CN114068949A - High-performance titanium-based low-platinum catalyst, preparation method thereof and application thereof in fuel cell - Google Patents
High-performance titanium-based low-platinum catalyst, preparation method thereof and application thereof in fuel cell Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 177
- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- 239000010936 titanium Substances 0.000 title claims abstract description 61
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 60
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 47
- 239000000446 fuel Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 52
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 25
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 20
- 230000001603 reducing effect Effects 0.000 claims abstract description 15
- 239000012528 membrane Substances 0.000 claims abstract description 6
- 239000003011 anion exchange membrane Substances 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 238000000151 deposition Methods 0.000 claims description 21
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- 239000002243 precursor Substances 0.000 claims description 15
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- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 12
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- 229910052786 argon Inorganic materials 0.000 claims description 6
- FSKLOGLSYZIRMP-UHFFFAOYSA-N carbanide 2-methylcyclopenta-1,3-diene platinum(4+) Chemical group [CH3-].[CH3-].[CH3-].[Pt+4].CC=1C=C[CH-]C=1 FSKLOGLSYZIRMP-UHFFFAOYSA-N 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
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- 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 description 3
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- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
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- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002245 particle Substances 0.000 abstract description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 9
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
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- 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
-
- 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
-
- 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
-
- 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
- H01M4/96—Carbon-based electrodes
-
- 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 relates to the technical field of catalysts for fuel cells, in particular to a high-performance titanium-based low-platinum catalyst, a preparation method thereof and application thereof in fuel cells. The scheme introduces vacancy oxygen (Ov) into titanium oxide by a two-step method to be used as a carrier, promotes the atomic layer deposition technology to reduce low-load Pt particles, and leads the Pt particles and Ti to benOXAnd the catalyst and the carbon material form a 'triple-junction' structure, so that the condition that the catalyst effect is poor due to the fact that Pt and metal oxide nanoparticles are independently deposited on the surface of the carbon material is avoided. The catalyst can be applied to proton exchange membrane fuel cells, alkaline anion exchange membrane fuel cells or metal-air cellsIn the manufacturing process, the battery performance is improved, and the battery cost is reduced by reducing the Pt content.
Description
Technical Field
The invention relates to the technical field of catalysts for fuel cells, in particular to a high-performance titanium-based low-platinum catalyst, a preparation method thereof and application thereof in fuel cells.
Background
The fuel cell, as a new energy conversion device, can directly and continuously convert the chemical energy of fuel and oxidant into electric energy, has the advantages of low noise, high response speed, high modularization degree, high operation quality, high energy conversion efficiency and the like, attracts the attention of all countries in the world in recent years, and is widely applied to the fields of transportation, energy storage power stations, aerospace and the like. The cathode Oxygen Reduction Reaction (ORR) kinetics of fuel cells are slow, producing large polarization (up to 300400mV), which greatly affects the output performance of the cell. Therefore, the research on the mechanism of the cathode oxygen reduction reaction and the development of high-performance electrocatalysts have become one of the major concerns of researchers. At present, the cathode oxygen reduction catalyst is mainly carbon-supported platinum (Pt), but Pt is expensive, and electrochemical corrosion of the carbon support can cause agglomeration and sintering of Pt particles, so that the electrochemical surface area (ECSA) and the catalytic activity are reduced, further the stability is greatly reduced, and the large-scale application of the catalyst is limited. Therefore, the development and preparation of cathode catalytic materials with low Pt content and high catalytic activity and stability are fields with great research significance at present.
To address this problem, strategies have generally been employed to incorporate metal oxides into the material system, such as titanium dioxide (TiO)2) Nanoparticles are a commonly used carrier, but their small specific surface area and electrical conductivity greatly limit their application in the field of electrocatalysis. Despite the TiO content2Nanotubes have a larger specific surface area and a faster charge transport rate due to their regular tubular structure and fewer grain boundaries, but still have poor electrical conductivity compared to carbon materials. The presence of Ti in the titanium-based oxide systemnO2n-1(Magneti phase, n is a number between 1 and 10), with Ti being more typical4O7Has the advantages ofHigh conductivity (greater than 10 at room temperature)3S cm-1) Excellent thermal stability and corrosion resistance in acidic media have been used as support materials for Pt. However, in the existing catalyst system of "platinum-metal oxide-carbon support", most of Pt and metal oxide nanoparticles are inevitably deposited on the surface of the carbon material alone, and the advantage of interaction of components cannot be exerted.
Disclosure of Invention
The invention aims to provide a high-performance titanium-based low-platinum catalyst to solve the technical problem of poor catalyst effect caused by independent deposition of platinum and metal oxide nanoparticles on the surface of a carbon material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a high-performance titanium-based low-platinum catalyst comprises the following steps in sequence:
s1: dispersing a carbon material in water to obtain a solution A; uniformly mixing an acid solution and a titanium source to obtain a solution B; mixing the solution A and the solution B, carrying out hydrothermal reaction, taking a solid phase, and drying to obtain composite carrier powder;
s2: coating the composite carrier powder on a substrate to form a composite carrier layer; trimethyl (methylcyclopentadienyl) platinum (IV) and oxygen are taken as precursors, nitrogen is taken as carrier gas, and platinum is deposited on the composite carrier layer by an atomic layer deposition method to obtain the low-platinum catalyst;
s3: and sintering the low platinum catalyst in an atmosphere formed by inert gas and reducing gas to obtain the high-performance titanium-based low platinum catalyst.
The scheme also provides a high-performance titanium-based low-platinum catalyst which comprises a carrier formed by a carbon material, wherein platinum and Ti are loaded on the carriernOXWherein x is 2n to 1, and n is 1 to 6; the platinum loading of the catalyst is 4.4-15 wt.%; in the catalyst, the content of vacancy oxygen is 33-65%.
The scheme also provides the application of the high-performance titanium-based low-platinum catalyst in a proton exchange membrane fuel cell, an alkaline anion exchange membrane fuel cell or a metal-air cell.
The principle and the advantages of the scheme are as follows:
the present invention facilitates atomic layer deposition techniques to reduce low loadings of Pt particles by introducing vacancy oxygen (Ov) into titanium oxide and acting as a support in a "two-step process" (S1 and S3). Vacancy oxygen is introduced in both hydrothermal preparation (S1) and hydrogen treatment (S3), wherein the vacancy oxygen in the hydrothermal part is beneficial to atomic layer deposition, and the vacancy oxygen in the hydrogen treatment is beneficial to material property modification. The preparation method of the scheme obviously improves titanium oxide (Ti)nOX) Mid-vacancy oxygen content, vacancy oxygen-enriched TinOXMore easily anchoring Pt atoms, leading Pt precursor to be accurately adsorbed and reduced on Ti in situnOXThe surface effectively avoids the agglomeration phenomenon, so that Pt particles and TinOXForm a three-junction structure with carbon materials, i.e. Pt particles, TinOXAnd carbon material are tightly combined. The construction of an effective 'triple junction' structure is beneficial to improving the performance of the catalyst of the system, and the occurrence of poor catalyst effect caused by the independent deposition of Pt and metal oxide nano particles on the surface of a carbon material is avoided. The unique interface structure (more vacancy oxygen) constructed by the method enhances Pt and TinOXThe strong interaction between the interfaces effectively improves the utilization rate of Pt, thereby improving the activity and stability of the oxygen reduction reaction of the Pt-based catalyst. Further, Ti is introducednOXThe operation method of the vacancy oxygen has the advantages of high safety and simple and convenient operation, and the obtained product has good dispersibility.
The scheme uses an atomic layer deposition means. Atomic layer deposition, as a chemical vapor deposition technique, is an ideal method for preparing metal and metal compound films, as well as highly dispersed noble metal nanoparticles and nanocluster catalysts. According to the method, a gas-phase Pt precursor is alternately pulsed and fed into the reactor to form chemical adsorption on the deposition matrix and react, so that an atomic-scale catalyst is formed, the means of atomic layer deposition for obviously reducing the amount of Pt and the introduction of vacancy oxygen are synergistic, namely the introduction of the vacancy oxygen realizes the anchoring of Pt atoms, the migration and agglomeration of Pt can be effectively avoided in the process of reducing Pt in the atomic layer deposition, the particle size of Pt is reduced, the utilization rate of Pt is improved, and the catalyst product shows excellent catalytic efficiency and stability. According to the deposition mechanism of ALD, how to more effectively deposit Pt nanoparticles on the surface of metal oxide, thereby forming a "triple junction" structure is a technical difficulty. It is a great challenge how to accurately and uniformly deposit Pt and metal oxides on a support material and enhance interfacial interactions and improve catalyst activity and stability. The process sequence of the scheme is very critical to solve the problems. The step S1 provides a precisely confined deposition site, and samples that do not pass S1 also experience S2 and may experience agglomeration, affecting performance. The atomic deposition (S3) must be performed before sintering (S2). If the oxide is excessively reduced before S2 by S3, the oxygen-containing functional group is reduced, and the deposition effect and the catalyst performance of Pt in S2 are affected.
The catalyst prepared by the scheme has a rich 'three-knot' structure, wherein TinOXRich in vacancy oxygen (up to 33.4-65.4%, even 50.2-65.4%), Pt and TinOXClosely contacted and uniformly distributed on the surface of the carbon material carrier. The structure not only reduces the Pt content, but also enables the catalyst to show higher activity and stability for oxygen reduction reaction. Moreover, the catalyst synthesized by the scheme has the advantages, so that the catalyst can be applied to the manufacture of proton exchange membrane fuel cells, alkaline anion exchange membrane fuel cells or metal-air cells to improve the performance of the cells, and the cell cost is reduced by reducing the Pt content. In addition, TinOXThe composite carrier formed by the carbon material has excellent corrosion resistance under acidic conditions and high potential, and the battery performance is further improved.
To sum up, this scheme's beneficial effect lies in:
(1) compared with the prior art, the preparation method is simple and easy to operate, and utilizes TinOXThe vacancy oxygen in the carbon material can effectively and accurately control the platinum deposition site, thereby avoiding the independent deposition of Pt on the carbon material and avoiding the agglomeration of Pt and the waste of raw materials.
(2) Composite carrierTinOXthe/C has excellent corrosion resistance under acidic conditions and high potential, and avoids Pt particle migration and agglomeration caused by carrier corrosion.
(3) Ti in high-performance titanium-based low-platinum catalystnOXRich in vacancy oxygen, more easily anchored platinum atom, and the Pt precursor is accurately adsorbed and reduced in situ on TinOXSurface, strengthened Pt-TinOXStrong interaction between them. The structure ensures that the catalyst is fully contacted with the electrolyte, effectively improves the utilization rate of Pt, and further improves the oxygen reduction reaction activity of the Pt catalyst; effectively avoids Pt dissolution/migration, greatly improves the stability and has good application prospect in the field of composite electrodes.
(4) The deposition process is short in time and extremely high in efficiency, so that the method is extremely easy to carry out scale-up production. Has wide application prospect in proton exchange membrane fuel cells, direct methanol fuel cells and metal-air cells.
Further, in S1, the temperature of the hydrothermal reaction is 120-200 ℃, and the reaction time is 2-6 h. Too high a temperature, too long a reaction time, too low a temperature, and too short a reaction time, all will be applied to TiO2The crystallinity of (a) is affected, resulting in poor effect of introducing vacancy oxygen and poor catalytic effect of the obtained catalyst.
Further, the acid solution is a hydrochloric acid aqueous solution, the volume ratio of hydrochloric acid to water is 1: 2-10, and the addition amount of the titanium source is 1-5 mL of the titanium source added in each 10mL of the acid solution; the dosage ratio of the carbon material to the titanium source is 50 mg: 1 ml-500 mg: 1 ml. The low proportion of the carbon material can lead to poor conductivity of the material; too little titanium source and TiO in the hydrothermal process2The amount of the produced Pt is too small, which is not favorable for the load of the Pt atomic layer deposition. The technical scheme adopts the dosage ratio to ensure that the material has good conductivity and suitable TiO2The amount of production.
Further, the carbon material includes at least one of XC-72, XC-72R, Black Pearls 2000, acetylene Black, Ketjen Black series conductive carbon Black, and carbon nanotubes; the titanium source comprises at least one of titanium isopropoxide, titanium tetrachloride, tetrabutyl titanate, titanium metatitanic acid sulfate and sodium titanate.
XC-72 (American CARBOT company), XC-72R (American CARBOT company), Black Pearls 2000 (American CARBOT company), acetylene Black, Ketjen Black series conductive carbon Black (Japanese lion king company) or carbon nano tubes can be used as the carbon carrier of the catalyst in the scheme. Titanium isopropoxide, titanium tetrachloride, tetrabutyl titanate, titanium metatitanic acid sulfate and sodium titanate can also be used as the titanium source of the catalyst. These materials are stable in performance and readily available.
Further, in S2, the substrate coated with the composite carrier powder is located in a reaction chamber, the temperature of the reaction chamber is 150 to 300 ℃, and the temperature of trimethyl (methylcyclopentadienyl) platinum (IV) is 65 ℃; the atomic layer deposition period is 5-50 cycles; in each cycle, introducing trimethyl (methylcyclopentadienyl) platinum (IV) into the reaction cavity at a flow rate of 100-400 sccm in a pulse mode for 1-300 s; then, purging the nitrogen for 1-300 s at the flow rate of 100-400 sccm; then, introducing oxygen into the reaction cavity in a flow rate of 100-400 sccm and a pulse mode for 1-300 s; finally, the nitrogen is purged for 1-300 s at a flow rate of 100-400 sccm. The reaction conditions realize uniform deposition of Pt particles, and the gas phase Pt precursor is alternately pulsed into the reactor to form chemical adsorption on the deposition substrate and react to form the atomic-scale catalyst.
Further, in S3, the volume ratio of the reducing gas to the inert gas is 1: 10-1: 1; the reducing gas includes at least one of hydrogen, methane, and carbon monoxide, and the inert gas includes at least one of helium, argon, and nitrogen. The reducing gas is too little, and the reducing effect on the Pt precursor is insufficient; however, the amount of the reducing gas is too large, so that the reduction effect of the Pt precursor cannot be effectively improved, and the problem of low gas utilization rate exists.
Further, in S3, during the sintering process, the temperature is raised to 800-1200 ℃ at a rate of 2-10 ℃/min, and then the temperature is maintained for 1-5 h, and the flow rate of the reducing gas is controlled to 10-200 sccm and the flow rate of the inert gas is controlled to 100-200 sccm while the temperature is maintained. At temperatures below 800 c, the resulting product differs from the product obtained in the present solution in the crystalline phase, resulting in poor catalytic performance of the product. The sintering temperature of 1200 ℃ reaches the upper limit of the use temperature of the tube furnace heating method, and the temperature can not be increased any more.
Drawings
FIG. 1 is an X-ray diffraction pattern of a high performance titanium-based low platinum catalyst of example 1 of the present invention.
FIG. 2 shows the electron spin resonance spectra of the high performance titanium-based low platinum catalyst of example 1 and comparative example 1 of the present invention.
FIG. 3 is an X-ray photoelectron spectrum of the high performance titanium-based low platinum catalyst of example 1 and comparative example 1 of the present invention.
FIG. 4 is a graph comparing polarization curves of high performance titanium-based low platinum catalysts of example 1 and comparative example 1 of the present invention in an oxygen reduction reaction.
FIG. 5 is a graph comparing polarization curves of the high performance titanium-based low platinum catalyst of example 1 of the present invention and commercial Pt/C in an oxygen reduction reaction.
FIG. 6 shows 10000 cycles stability test results for high performance Ti-based low Pt catalyst and commercial Pt/C electrode of example 1 of the present invention.
FIG. 7 is a comparison of the discharge curves of the high performance titanium-based low platinum catalyst prepared in example 1 of the present invention before and after 3000 cycles in a hydrogen-oxygen fuel cell.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto. Unless otherwise specified, the technical means used in the following examples and experimental examples are conventional means well known to those skilled in the art, and the materials, reagents and the like used therein are commercially available.
Example 1:
the preparation method of the high-performance titanium-based low-platinum catalyst for the fuel cell comprises the following specific steps:
s1: weighing 400mg of X72R carbon powder, dispersing in 10mL of deionized water, adding a stirrer, and uniformly stirring for 10min at room temperature by using a magnetic stirrer, wherein the label is solution A; dropping 1mL of titanium isopropoxide into 10mL of hydrochloric acid aqueous solution (the volume ratio of hydrochloric acid to water is 1: 2-10, and the volume ratio is 1: 10), and uniformly stirring by ultrasonic waves to mark as solution B. A, B solution is mixed, after even stirring, the solution after even mixing is put into a 50mL polytetrafluoroethylene reaction kettle, and the oven parameter is set as 170 ℃, and the hydrothermal reaction is carried out for 5 hours. After the hydrothermal kettle is naturally cooled to room temperature, repeatedly washing and filtering the solid obtained by the reaction with deionized water, and drying in a vacuum oven at 80 ℃ for 12 hours;
s2: and (3) uniformly coating the composite carrier powder prepared by the step (S1) on a glass slide, putting the glass slide into a deposition chamber of an atomic layer deposition device, and depositing by taking trimethyl (methylcyclopentadienyl) platinum (IV) as a precursor and oxygen as a carrier gas and nitrogen as a carrier gas. Setting the temperature of a sample stage to be 300 ℃, the temperature of a platinum precursor to be 65 ℃ (the temperature of a platinum source can be selected to be 55-75 ℃), and the flow of carrier gas to be 200 sccm; the platinum precursor was pulsed at 100sccm for 2s, purged with nitrogen at 200sccm for 20s, and after the oxygen pulse at 200sccm for 2s, purged with nitrogen at 200sccm for 20s, forming a deposition cycle. Setting the number of deposition turns to be 15 turns;
s3: and placing the sample subjected to atomic layer deposition into a tube furnace, transferring the sample into a quartz boat, placing the quartz boat in a constant-temperature area in the middle of a high-temperature tube furnace, heating the sample to 950 ℃ in mixed gas of hydrogen and argon (1: 3) at a heating rate of 5 ℃/min, and sintering the sample for 4 hours (the flow rates of the hydrogen and the argon are respectively 60 sccm and 180 sccm). And grinding and collecting a sample after sintering is finished to obtain the atomic layer deposition low-platinum loaded titanium-based composite catalyst.
The X-ray diffraction pattern of the titanium-based supported low platinum catalyst prepared in inventive example 1 is shown in fig. 1. Among them, the diffraction angle 2 θ was 41.1 ° and the diffraction peak was carbon, and 39.7 ° corresponded to the Pt (111) crystal plane. Peaks shown at 25.1 °, 41.2 ° and 51.2 ° correspond to Ti, respectively3O5The (110), (024) and (511) planes of (A) and (B), 30.7 DEG, 50.0 DEG and 62.6 DEG respectively correspond to Ti4O7The (122), (304) and (340) crystal planes of (A) and (B), 36.1 DEG and 68.6 DEG respectively correspond to Ti6O11The (1211) and (322) planes of (a). The results show that the catalyst obtained in example 1 has a non-stoichiometric Ti/O ratio of titanium oxide in the form of TinOxX is 2n-1 and is well complexed with platinum and carbon. Platinum loading by nitrolysis of 5mg catalyst, ICP measurement gave the platinum loading of 4.4 wt.% (mass fraction of platinum to total catalyst) for this example. The catalyst prepared according to the scheme has a vacancy oxygen content of 65.4% of all oxygen atoms as measured by XPS detection analysis.
Examples 2-5 are essentially the same as example 1, except for the setting of the partial parameter conditions and the selection of the materials, as specified in Table 1.
Table 1: parameter settings and experimental results of examples 1-5
The dosage of # is the milliliter number of the titanium source added in each 10ml of the acid solution; the amount is the ratio of the amount of the carbon material to the amount of the titanium source.
Comparative example 1
Essentially the same procedure as in example 1, except that: in step S1, commercial TiO is directly used2(P25) in place of solution B. A sample was obtained directly after the end of the deposition in step (2) and was labeled comparative example 1.
The electron spin resonance spectrograms of example 1 and comparative example 1 of the present invention are shown in fig. 2. The catalyst obtained in example 1 has a stronger electron spin resonance wave signal than that of comparative example 1, which indicates that the catalyst obtained in example 1 has more surface vacancy oxygen, and thus, is more likely to excite electrons and has higher electrical conductivity. In addition, these surface-vacancy oxygens can effectively anchor Pt atoms, TinOXStrong interactions occur between Pt.
The X-ray photoelectron spectra of example 1 and comparative example 1 of the present invention are shown in fig. 3. FIG. 3(a) is a diagram of a Pt 4f peak, corresponding to about 70.2eV and 77.5eV for zero valence Pt 0 and oxidized Pt II, respectively. Compared with the Pt II peak in the comparative example 1, the Pt II peak in the example 1 is reduced, the proportion of Pt 0 in the zero valence state is relatively increased, and the oxygen reduction is more favorableAnd (4) carrying out primary reaction. FIG. 3(b) is a spectrum of the O1 s partial peak, and the peak around 530eV corresponds to the lattice oxygen. The lattice oxygen content of example 1 is significantly reduced compared to comparative example 1, indicating that the vacancy oxygen content is higher, which is more favorable for strengthening Pt and TinOXThe two interact with each other at the interface.
The materials prepared in example 1 and comparative example 1 (as catalysts) were tested for oxygen reduction performance as follows: 5mg of the catalyst was dispersed in a mixed solution of 1mI water and isopropyl alcohol, and 50. mu.L of Nafion solution was added thereto to sonicate the suspension. Transferring 10 mu L of the evenly mixed slurry by using a liquid transfer gun, dripping the slurry on a pretreated disk electrode, and airing the slurry at room temperature for later use. The electrochemical test uses an Autolab electrochemical workstation, adopts a traditional three-electrode system, and takes a modified disk electrode as a working electrode (0.196 cm)2) Platinum is used as a counter electrode, a silver/silver chloride (Ag/AgCl) electrode is used as a reference electrode, and electrochemical tests are carried out at room temperature and 0.1mol/L HClO4Is carried out in (1).
The polarization curves of the materials prepared in example 1 of the present invention and comparative example 1 in the oxygen reduction reaction are shown in FIG. 4 (test conditions: rotating disk electrode, O)2Saturated 0.1mol/L HClO4The sweep rate of the solution is 10mV s-1Rotation speed 1600 rpm). It can be seen that the half-wave potential in the polarization curve of the oxygen reduction reaction in example 1 is significantly shifted forward compared to that in comparative example 1, which proves that the introduction of vacancy oxygen can effectively adjust the electronic structure of platinum, so that the catalytic activity is significantly improved.
The polarization curves of inventive example 1 and commercial Pt/C in the oxygen reduction reaction are shown in FIG. 5. Figure 5 shows that example 1, prepared according to the inventive process of this patent, has a significantly improved catalytic activity over commercial platinum carbon at platinum levels (4.4 wt.%) well below commercial 20% Pt/C, with a significant positive shift in both the onset and half-wave potentials, indicating that the platinum catalyst has superior catalytic performance after vacancy electron modulation.
The stability of the low platinum loaded titanium-based composite catalyst prepared in example 1 of the present invention and the commercial Pt/C electrode after 10000 scans is shown in fig. 6. The stability of the catalyst was tested at 0.1mol/L HClO saturated with oxygen4In solution intoLine-by-line multi-circle cyclic voltammetry scanning, the scanning range is 0.6-1.1V (vs. RHE), and the scanning speed is 100mV s-1The number of scanning turns was 10000 turns, after which 0.1M HClO saturated in oxygen was used4Linear voltammetric sweep tests were performed in the electrolyte and the curves were recorded. FIG. 6 shows that commercial Pt/C has a significant decrease in catalytic activity after 10000 cycles of cyclic voltammetry, with a negative shift of 30mV for the half-wave potential, while the electronically regulated catalyst of example 1 has no significant change in activity after 10000 cycles, indicating that Ti is presentnOxThe vacancy on the catalyst can effectively anchor Pt, enhance the interaction between Pt and the carrier and has positive significance on the stability of the catalyst.
The stability test of the low platinum supported titanium based composite catalyst prepared in example 1 of the present invention in a hydrogen-oxygen fuel cell is shown in fig. 7. The specific steps of the battery assembly are as follows: the catalyst dispersion was sprayed on a proton exchange membrane, and the catalyst prepared in example 1 was used in a cathode and commercial platinum carbon in an anode, wherein the platinum contents in the cathode and the anode were 0.1mg, respectivelyPt cm-2And 0.05mgPtcm-2. The hydrogen-oxygen fuel cell uses an Arbin fuel cell testing system, hydrogen is introduced into an anode, oxygen is introduced into a cathode, and the testing temperature is 65 ℃. As shown in FIG. 7, the open circuit voltage of example 1 reached 0.92V, and the maximum power density reached 630mWcm-2And the catalyst still keeps 93.6 percent after 3000 times of cyclic discharge, which shows that the catalyst has better actual catalytic activity and stability.
Comparative example 2
This comparative example is basically the same as example 1 except that the temperature of the sintering treatment was raised to 600 ℃ at a rate of 5 ℃/min. The sintering temperature of comparative example 2 was too low compared to example 1, and the results show that TiO2Is not reduced and is only changed into perovskite crystalline phase TiO2Not forming non-stoichiometric TinOXAnd the components can not introduce vacancy oxygen and improve the conductivity.
Comparative example 3
This comparative example is substantially the same as example 1 except that the amount ratio of the carbon material to titanium isopropoxide was 45 mg: 1 ml. The comparative example 3 has a too low proportion of carbon material and a poor conductivity as compared to example 1.
Comparative example 4
This comparative example is substantially the same as example 1 except that the amount ratio of the carbon material to titanium isopropoxide was 550 mg: lml. Comparative example 4, too little titanium source and TiO in hydrothermal Process compared to example 12The amount of the produced Pt is too small, which is not favorable for the load of the Pt atomic layer deposition.
Comparative example 5
This comparative example is basically the same as example 1 except that S3 in example 1 was first performed and S2 in example 1 was then performed. The method specifically comprises the following steps:
and (3) placing the composite carrier powder prepared by the step S1 in a quartz boat, moving the quartz boat to a tubular furnace, placing the quartz boat in a constant-temperature area in the middle of a high-temperature tubular furnace, heating the quartz boat to 950 ℃ at a heating rate of 5 ℃/min in a mixed gas of hydrogen and argon (1: 3), and sintering the quartz boat for 4 hours (the flow rates of the hydrogen and the argon are 60 sccm and 180sccm respectively). And after sintering, putting the sintered material into a deposition chamber of an atomic layer deposition device, and depositing by taking trimethyl (methyl cyclopentadienyl) platinum (IV) as a precursor and oxygen as a carrier gas and nitrogen as a carrier gas. Setting the temperature of a sample stage to be 300 ℃, the temperature of a platinum precursor to be 65 ℃ (the temperature of a platinum source can be selected to be 55-75 ℃), and the flow of carrier gas to be 200 sccm; the platinum precursor was pulsed at 100sccm for 2s, purged with nitrogen at 200sccm for 20s, and after the oxygen pulse at 200sccm for 2s, purged with nitrogen at 200sccm for 20s, forming a deposition cycle. The number of deposition turns was set to 15. And grinding the mixture after the above process is finished, and collecting a sample to obtain the atomic layer deposition low-platinum loaded titanium-based composite catalyst.
Compared with example 1, the comparative example 5 is subjected to hydrogen sintering reduction, surface oxygen atoms are seriously lost, so that Pt precursor adsorption sites are lacked in the atomic layer deposition process, and the platinum loading capacity is reduced.
Comparative example 6
This comparative example is substantially the same as example 1 except that the hydrothermal reaction temperature of S1 was 100 ℃. Too low hydrothermal temperature affects TinOxThe crystallinity of (3) results in undesirable catalytic effect of the catalyst.
Table 2: results of Performance test of the catalysts of comparative examples 1 to 6
The foregoing is merely an example of the present invention and common general knowledge in the art of designing and/or characterizing particular aspects and/or features is not described in any greater detail herein. It should be noted that, for those skilled in the art, without departing from the technical solution of the present invention, several variations and modifications can be made, which should also be regarded as the protection scope of the present invention, and these will not affect the effect of the implementation of the present invention and the practicability of the patent. The scope of the claims of the present application shall be determined by the contents of the claims, and the description of the embodiments and the like in the specification shall be used to explain the contents of the claims.
Claims (10)
1. A preparation method of a high-performance titanium-based low-platinum catalyst is characterized by comprising the following steps: comprises the following steps in sequence:
s1: dispersing a carbon material in water to obtain a solution A; uniformly mixing an acid solution and a titanium source to obtain a solution B; mixing the solution A and the solution B, carrying out hydrothermal reaction, taking a solid phase, and drying to obtain composite carrier powder;
s2: coating the composite carrier powder on a substrate to form a composite carrier layer; depositing platinum on the composite carrier layer by using an atomic layer deposition method by using a platinum source and oxygen as precursors and nitrogen as carrier gas to obtain a low-platinum catalyst;
s3: and sintering the low platinum catalyst in an atmosphere formed by inert gas and reducing gas to obtain the high-performance titanium-based low platinum catalyst.
2. The method of claim 1, wherein the catalyst is prepared by the following steps: in S1, the temperature of the hydrothermal reaction is 120-200 ℃, and the reaction time is 2-6 h.
3. The method for preparing a high performance titanium-based low platinum catalyst according to claim 2, wherein: the acid solution is a hydrochloric acid water solution, the volume ratio of hydrochloric acid to water is 1: 2-10, and the addition amount of the titanium source is 1-5 mL of the titanium source added in each 10mL of the acid solution; the dosage ratio of the carbon material and the titanium source is 50 mg: lml-500 mg: 1 ml.
4. The method for preparing a high performance titanium-based low platinum catalyst according to claim 3, wherein: the carbon material comprises at least one of XC-72, XC-72R, Black Pearls 2000, acetylene Black, Ketjen Black series conductive carbon Black and carbon nano tubes; the titanium source comprises at least one of titanium isopropoxide, titanium tetrachloride, tetrabutyl titanate, titanium metatitanic acid sulfate and sodium titanate.
5. The method of claim 1, wherein the catalyst is prepared by the following steps: in S2, the substrate coated with the composite carrier powder is located in a reaction chamber, and the temperature of the reaction chamber is 150-300 ℃; the platinum source is trimethyl (methylcyclopentadienyl) platinum (IV), and the temperature of the platinum source is 55-75 ℃; the atomic layer deposition period is 5-50 cycles; in each cycle, a platinum source is introduced into the reaction cavity in a flow rate of 100-400 sccm and a pulse mode for 1-300 s; then, purging the nitrogen for 1-300 s at the flow rate of 100-400 sccm; then, introducing oxygen into the reaction cavity in a flow rate of 100-400 sccm and a pulse mode for 1-300 s; finally, the nitrogen is purged for 1-300 s at a flow rate of 100-400 sccm.
6. The method of claim 1, wherein the catalyst is prepared by the following steps: in S3, the volume ratio of the reducing gas to the inert gas is 1: 10-1: 1; the reducing gas includes at least one of hydrogen, methane, and carbon monoxide, and the inert gas includes at least one of helium, argon, and nitrogen.
7. The method for preparing a high performance titanium-based low platinum catalyst according to claim 6, wherein: in S3, the temperature is raised to 800-1200 ℃ at a speed of 2-10 ℃/min during the sintering treatment, then the temperature is maintained for 1-5 h, the flow rate of the reducing gas is controlled to be 10-200 sccm while the temperature is maintained, and the flow rate of the inert gas is controlled to be 100-200 sccm.
8. A catalyst prepared by the process of any one of claims 1 to 7 for the preparation of a high performance titanium based low platinum catalyst.
9. The catalyst of claim 8, wherein: comprising a carrier formed of a carbon material having platinum and Ti supported thereonnOXWherein x is 2n to 1, and n is 1 to 6; the platinum loading of the catalyst is 4.4-15 wt.%; in the catalyst, the content of vacancy oxygen is 33.4-65.4%.
10. Use of the catalyst of claim 9 in a proton exchange membrane fuel cell, an alkaline anion exchange membrane fuel cell or a metal air cell.
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