CN110961162A - Catalyst carrier, precious metal catalyst, and preparation method and application thereof - Google Patents
Catalyst carrier, precious metal catalyst, and preparation method and application thereof Download PDFInfo
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- CN110961162A CN110961162A CN201911249175.5A CN201911249175A CN110961162A CN 110961162 A CN110961162 A CN 110961162A CN 201911249175 A CN201911249175 A CN 201911249175A CN 110961162 A CN110961162 A CN 110961162A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000010970 precious metal Substances 0.000 title description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 48
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000001301 oxygen Substances 0.000 claims abstract description 29
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 29
- 150000003623 transition metal compounds Chemical class 0.000 claims abstract description 27
- 238000006722 reduction reaction Methods 0.000 claims abstract description 26
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- 238000000034 method Methods 0.000 claims abstract description 14
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- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 claims description 2
- 229940005991 chloric acid Drugs 0.000 claims description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000000265 homogenisation Methods 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 8
- 238000002604 ultrasonography Methods 0.000 claims 1
- 230000009467 reduction Effects 0.000 abstract description 12
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- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 238000003487 electrochemical reaction Methods 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 112
- 229910052697 platinum Inorganic materials 0.000 description 48
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 28
- 229910003468 tantalcarbide Inorganic materials 0.000 description 27
- 239000002105 nanoparticle Substances 0.000 description 20
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 19
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 16
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 7
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
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- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 229910004537 TaCl5 Inorganic materials 0.000 description 2
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Images
Classifications
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- B01J35/615—
-
- 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
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- B01J35/33—
-
- B01J35/397—
-
- B01J35/51—
Abstract
The invention relates to a catalyst carrier, a noble metal catalyst, and a preparation method and application thereof. The cross-linked polystyrene microsphere is taken as a sacrificial template, the hollow carbon microsphere coated by the transition metal compound is prepared by combining solvothermal and one-step carbonization methods, and is taken as a carrier, and noble metal nano particles are loaded by a wet chemical reduction method so as to be uniformly anchored on the surface of the hollow carbon microsphere coated by the transition metal compound. The catalyst has the advantages of strong electrochemical corrosion resistance and large specific surface area, and shows excellent catalytic performance in electrochemical reactions such as oxygen reduction, hydrogen precipitation, methanol oxidation and the like.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, relates to a catalyst carrier, a noble metal catalyst, and preparation methods and applications thereof, and particularly relates to a transition metal compound coated hollow carbon microsphere carrier supported noble metal nanoparticle catalyst, a preparation method thereof, and an application thereof in electrochemical catalytic reaction.
Background
The energy and environmental challenges facing the world today are becoming more severe and the development of green, clean, renewable energy sources is at hand. Hydrogen is considered to be an ideal energy carrier due to the characteristics of zero pollution, high energy density and the like. Under the background of hydrogen economy, the technology of hydrogen production by water electrolysis becomes one of efficient energy conversion technologies for obtaining high-purity hydrogen fuel, and finally, hydrogen energy is popularized and used through renewable energy conversion technologies such as fuel cells and the like. In order to improve the energy conversion efficiency of devices such as fuel cells, water electrolysis and the like and accelerate the kinetic rate of the reaction process, the development of the platinum-based electro-catalytic material with high activity and high stability has important significance for promoting the research of related fields.
Group IVB-VIB transition metal compounds are considered ideal supports for platinum-based catalysts due to their good stability in acidic systems. Moreover, because of the strong metal-carrier interaction between the transition metal compound and the noble metal platinum, the effect of the method on enhancing the electrocatalytic activity and stability of the platinum nano-particles is remarkable. However, the specific surface area of the metal compound is generally low, which is not favorable for the dispersion of platinum nanoparticles; secondly, it is less conductive and not conducive to electron transfer during electrocatalytic reactions. Therefore, the carrier prepared with the high specific surface area, the high conductivity and the good acid resistance has important application prospect when being used for anchoring the platinum nano-particles.
In order to solve the problem, a carbon material modified by a metal compound is generally used as a platinum-based catalyst carrier, and the advantages of high conductivity and large specific surface area of the carbon material and a strong noble metal anchoring site provided by the metal compound are utilized, so that the stability of the platinum-based catalyst is improved, and the service life of a device is prolonged. However, in long term working environments, such as acidic systems and high oxidation potentials, carbon materials will face serious electrochemical corrosion problems. Although modification of the metal compound can improve the corrosion resistance of the carbon support to some extent, the portion of the carbon material directly exposed to the electrolyte solution is still inevitably faced with the problem of electrochemical corrosion. Therefore, in order to obtain a platinum-based catalyst having excellent stability, it is necessary to perform reasonable structural design of the transition metal compound-modified carbon support.
Disclosure of Invention
In order to solve the above problems in the prior art, the present invention provides a catalyst carrier, in which a transition metal compound is used to coat a carbon microsphere structure, the carrier has a large specific surface area, which is beneficial to the dispersion of noble metal nanoparticles, and the formation of the coating structure is beneficial to the enhancement of the electrochemical corrosion resistance of the carbon material. Another object of the present invention is to provide a noble metal catalyst comprising the above catalyst carrier, and a preparation method and applications thereof, in which noble metal nanoparticles are strongly anchored on the surface of the carrier, and the catalyst exhibits excellent performance in electrochemically catalyzing reactions such as hydrogen evolution, oxygen reduction, and methanol oxidation.
In order to realize the purpose of the invention, the invention adopts the following technical scheme: a catalyst support comprising: the carbon microsphere is of a hollow structure; and the transition metal compound is coated on the surface of the carbon microsphere.
In a preferred embodiment of the present invention, the transition metal compound is selected from one or more of groups IVB-VIB, Ti, Zr, V, Nb, Ta, Mo, W.
The invention also provides a noble metal catalyst, which comprises the catalyst carrier and noble metal nano-particles dispersed on the catalyst carrier.
In a preferred embodiment of the present invention, the noble metal catalyst loading is between 1% and 40%.
The invention also protects the preparation method of the noble metal catalyst, absolute ethyl alcohol is used as a solvent, the crosslinked polystyrene microsphere is used as a sacrificial template, a solvothermal method is adopted to prepare a precursor of the crosslinked polystyrene microsphere coated by the transition metal compound, and the composition of the transition metal compound phase is regulated and controlled by controlling the carbonization temperature, so that a carrier with rich noble metal anchoring sites is formed; and (3) uniformly anchoring the noble metal on the surface of the hollow carbon microsphere coated by the transition metal compound by adopting a wet chemical method.
In a preferred embodiment of the present invention, the preparation method comprises the following specific steps:
(1) sulfonating the crosslinked polystyrene microspheres by using a sulfonating agent;
(2) respectively dispersing transition metal chloride and crosslinked polystyrene microspheres in an absolute ethyl alcohol solution, and performing ultrasonic homogenization;
(3) uniformly mixing the two solutions obtained in the steps (1) and (2), and adding glacial acetic acid;
(4) transferring the mixed solution obtained in the step (3) to a polytetrafluoroethylene reaction kettle for solvothermal reaction, and filtering, washing and drying the obtained solution to obtain light yellow powder;
(5) carbonizing the light yellow powder obtained in the step (4) in an inert atmosphere to prepare a hollow carbon microsphere carrier coated by a transition metal compound with a large specific surface area;
(6) and (3) dispersing the transition metal compound coated hollow carbon microsphere carrier obtained in the step (5) in an ethylene glycol solution, adding noble metal acid or salt, adjusting the pH value, and then carrying out oil bath reaction to prepare the noble metal catalyst.
In a preferred embodiment of the present invention, in step (1), the sulfonating agent comprises one or more of concentrated sulfuric acid, chlorosulfonic acid, sulfamic acid and sulfite.
In a preferred embodiment of the present invention, in the step (2), the mass ratio of the transition metal chloride to the crosslinked polystyrene microspheres is 0.25 to 4.
In a preferred embodiment of the present invention, in step (3), the solution mixing method specifically comprises a combination of one or more of stirring, sonication and shaking, or a recycling of multiple modes, each mode lasting from 0.5 to 24 hours.
In a preferred embodiment of the present invention, in the step (4), the solvent is subjected to a thermal reaction at a temperature of 100 to 220 ℃ for 6 to 36 hours.
In a preferred embodiment of the present invention, in the step (5), the carbonization treatment comprises two stages of heat preservation, wherein the heat preservation is performed at 300-400 ℃ for 0.5-4 h, and then the heat preservation is performed at a high temperature of 700-1100 ℃ for 0.5-6 h.
In a preferred embodiment of the present invention, in the step (6), the noble metal acid or salt is selected from the group consisting of noble metal chloric acid or chlorate; the pH range is 7-12, and the oil bath temperature is 120-160 ℃.
The invention also protects the application of the noble metal catalyst in electrochemical catalytic oxygen reduction reaction, hydrogen precipitation reaction and methanol oxidation reaction.
Compared with the prior art, the invention has the following advantages:
1. the preparation method of the transition metal compound coated hollow carbon microsphere supported noble metal nanoparticle catalyst provided by the invention comprises the steps of taking absolute ethyl alcohol as a solvent, taking a crosslinked polystyrene microsphere as a sacrificial template, preparing a transition metal compound coated crosslinked polystyrene microsphere precursor by adopting a solvothermal method, controlling the phase composition of a metal compound by controlling the carbonization temperature, particularly performing two optimized heat preservation processes, so that the prepared carrier has rich noble metal strong anchoring sites, uniformly anchoring noble metals on the surface of the transition metal compound coated hollow carbon microsphere by combining a wet chemical method, and finally obtaining the transition metal compound coated hollow carbon microsphere carrier supported noble metal nanoparticle catalyst. Compared with the traditional noble metal catalyst preparation method, the method has obvious advantages in preparing the carrier with large specific surface area, high conductivity and good acid resistance.
2. The hollow carbon microsphere carrier coated by the transition metal compound prepared by the invention has larger specific surface area up to 471 m2g-1The uniform dispersion of the platinum nano-particles is ensured, so that the catalyst has higher utilization rate of noble metal.
3. The hollow carbon microsphere carrier coated by the transition metal compound prepared by the invention has high conductivity, strong electrochemical corrosion resistance and strong noble metal anchoring sites, so that the electrocatalytic stability of the noble metal catalyst is obviously improved.
4. The preparation method of the transition metal compound coated hollow carbon microsphere carrier supported noble metal nanoparticle catalyst provided by the invention has the advantages of simple preparation process, low price, short period, environmental friendliness and high repeatability, and is suitable for industrial production.
Drawings
The invention will be further described with reference to the accompanying drawings, which are only schematic illustrations and illustrations of the invention, and do not limit the scope of the invention.
FIG. 1 is a high resolution scanning electron microscope image of a hollow carbon microsphere carrier coated with tantalum pentoxide/tantalum carbide composite prepared in example 1 of the present invention;
FIG. 2 is a nitrogen adsorption-desorption curve of a tantalum pentoxide/tantalum carbide composite coated hollow carbon microsphere carrier prepared in example 1 of the present invention;
FIG. 3 is a high-resolution TEM image of a noble metal platinum nanoparticle catalyst supported on a hollow carbon microsphere carrier coated with tantalum pentoxide/tantalum carbide in example 1 of the present invention;
FIG. 4 is a graph showing the oxygen reduction polarization curve of the noble metal platinum nanoparticle catalyst supported on the hollow carbon microsphere carrier coated with tantalum pentoxide/tantalum carbide in accordance with example 1 of the present invention;
FIG. 5 is a graph showing the test results of the accelerated stability test of the noble metal platinum nanoparticle catalyst supported on the tantalum pentoxide/tantalum carbide composite-coated hollow carbon microsphere carrier prepared in example 1 of the present invention;
FIG. 6 is a high-resolution TEM image of a Ta pentoxide-modified CNT-loaded Pt nanoparticle catalyst prepared according to a comparative example of the present invention;
FIG. 7 is a graph showing the results of accelerated stability test of the catalyst prepared by comparative example according to the present invention.
Detailed Description
In order to clearly understand the objects, technical solutions and technical effects of the present invention, the present invention will now be described in further detail with reference to the accompanying drawings and specific embodiments.
Example 1
Preparation of tantalum pentoxide/tantalum carbide composite coated hollow carbon microsphere carrier negativePlatinum nanoparticle-supported catalyst (Pt/Ta)2O5-TaC/C), 12 mL of a mixture of styrene monomer and 0.7 g of divinylbenzene crosslinking agent was added to a three-necked flask, 130mL of deionized water was added, and heated at 70 ℃ in an oil bath, stirred at 350 rpm, while purging with argon for 1 hour to remove dissolved oxygen. Then, 10 mL of a solution having a mass fraction of 0.005 g mL was added-1And heating the mixture at 70 ℃ for 10 h under the condition of introducing argon. After the solution is cooled, saturated sodium chloride is added for demulsification, the obtained monodisperse crosslinked polystyrene microspheres are collected by filtration, washed by deionized water and then dried at 60 ℃.3 g of crosslinked polystyrene microspheres were stirred for 6 h at 350 rpm at 40 ℃ by dispersing them in 100 mL of concentrated sulfuric acid solution. After cooling, the product was washed with deionized water until the pH of the washing solution reached 7, and then filtered and dried to obtain pale yellow sulfonated crosslinked styrene microspheres.
0.2 g of sulfonated crosslinked styrene microspheres and 0.284 g of TaCl5Dispersing in 27 and 13 mL absolute ethyl alcohol respectively, and carrying out ultrasonic treatment for 0.5 h. Then adding the sulfonated crosslinked styrene microsphere suspension into TaCl drop by drop5In ethanol solution, ultrasonic treatment is carried out for 0.5 h. Adding 0.05 g of glacial acetic acid into the solution, transferring the obtained light yellow suspension into a reaction kettle with a polytetrafluoroethylene inner container, and heating at 150 ℃ for 12 h. And after cooling, filtering, washing and drying to obtain the tantalum oxide coated crosslinked polystyrene microsphere precursor. The carbonization treatment adopts two-stage heating process in argon atmosphere, and the heating rate is 5 ℃ for min-1Heating to 350 ℃ for two hours, and then heating at the rate of 2 ℃ for min-1And raising the temperature to 1000 ℃ and preserving the temperature for two hours. Naturally cooling to obtain the tantalum pentoxide coated hollow carbon microsphere carrier. 100 mg of tantalum pentoxide coated hollow carbon microsphere carrier is dispersed in 100 mL of ethylene glycol and subjected to ultrasonic treatment for 0.5 h. Subsequently, 5.12 mL of a solution having a mass fraction of 0.01 mol L was added-1A solution of chloroplatinic acid was added to the above solution. By adding 1 mol of L-1The pH value of the solution is adjusted to 10 by NaOH solution, and the solution is heated and stirred for 3 hours at 130 ℃ in an oil bath kettle. After cooling, washing, filtering and drying, collecting Pt/Ta2O5-a TaC/C catalyst.
FIG. 4 is the Pt/Ta finally obtained under the conditions described in example 12O5Polarization curve of the TaC/C catalyst oxygen reduction reaction. Test conditions were 0.1M HClO at oxygen saturation4The sweep rate was 10 mV/s under the solution and 1600 rpm. The test samples contained in the figure are respectively a platinum nanoparticle catalyst (Pt/Ta) supported on a tantalum pentoxide/tantalum carbide composite coated hollow carbon microsphere carrier2O5TaC/C) and commercial platinum carbon (20% Pt/C). Calculated from the oxygen reduction polarization curve, Pt/Ta2O5Kinetic Current Density of TaC/C and Pt/C catalysts at 0.9V vs. RHE ((R))J k) Are respectively 4.45 mAcm-2And 1.63 mA cm-2。Pt/Ta2O5The platinum loading on the electrode surface (m) in TaC/C and Pt/C catalystspt) Are respectively 15ug cm-2And 20 ug cm-2. Mass Activity (MA) by the formula MA =J k/mptCan obtain, Pt/Ta2O5The mass activity of the TaC/C and Pt/C catalysts is 0.297A mg respectively–1 PtAnd 0.081A mg–1 Pt，Pt/Ta2O5the-TaC/C electrocatalytic oxygen reduction activity is obviously superior to that of commercial platinum carbon.
FIG. 5 is the Pt/Ta finally obtained under the conditions described in example 12O5Potential cycling accelerated stability test of the TaC/C catalyst oxygen reduction reaction. Potential cycling test conditions were 0.1M HClO saturated in nitrogen4Under the solution, the scanning range is 0.6-1.1V vs. RHE, and the scanning speed is 100 mV/s. The polarization curves before and after cycling were recorded under 0.1M HClO at oxygen saturation4The sweep rate was 10 mV/s under the solution and 1600 rpm. Observation of Pt/Ta2O5Polarization curves before and after TaC/C catalyst stability test, Pt/Ta after 10000 cycles of potential cycling2O5The half-wave potential of the-TaC/C is attenuated by only 3 mV, and the stability of the oxygen reduction reaction is excellent. The test results of other examples are also similar to example 1, and it can be seen that the transition metal compound-coated hollow carbon microsphere carrier-supported platinum nanoparticle catalyst prepared by the method of the present invention has a large specific surface area and a high specific surface areaConductivity and strong electrochemical corrosion resistance, and has high electrocatalytic oxygen reduction performance.
Example 2
The operation conditions were the same as in example 1, except that in the carbonization step and the second temperature rise step, the temperature was 800 ℃, and a platinum nanoparticle catalyst supported on a tantalum pentoxide-coated hollow carbon microsphere carrier was prepared. The specific surface area of the tantalum pentoxide coated hollow carbon microsphere carrier is 249.1 m2g-1. The kinetic current density of the platinum catalyst based on the carrier under the condition of 0.9V vs. RHE can be calculated by an oxygen reduction polarization curve (J k) Are respectively 1.85 mA cm-2The amount (m) of platinum carried on the electrode surfacept) Are respectively 15ug cm-2. It can thus be calculated that the platinum catalyst based on the carrier had an oxygen reduction reaction mass activity of 0.123A mg under the condition of 0.9V–1 PtSuperior to commercial platinum carbon catalysts. The sample is subjected to a potential cycling accelerated stability test under the same test conditions as in example 1, and after 10000 potential cycles, the half-wave potential attenuation is 7 mV.
Example 3
The operation conditions were the same as in example 1 except that in the carbonization step, the temperature in the second temperature raising step was 1100 ℃, and a platinum nanoparticle catalyst supported on a tantalum carbide-coated hollow carbon microsphere carrier was prepared. The specific surface area of the tantalum carbide coated hollow carbon microsphere carrier is 442.5 m2g-1. The dynamic current density of the platinum catalyst based on the carrier under the condition of 0.9 Vvs. RHE can be calculated by an oxygen reduction polarization curve (J k) Are respectively 2.31 mA cm-2The amount (m) of platinum carried on the electrode surfacept) Are respectively 15ug cm-2. It can thus be calculated that the platinum catalyst based on the carrier had an oxygen reduction reaction mass activity of 0.154A mg at 0.9V–1 PtSuperior to commercial platinum carbon catalysts. The sample is subjected to a potential cycling accelerated stability test under the same test conditions as in example 1, and after 10000 potential cycles, the half-wave potential attenuation is 10 mV.
Example 4
The operation conditions were the same as example 1, except that the solvothermal reaction temperature was 100 ℃ and the reaction time was 36 hours, and a platinum nanoparticle catalyst supported on a tantalum pentoxide/tantalum carbide composite-coated hollow carbon microsphere carrier was prepared. The specific surface area of the tantalum pentoxide/tantalum carbide composite coated hollow carbon microsphere carrier is 395.5 m2g-1. The kinetic current density of the platinum catalyst based on the carrier under the condition of 0.9V vs. RHE can be calculated by an oxygen reduction polarization curve (J k) Respectively is 2.76 mAcm-2The amount (m) of platinum carried on the electrode surfacept) Are respectively 15ug cm-2. It can thus be calculated that the platinum catalyst based on this carrier had an oxygen reduction reaction mass activity of 0.184A mg at 0.9V–1 PtSuperior to commercial platinum carbon catalysts. The sample is subjected to a potential cycling accelerated stability test under the same test conditions as in example 1, and after 10000 potential cycles, the half-wave potential attenuation is 4 mV.
Example 5
The operation conditions were the same as example 1, except that the solvothermal reaction temperature was 220 ℃ and the reaction time was 24 hours, and a platinum nanoparticle catalyst supported on a tantalum pentoxide/tantalum carbide composite-coated hollow carbon microsphere carrier was prepared. The specific surface area of the tantalum pentoxide/tantalum carbide composite coated hollow carbon microsphere carrier is 453.5 m2g-1. The kinetic current density of the platinum catalyst based on the carrier under the condition of 0.9V vs. RHE can be calculated by an oxygen reduction polarization curve (J k) Are respectively 3.47 mAcm-2The amount (m) of platinum carried on the electrode surfacept) Are respectively 15ug cm-2. It can thus be calculated that the platinum catalyst based on this carrier had an oxygen reduction reaction mass activity of 0.231A mg under the condition of 0.9V–1 PtSuperior to commercial platinum carbon catalysts. The sample is subjected to a potential cycling accelerated stability test under the same test conditions as in example 1, and after 10000 potential cycles, the half-wave potential attenuation is 6 mV.
Example 6
The operation conditions were the same as example 2 except that noble metal nanoparticles were supportedIn the particle reaction process, the solution pH value is 12, the oil bath temperature is 120 ℃, and the tantalum pentoxide coated hollow carbon microsphere carrier supported platinum nanoparticle catalyst is prepared. The specific surface area of the tantalum pentoxide coated hollow carbon microsphere carrier is 249.1 m2g-1. The kinetic current density of the platinum catalyst based on the carrier under the condition of 0.9V vs. RHE can be calculated by an oxygen reduction polarization curve (J k) Are respectively 1.61mAcm-2The amount (m) of platinum carried on the electrode surfacept) Are respectively 15ug cm-2. It can thus be calculated that the platinum catalyst based on this carrier had an oxygen reduction reaction mass activity of 0.107A mg under the condition of 0.9V–1 PtSuperior to commercial platinum carbon catalysts. The sample is subjected to a potential cycling accelerated stability test under the same test conditions as in example 1, and after 10000 potential cycles, the half-wave potential attenuation is 11 mV.
Example 7
The operation conditions were the same as example 3, except that in the reaction process of loading noble metal nanoparticles, the solution pH was 7, the oil bath temperature was 160 ℃, and the tantalum carbide-coated hollow carbon microsphere supported platinum nanoparticle catalyst was prepared. The specific surface area of the tantalum carbide coated hollow carbon microsphere carrier is 442.5 m2g-1. The kinetic current density of the platinum catalyst based on the carrier under the condition of 0.9V vs. RHE can be calculated by an oxygen reduction polarization curve (J k) Are respectively 1.92 mA cm-2The amount (m) of platinum carried on the electrode surfacept) Are respectively 15ug cm-2. It can thus be calculated that the platinum catalyst based on the carrier has an oxygen reduction reaction mass activity of 0.128A mg at 0.9V–1 PtSuperior to commercial platinum carbon catalysts. The sample is subjected to a potential cycling accelerated stability test under the same test conditions as in example 1, and after 10000 potential cycles, the half-wave potential attenuation is 9 mV.
Comparative example
Uniformly dispersing 100 mg of acidified carbon nano-tube in 50 mL of ethanol solution, and simultaneously, dispersing 100 mg of TaCl5Dispersed in a mixed solution of 140. mu.L of benzyl alcohol and 10 mL of anhydrous ethanol.The obtained TaCl is added5The solution was added dropwise to the acidified carbon nanotube suspension, stirred for 12 h, then transferred to a microwave hydrothermal reactor and heated at 150 ℃ for 1 h. After cooling, it was filtered, washed and dried at 80 ℃. Finally, the tantalum pentoxide modified carbon nanotube composite carrier is obtained by heating at 800 ℃ for 3 h in argon atmosphere, and the platinum nanoparticle loading process is carried out as in example 1 to obtain the tantalum pentoxide modified carbon nanotube composite carrier-supported platinum nanoparticle catalyst (Pt-Ta)2O5/CNT). The specific surface area of the tantalum pentoxide modified carbon nanotube composite carrier is 67.5 m2g-1. The kinetic current density of the platinum catalyst based on the carrier under the condition of 0.9V vs. RHE can be calculated by an oxygen reduction polarization curve (J k) Are respectively 4.6 mA cm-2The amount (m) of platinum carried on the electrode surfacept) Are respectively 20 ugcm-2. It can thus be calculated that the platinum catalyst based on the carrier had an oxygen reduction reaction mass activity of 0.23A mg under the condition of 0.9V–1 PtSuperior to commercial platinum carbon catalysts. The sample was subjected to a potential cycling accelerated stability test under the same conditions as in example 1, and FIG. 7 shows a polarization curve before and after the stability test, after 10000 cycles of potential cycling, Pt-Ta2O5The half-wave potential decay of the/CNT is 15 mV. The stability of the platinum nanoparticle catalyst loaded on the tantalum pentoxide/tantalum carbide composite coated hollow carbon microsphere carrier prepared in example 1 is obviously superior to that of the platinum nanoparticle catalyst loaded on the tantalum pentoxide modified carbon nanotube composite carrier.
The carbon microspheres are not limited to microsphere structures, and the carbon material is selected from one of carbon spheres, carbon tubes and carbon rods. It should be understood that although the present description has been described in terms of various embodiments, not every embodiment includes only a single embodiment, and such description is for clarity purposes only, and those skilled in the art will recognize that the embodiments described herein may be combined as suitable to form other embodiments, as will be appreciated by those skilled in the art.
The invention has been described in an illustrative manner, and it is to be understood that the invention is not limited in its implementation to the details of construction and to the arrangements of the components set forth in the description, but is capable of equivalent embodiments or modifications, such as combinations of features, divisions or repetitions, or application of the concepts and arrangements of the invention without modification in other applications, all without departing from the spirit and scope of the invention.
Claims (10)
1. A catalyst carrier characterized by comprising: the carbon microsphere is of a hollow structure; and the transition metal compound is coated on the surface of the carbon microsphere.
2. The catalyst carrier according to claim 1, wherein the transition metal compound is selected from one or more of groups IVB-VIB, Ti, Zr, V, Nb, Ta, Mo, W.
3. A noble metal catalyst comprising the catalyst carrier of any one of claims 1 to 2 and noble metal nanoparticles dispersed on the catalyst carrier.
4. The noble metal catalyst of claim 3, wherein the noble metal catalyst loading is between 1% and 40%.
5. The preparation method of the noble metal catalyst according to claim 3 or 4, characterized in that absolute ethyl alcohol is used as a solvent, a crosslinked polystyrene microsphere is used as a sacrificial template, a transition metal compound coated crosslinked polystyrene microsphere precursor is prepared by a solvothermal method, and the composition of a transition metal compound phase is regulated by controlling the carbonization temperature to form a carrier with rich noble metal anchoring sites; and (3) uniformly anchoring the noble metal on the surface of the hollow carbon microsphere coated by the transition metal compound by adopting a wet chemical method.
6. The method for preparing a noble metal catalyst according to claim 5, comprising the steps of:
(1) sulfonating the crosslinked polystyrene microspheres by using a sulfonating agent;
(2) respectively dispersing transition metal chloride and crosslinked polystyrene microspheres in an absolute ethyl alcohol solution, and performing ultrasonic homogenization;
(3) uniformly mixing the two solutions obtained in the steps (1) and (2), and adding glacial acetic acid;
(4) transferring the mixed solution obtained in the step (3) to a polytetrafluoroethylene reaction kettle for solvothermal reaction, and filtering, washing and drying the obtained solution to obtain light yellow powder;
(5) carbonizing the light yellow powder obtained in the step (4) in an inert atmosphere to prepare a hollow carbon microsphere carrier coated by a transition metal compound with a large specific surface area;
(6) and (3) dispersing the transition metal compound coated hollow carbon microsphere carrier obtained in the step (5) in an ethylene glycol solution, adding noble metal acid or salt, adjusting the pH value, and then carrying out oil bath reaction to prepare the noble metal catalyst.
7. The preparation method according to claim 6, wherein in the step (1), the sulfonating agent comprises one or more of concentrated sulfuric acid, chlorosulfonic acid, sulfamic acid and sulfite; and/or the presence of a gas in the gas,
in the step (2), the mass ratio of the transition metal chloride to the crosslinked polystyrene microspheres is 0.25-4; and/or the presence of a gas in the gas,
in the step (3), the solution mixing method specifically comprises one or more of stirring, ultrasound and shaking, or multiple modes of recycling, wherein the duration time of each mode ranges from 0.5 to 24 hours.
8. The preparation method according to claim 6, wherein in the step (4), the solvothermal reaction is carried out at a temperature of 100-220 ℃ for 6-36 h; and/or the presence of a gas in the gas,
in the step (5), the carbonization treatment comprises two sections of heat preservation processes, wherein the heat preservation is carried out for 0.5-4 hours at the temperature of 300-400 ℃ and then for 0.5-6 hours at the high temperature of 700-1100 ℃; and/or the presence of a gas in the gas,
in the step (6), the noble metal acid or salt is selected from noble metal chloric acid or chlorate; the pH range is 7-12, and the oil bath temperature is 120-160 ℃.
9. Use of the noble metal catalyst of claim 3 or 4 in electrochemically catalysed oxygen reduction reactions, hydrogen evolution reactions and methanol oxidation reactions.
10. Use of the noble metal catalyst prepared by the preparation method according to any one of claims 5 to 8 in electrochemically catalyzed oxygen reduction reactions, hydrogen evolution reactions and methanol oxidation reactions.
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