance. Chinese patent publication No. CN 108711617 a discloses a method for coating titanium dioxide nanoparticles with carbon, which uses humic acid as a carbon source for coating titanium oxide particles, and after roasting, the carbon-coated titanium dioxide nanoparticles are oxidized and used as a negative electrode material of a lithium ion battery. The literature (Journal of Power Sources, 2006, 159, 219-222) reports that polyacrylonitrile-coated titanium oxide nanoparticles are heat-treated in argon to obtain carbon-coated titanium oxide nanoparticles for use as negative electrode materials of lithium ion batteries. Although the method improves the conductivity of titanium oxide to some extent, the amorphous carbon layer formed on the surface has poor stability, and the nanoparticles are stacked to cause difficulties in transferring reactants, and thus the method cannot be applied as a fuel cell catalyst carrier.
The invention content is as follows:
aiming at the defects of the prior art, the invention aims to provide the preparation method of the carbon-coated titanium dioxide nanoflower composite carrier with high conductivity, high stability and favorable reactant transmission.
Carbon-coated TiO2The preparation method of the nanometer flower carrier and the Pt-supported nanometer particle and Pt alloy nanometer particle catalyst comprises the following steps:
(1) dissolving n-butyl titanate in glacial acetic acid and uniformly stirring to obtain a milky white solution; heating the mixed solution in a hydrothermal kettle, keeping the temperature for a certain time, cooling the hydrothermal kettle naturally, washing the obtained milky colloid or precipitate or the mixture of the milky colloid and the precipitate with deionized water, and drying the product to obtain TiO2Nanometer flower precursor (p-TiO)2)；
Preferably, the volume ratio of the n-butyl titanate to the glacial acetic acid is 1: 10-1: 100;
preferably, the hydrothermal heat preservation time is 6-72 h.
(2) Flower-shaped TiO obtained in the step (1)2The precursor is put in a muffle furnace at 1-20 ℃ for min-1Heating to 500 ℃ at a heating rate, then preserving heat for 0.5-6h, and naturally cooling to obtain TiO2A nanoflower;
(3) TiO obtained in the step (2)2Adding nanoflower into Tris-buffer solution (pH 8.5) under ultrasonic treatment to form suspension, adding dopamine into the mixture under stirring, stirring the mixture at room temperature to complete dopamine polymerization, and coating TiO2Nano flower, finally centrifugally washing and drying the suspension to obtain polydopamine-coated TiO2Nano flower: (4) heating the sample obtained in the step (3) to 150 ℃ in an inert atmosphere of argon or nitrogen and preserving heat for 0.1-3 hours, then heating to 500-1000 ℃ and preserving heat for 0.5-6 hours to obtain the carbon-coated TiO2A nanoflower;
(5) regulating the pH value of the ethylene glycol solution of chloroplatinic acid to 8-14 by using NaOH; heating the mixed solution to 130-160 ℃, preserving the heat for 0.5-6 hours, and adding carbon-coated TiO according to the proportion after the solution is cooled to room temperature2Adding inorganic acid to adjust pH to 4-7, and stirringStirring the solution for 1 to 24 hours, then filtering and washing the sample, and finally drying the sample in vacuum to obtain the carbon-coated TiO loaded with the platinum nanoparticles2A nanoflower;
preferably, the concentration of the ethylene glycol solution of chloroplatinic acid is 0.5 to 10 mg of platinum per ml;
preferably, the inorganic acid may be hydrochloric acid or sulfuric acid or nitric acid.
(6) Regulating the pH value of a glycol solution of chloroplatinic acid and transition metal salt to 8-14 by using NaOH; heating the mixed solution to 130-160 ℃, preserving the heat for 0.5-6 hours, and adding carbon-coated TiO according to the proportion after the solution is cooled to room temperature2Adding inorganic acid into the nano-flower composite carrier to adjust the pH value of the solution to 4-7, stirring the solution for 1-24 hours, filtering and washing a sample, and finally drying in vacuum to obtain the carbon-coated TiO loaded with the platinum alloy nano-particles2A nanoflower;
preferably, the transition metal salt may be a nitrate or chloride salt of Fe, Co and Ni.
Compared with the prior art, the invention has the following advantages and effects:
the invention prepares carbon-coated TiO2The nano flower electro-catalysis carrier greatly improves the conductivity and the specific surface area of the titanium dioxide, and is an excellent electro-catalyst carrier. The carrier is a catalyst with good electrochemical catalytic activity and stability for oxygen reduction reaction after carrying Pt or Pt alloy. The preparation method is simple in preparation process, suitable for large-scale production and has a remarkable application prospect.
Description of the drawings:
figure 1 SEM image of sample prepared in example 5.
Figure 2 TEM images of samples prepared in example 5.
Figure 3 XRD spectrum of the sample prepared in example 5.
FIG. 4 resistivity of the samples of examples 1, 2, 3, 4 and comparative examples.
FIG. 5 polarization curves for the oxygen reduction reaction and after stability testing of the samples prepared in example 5 and the comparative commercial Pt/C catalyst (Zhuangxinwan).
The specific implementation mode is as follows:
the invention is further illustrated below with reference to specific examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Comparative example
Dissolving 2ml of n-butyl titanate in 60ml of glacial acetic acid, and uniformly stirring to obtain a milky white solution; heating the mixed solution in a hydrothermal kettle to 140 ℃, and preserving heat for 12 h; after the hydrothermal kettle is naturally cooled, obtaining milk white colloid or precipitation product or mixture of the two, centrifugally washing the obtained milk white colloid or precipitation product or mixture of the two with deionized water, and finally drying the product to obtain white flower-shaped titanium dioxide precursor p-TiO2. Then adding p-TiO in air atmosphere2At a heating rate of 2 deg.C for min-1Heating to 500 ℃ and preserving heat for 3h to obtain flower-shaped titanium dioxide powder.
Example 1
Dissolving 2ml of n-butyl titanate in 60ml of glacial acetic acid, and uniformly stirring to obtain a milky white solution; heating the mixed solution in a hydrothermal kettle to 140 ℃, and preserving heat for 12 h; after the hydrothermal kettle is naturally cooled, obtaining milk white colloid or precipitation product or mixture of the two, centrifugally washing the obtained milk white colloid or precipitation product or mixture of the two with deionized water, and finally drying the product to obtain white flower-shaped titanium dioxide precursor p-TiO2. Then adding p-TiO in air atmosphere2At a heating rate of 2 deg.C for min-1Heating to 500 ℃ and preserving heat for 3h to obtain flower-shaped titanium dioxide powder. 150mg of flower-like titanium dioxide powder was added to 50mL of tris buffer (pH:8.5) and homogenized by sonication to form a suspension, and then 150mg of dopamine was added and stirred at room temperature for 48 hours. And then centrifugally washing and drying to obtain the polydopamine-coated flower-shaped titanium dioxide. Then placing the mixture in Ar atmosphere at 3 ℃ for min-1Heating to 150 deg.C, maintaining for 1h, and then keeping at 5 deg.C for min-1Heating to 700 deg.C and keeping the temperature2h, obtaining carbon-coated flower-shaped titanium dioxide TiO2@NC-700。
Example 2
Dissolving 2ml of n-butyl titanate in 60ml of glacial acetic acid, and uniformly stirring to obtain a milky white solution; heating the mixed solution in a hydrothermal kettle to 140 ℃, and preserving heat for 12 h; after the hydrothermal kettle is naturally cooled, obtaining milk white colloid or precipitation product or mixture of the two, centrifugally washing the obtained milk white colloid or precipitation product or mixture of the two with deionized water, and finally drying the product to obtain white flower-shaped titanium dioxide precursor p-TiO2. Then adding p-TiO in air atmosphere2At a heating rate of 2 deg.C for min-1Heating to 500 ℃ and preserving heat for 3h to obtain flower-shaped titanium dioxide powder. 150mg of flower-like titanium dioxide powder was added to 50mL of tris-hydroxymethyl aminomethane buffer (pH:8.5) and homogenized by sonication to form a suspension, and then 150mg of dopamine was added thereto and stirred at room temperature for 48 hours. And then centrifugally washing and drying to obtain the polydopamine-coated flower-shaped titanium dioxide. It is heated at 3 deg.C for min in Ar atmosphere-1Heating to 150 deg.C, maintaining for 1h, and then keeping at 5 deg.C for min-1Heating to 800 deg.C and keeping the temperature for 2h to obtain carbon-coated flower-like titanium dioxide TiO2@NC-800。
Example 3
Dissolving 2ml of n-butyl titanate in 60ml of glacial acetic acid, and uniformly stirring to obtain a milky white solution; heating the mixed solution in a hydrothermal kettle to 140 ℃, and preserving heat for 12 h; after the hydrothermal kettle is naturally cooled, obtaining milk white colloid or precipitation product or mixture of the two, centrifugally washing the obtained milk white colloid or precipitation product or mixture of the two with deionized water, and finally drying the product to obtain white flower-shaped titanium dioxide precursor p-TiO2. Then adding p-TiO in air atmosphere2At a heating rate of 2 deg.C for min-1Heating to 500 ℃ and preserving heat for 3h to obtain flower-shaped titanium dioxide powder. 150mg of flower-like titanium dioxide powder was added to 50mL of tris-hydroxymethyl aminomethane buffer (pH:8.5) and homogenized by sonication to form a suspension, and then 150mg of dopamine was added thereto and stirred at room temperature for 48 hours. And then centrifugally washing and drying to obtain the polydopamine-coated flower-shaped titanium dioxide. It is heated at 3 deg.C for min in Ar atmosphere-1Heating to 150 deg.C, maintaining for 1h, and then keeping at 5 deg.C for min-1Heating to 900 ℃ and preserving heat for 2h to obtain carbon-coated flower-shaped titanium dioxide TiO2@NC-900。
Example 4
Dissolving 2ml of n-butyl titanate in 60ml of glacial acetic acid, and uniformly stirring to obtain a milky white solution; heating the mixed solution in a hydrothermal kettle to 140 ℃, and preserving heat for 12 h; after the hydrothermal kettle is naturally cooled, obtaining milk white colloid or precipitation product or mixture of the two, centrifugally washing the obtained milk white colloid or precipitation product or mixture of the two with deionized water, and finally drying the product to obtain white flower-shaped titanium dioxide precursor p-TiO2. Then adding p-TiO in air atmosphere2At a heating rate of 2 deg.C for min-1Heating to 500 ℃ and preserving heat for 3h to obtain flower-shaped titanium dioxide powder. 150mg of flower-like titanium dioxide powder was added to 50mL of tris-hydroxymethyl aminomethane buffer (pH:8.5) and homogenized by sonication to form a suspension, and then 150mg of dopamine was added thereto and stirred at room temperature for 48 hours. And then centrifugally washing and drying to obtain the polydopamine-coated flower-shaped titanium dioxide. It is heated at 3 deg.C for min in Ar atmosphere-1Heating to 150 deg.C, maintaining for 1h, and then keeping at 5 deg.C for min-1Heating to 1000 ℃ and preserving heat for 2h to obtain carbon-coated flower-shaped titanium dioxide TiO2@NC-1000。
Example 5
13.33ml of ethylene glycol solution of chloroplatinic acid (concentration of Pt is 1.5mg ml) was measured out-1) Adding into 20ml of glycol, stirring uniformly, then adding 10ml of NaOH glycol solution with the concentration of 1M, and mixing uniformly; heating the mixed solution to 140 ℃ and preserving heat for 4 hours; after the solution had cooled to room temperature, the TiO obtained in example 3 was added2@ NC-800 carrier 80mg, stirring, adjusting pH of the suspension to 4-7 with 1M HCl solution, stirring for 4h, filtering, washing, and vacuum drying to obtain Pt-TiO loaded with platinum nanoparticles2@ NC-800 sample.
As can be seen from FIGS. 1, 2 and 3, Pt-TiO2The @ NC-800 sample retained TiO2Morphology of nanoflower, TiO2The surface of the carrier is coated by a carbon layer (red marked area in figure 2), and Pt nano particles are uniformly dispersed in the carbon-coated TiO2A carrier surface.
Example 6
12.11ml of ethylene glycol solution of chloroplatinic acid (concentration of Pt is 1.5mg ml) was measured out-1) L0.365 ml of ethylene glycol solution of cobalt acetate (Co concentrate)The degree is 5mg ml-1) Adding the mixture into 20ml of glycol, stirring uniformly, then adding 10ml of NaOH glycol solution with the concentration of 1M, and mixing uniformly; heating the mixed solution to 170 ℃ and preserving heat for 4 hours; after the solution had cooled to room temperature, the TiO obtained in example 3 was added2@ NC-800 carrier 80mg, stirring well, then adjusting the pH of the suspension to 4-7 with 1M HCl solution, stirring for 4h, filtering, washing and vacuum drying to obtain a sample carrying platinum alloy nanoparticles.
Effect example 1
The resistivity of the titanium dioxide nanoflowers obtained in the comparative example is compared with that of the carbon-coated titanium dioxide nanoflowers obtained in examples 1, 2, 3 and 4 of the invention, and as can be seen from fig. 4, the resistivity of the titanium dioxide nanoflowers to 30000 ohm/cm, the resistivity of the carbon-coated titanium dioxide nanoflowers to be lower than 180 ohm/cm, and the conductivity is remarkably improved.
Effect example 2
The Pt-loaded carbon-coated titania nanoflowers obtained in example 5 according to the present invention were used to catalyze an oxygen reduction reaction under the following test conditions: the electrolyte is 0.1M HClO saturated with oxygen4Electrode rotation speed 1600rpm, sweep rate: 10mV s-1Cycling is carried out 10000 times at 0.6-1.0V (relative to a reversible hydrogen electrode). As can be seen from FIG. 5, the initial oxygen reduction activity of the carbon-coated catalyst is similar to that of commercial Pt/C, and the half-wave potential is 0.91V; after the stability cycle test, the commercial Pt/C half-wave potential negative shift is 50mV, and the attenuation is obvious; the carbon-coated titanium dioxide nanoflower obtained by the method has no negative shift and positive shift of 20mV, and is obviously superior to commercial Pt/C.
Claims (6)
1. A preparation method of a carbon-coated titanium dioxide nanometer flower carrier and an application of the carbon-coated titanium dioxide nanometer flower carrier in carrying platinum or platinum alloy nanometer catalysts are characterized in that the method comprises the following steps:
(1) glacial acetic acid and tetrabutyl titanate generate flower-shaped TiO through hydrothermal reaction2A precursor;
(2) flower-shaped TiO obtained in the step (1)2Roasting the precursor in the air to obtain three-dimensional flower-shaped TiO2；
(3) TiO obtained in the step (2)2Stirring the nanoflower and Dopamine (DA) in a trihydroxymethyl aminomethane-buffer solution, and coating the dopamine on flower-shaped TiO in a polymerization manner2Surface to obtain polydopamine coated TiO2Nanometer flower (TiO)2@PDA)；
(4) TiO obtained in the step (3)2The nanometer flower is heat treated in inert atmosphere to obtain carbon-coated titanium dioxide nanometer flower carrier (TiO)2@NC-T)；
(5) TiO obtained in step (4)2The @ NC-T carrier can be applied to the cathode oxygen reduction reaction of the fuel cell after carrying platinum or platinum alloy nano particles.
2. The method as claimed in claim 1, wherein the flower-like titanium dioxide precursor in step (1) is prepared by hydrothermal reaction at 120-180 ℃ for 6-72h using glacial acetic acid and tetrabutyl titanate as reactants.
3. The method according to claim 1, wherein the TiO in the step (2)2The nanometer flower is made of flower-shaped TiO2The precursor is heated in air at 2-20 deg.C for min-1The temperature rise rate is raised to 400-800 ℃, and the temperature is maintained for 0.5-6 h.
4. The method according to claim 1, wherein the polydopamine-coated TiO in the step (3)2The nanometer flower is prepared by adding 0.05-100mg ml of Tris buffer solution (pH 6-10)-1The dopamine of (1).
5. The method of claim 1, wherein the carbon-coated titanium dioxide nanoflower carrier TiO in the step (4)2@ NC-T is prepared by mixing flower-like TiO2@ PDA under inert atmosphere, including N2Gas and Ar gas, and the temperature is 500-1000 ℃.
6. The method according to claim 1, wherein the amount of the platinum or platinum alloy nanoparticles supported on the surface of the carbon-coated titanium dioxide nanoflower carrier in the step (5) is 5 to 80%.
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