CN111509236A - One-dimensional porous platinum-containing alloy nanowire catalyst and preparation method thereof - Google Patents
One-dimensional porous platinum-containing alloy nanowire catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of electrocatalysis, and particularly relates to a one-dimensional porous low-platinum nanowire catalyst applicable to oxygen reduction reaction in various energy conversion technologies and a preparation method thereof. Dissolving platinum metal salt and one or more other transition metal salts in a solvent, adding a surfactant and a reducing agent, and reacting at a certain temperature to prepare the platinum alloy nanowire with a one-dimensional structure morphology; and then, preparing the one-dimensional porous platinum-containing alloy nanowire in an acid corrosion mode. The catalyst has a one-dimensional nanowire and porous structure, has high oxygen reduction catalytic activity and stability, and can be applied to oxygen reduction catalysts in various energy conversion devices. The method has the characteristics of high yield, simple synthesis process, high catalytic activity, high efficiency and the like, is suitable for large-scale industrial production, and has important significance for promoting the commercialization process of various energy conversion devices.
Description
Technical Field
The invention belongs to the field of electrocatalysis, and particularly relates to a one-dimensional porous low-platinum nanowire catalyst applicable to oxygen reduction reaction in various energy conversion technologies and a preparation method thereof.
Background
With the rapid development of economic society, people are confronted with energy shortage and environmental problems, and development of green energy and exploration of new energy conversion technologies are imperative. The oxygen reduction reaction is the core reaction of many electrochemical energy technologies, especially proton exchange membrane fuel cells and metal air cells. Because the kinetics process of the oxygen reduction reaction is relatively slow, the catalyst widely adopted at present still uses expensive and scarce noble metal platinum as a main active component, and the high cost of the catalyst caused by the expensive and scarce noble metal platinum becomes an important factor for restricting the commercialization progress of fuel cells and a plurality of electrochemical energy technologies. Therefore, the preparation and research of the cathode oxygen reduction catalyst with low cost, high activity and high stability have very important significance for the development and popularization of a plurality of new energy technologies.
The method is considered to be a very effective method for improving the catalytic activity of the catalyst for oxygen reduction and reducing the catalyst cost by regulating and controlling the near-surface structure and components of the platinum-based catalyst, namely exposing the active area of the catalyst as much as possible and improving the utilization efficiency of platinum. The synergistic effect of the platinum-based catalyst (assembly, ligand and strain) brought about by doping with transition metals will optimize the binding strength of the platinum-oxygen intermediate; in addition, by preparing structures such as hollow nanospheres, nano-frames or nano-cages, catalytic active sites of the catalyst can be greatly exposed, the material transmission performance in the reaction process is enhanced, and the oxygen reduction catalytic activity of the catalyst is further improved. Chen et al first prepared PtNi rich in nickel metal by3Polyhedra, which are then dispersed in an inorganic hexane or chloroform solution and exposed to air at room temperature. By reaction over a period of two weeks, PtNi3Conversion of polyhedron to Pt by gradual corrosion3Ni hollow frame structure, and roasting at 400 deg.C under inert gas to obtain Pt with smooth platinum layer surface structure3Ni hollow frame structure, the catalyst shows extremely high electrocatalytic activity and stability (Science2014,343, 1339-1343). Xia et al by first preparing palladium nanocubes or octahedra, anddepositing 2-3 layers of platinum atomic layers on the surface by taking the palladium core platinum as a seed to prepare the Pd @ Pt core-shell structure cube or octahedron taking the palladium core platinum as a shell. Placing the product in hydrochloric acid and FeCl at 100 DEG C3The solution is mixed for 4 hours, and finally the platinum nanocages or platinum hollow octahedrons with hollow structures are obtained (Science 2015,349, 412-416). The catalyst also shows better oxygen reduction activity and stability due to greatly improving the utilization rate of platinum. However, we should see that the preparation of the hollow structure catalyst is complicated and the reported porous structure usually has a relatively large diameter; in addition, under actual operating conditions, the catalyst with the zero-dimensional structure is difficult to meet the requirements of long-life energy conversion devices and devices because nanoparticles fall off and migrate from the surface of the carbon carrier. In contrast, one-dimensional nanostructures are considered to have higher stability than the same material in the zero-dimension due to their unique anisotropy, high flexibility, and high electrical conductivity. On the other hand, different from the single contact point of the zero-dimensional nano-particles, the one-dimensional nano-structure has more contact sites with the carbon carrier, and the stability of the structure is also enhanced. Recently, yellow et al prepared one-dimensional platinum alloy nanowires such as PtCo, PtNi or PtCu by doping Co, Ni or Cu, etc., all showed higher oxygen reduction catalytic activity and stability compared with 0-dimensional platinum or platinum alloy, and also confirmed the advantage of one-dimensional structure applied to oxygen reduction reaction (nat. Commun.2016,7,11850; adv. Mater.2018,30,1705515). However, a large amount of noble metal platinum is still distributed in the one-dimensional platinum alloy catalyst, so that the utilization rate of platinum is low, and the reduction of the use cost of the catalyst is not facilitated.
In summary, despite many efforts to apply the platinum alloy catalyst with a hollow or one-dimensional structure to oxygen reduction in various energy conversion technologies, the existing catalyst still has the problems of complicated preparation technology, poor catalyst stability, being not beneficial to industrial production, and the like. In addition, in the current prior art and patents, no relevant report of applying the nanowire with one-dimensional porous platinum-based alloy to the actual fuel cell single cell test is found.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention provides a one-dimensional porous low-platinum nanowire catalyst and a preparation method thereof, wherein the method comprises the steps of dissolving a platinum metal salt and one or more other transition metal salts in a solvent, adding a surfactant and a reducing agent, stirring and ultrasonically reacting at a certain temperature to prepare a platinum alloy nanowire with a one-dimensional structure morphology; and then, preparing the one-dimensional porous platinum-containing alloy nanowire in an acid corrosion mode. The catalyst has a one-dimensional nanowire and porous structure, has high oxygen reduction catalytic activity and stability, and can be applied to oxygen reduction catalysts in various energy conversion devices. Compared with commercial platinum-carbon catalysts, under the condition of the same catalytic effect, the method can reduce the use amount of noble metals by 50-90%, and can greatly reduce the application cost of the oxygen reduction catalyst. The method has the characteristics of high yield, simple synthesis process, high catalytic activity, high efficiency and the like, is suitable for large-scale industrial production, and has important significance for promoting the commercialization process of the multi-energy conversion device.
In order to achieve the above objects, according to one aspect of the present invention, there is provided a method for preparing a one-dimensional porous low platinum nanowire, comprising the steps of:
(1) preparing a precursor solution: the precursor solution comprises a solution obtained by dissolving a platinum metal salt and one or more transition metal salts in a first solvent, a surfactant and a reducing agent;
(2) preparing a one-dimensional platinum-containing alloy nanowire: the precursor solution is subjected to oxidation reduction reaction at a certain temperature to synthesize a one-dimensional platinum-containing alloy nanowire;
(3) preparing a one-dimensional porous platinum-containing alloy nanowire: and (3) corroding the one-dimensional platinum-containing alloy nanowire obtained in the step (2) by an acid corrosion method to remove part of transition metal in the alloy nanowire, so as to obtain the one-dimensional porous platinum-containing alloy nanowire.
Preferably, the platinum metal salt in the step (1) is platinum acetylacetonate, chloroplatinic acid, potassium chloroplatinate or diamine tetrachloroplatinum, the transition metal salt is ferric acetylacetonate, cobalt acetylacetonate, nickel acetylacetonate, copper acetylacetonate, palladium acetylacetonate, ferric nitrate, ferric acetate, cobalt nitrate, copper nitrate, palladium chloride, cobalt acetate, copper chloride, niobium chloride, lead nitrate, tin oxide, molybdenum chloride or tantalum chloride, the concentration range of the platinum metal salt in the precursor solution is 0.1-10 mg/m L, and the concentration range of the transition metal salt in the precursor solution is 0.1-10 mg/m L.
Preferably, the surfactant in step (1) is one or more of polyvinylpyrrolidone, dodecyltrimethylammonium chloride and hexadecyltrimethylammonium bromide; the reducing agent is one or more of formaldehyde, ascorbic acid, glucose and sucrose; the first solvent is deionized water, alcohols, a mixture of the alcohols and ketone, a mixture of the alcohols and ester, oleylamine, octadecene or oleic acid; the reaction temperature of the oxidation-reduction reaction is 150-230 ℃; the reaction time is 1-15 h.
Preferably, the preparation method further comprises the following steps:
(4) and (4) uniformly mixing the one-dimensional porous platinum-containing alloy nanowire obtained in the step (3) with a carrier and a second solvent to obtain the loaded one-dimensional porous platinum-containing alloy nanowire.
Preferably, the second solvent is water, ethanol, acetone or cyclohexane; the carrier is a carbon material, nitride, carbide or phosphide; the carbon material is XC-72R carbon black, carbon nano tubes, carbon nano fibers or graphene.
Preferably, the loading amount of the one-dimensional porous platinum-containing alloy nanowire on the carrier is 1 wt% -60 wt%.
According to another aspect of the present invention, there is provided a one-dimensional porous platinum-containing alloy nanowire, comprising a one-dimensional platinum-containing alloy nanowire and a plurality of hollow sphere structures penetrating through the nanowire, wherein the length of the nanowire is 0.3 to 3 μm, the diameter of the hollow sphere structure is 3 to 15nm, the platinum content in the alloy nanowire is 40 to 95%, the alloy is an alloy of platinum and one or more transition metals, and the transition metal is Fe, Co, Ni, Cu, Sn, Pd, Nb, Mo, Pb, or Ta.
Preferably, the one-dimensional porous platinum-containing alloy nanowire is loaded on the surface of a carrier, wherein the carrier is a carbon material, a nitride, a carbide or a phosphide; the carbon material is XC-72R carbon black, carbon nano tubes, carbon nano fibers or graphene.
According to another aspect of the invention, an electrode material based on the one-dimensional porous platinum-containing alloy nanowire is provided, the surface of the electrode material is coated with a catalyst, and the active component of the catalyst is the one-dimensional porous platinum-containing alloy nanowire; the loading amount of platinum in the electrode material is 1-500 mu g/cm2。
Preferably, the electrode material is obtained by the following method: and mixing the one-dimensional porous platinum-containing alloy nanowire with an alcohol solution containing a binder, dispersing to prepare slurry, coating the slurry on the surface of a working electrode substrate, and drying to obtain the electrode material based on the one-dimensional porous platinum-containing alloy nanowire.
Preferably, the adhesive is polytetrafluoroethylene emulsion, fluorocarbon resin emulsion or perfluorosulfonic acid resin emulsion, and the mass percentage of the used amount of the adhesive is 0.5-20 wt% of the total amount of the one-dimensional porous platinum-containing nanowire and the dry polymer resin calculated by the dry polymer resin; the alcohol is absolute ethyl alcohol, methanol, isopropanol or ethylene glycol; the working electrode substrate is glassy carbon, foamed nickel, a titanium sheet, a titanium mesh, a platinized titanium sheet, a platinum sheet or a platinum mesh; the drying mode comprises natural air drying, radiation drying under an infrared lamp or drying in an oven.
According to another aspect of the invention, a battery material based on the one-dimensional porous platinum-containing alloy nanowire is provided, and the battery material comprises a proton exchange membrane, wherein a catalyst is loaded on two sides of the proton exchange membrane, and the active component of the catalyst is the one-dimensional porous platinum-containing alloy nanowire; the loading amount of platinum in the battery material is 0.1-0.5 mg/cm2。
In general, compared with the prior art, the above technical solution contemplated by the present invention can achieve the following beneficial effects:
(1) the invention provides a method for preparing a one-dimensional porous platinum alloy nanowire, which is characterized in that a platinum metal salt and one or more transition metal salts are dissolved in a solvent, a surfactant and a reducing agent are added, and the reaction is carried out at a certain temperature to prepare the platinum alloy nanowire with a one-dimensional structure appearance; and then, preparing the one-dimensional porous platinum-containing alloy nanowire in an acid corrosion mode. The synthesis method is simple and efficient, is simple and convenient to operate, does not need inert gas protection in the synthesis process, greatly reduces the use amount of noble metal platinum, can realize large-scale production and preparation of the catalyst, and can effectively reduce the industrial cost of the catalyst;
(2) the one-dimensional porous platinum-containing alloy nanowire provided by the invention comprehensively utilizes the characteristics of high utilization rate of platinum with a hollow nanostructure, high stability of the one-dimensional structure, excellent performance of an alloy catalyst and the like, so that the prepared one-dimensional porous platinum alloy nanowire has excellent oxygen reduction activity, stability and corrosion resistance, and can meet the application of the catalyst in various energy conversion processes;
(3) the one-dimensional porous platinum-containing alloy nanowire catalyst prepared by the invention has extremely high catalytic activity and stability for oxygen reduction reaction, and electrode tests show that the activity of the catalyst is 10-30 times that of the current commercial Pt/C catalyst, and the catalyst has excellent corrosion resistance and cycle stability. In addition, the membrane electrode single cell prepared by the catalyst also shows excellent activity in the test.
Drawings
FIG. 1 shows one-dimensional solid binary Pt prepared in example 13Ni2SEM and TEM images of nanowires.
FIG. 2 shows one-dimensional hollow binary Pt prepared in example 13Ni2TEM and HRTEM images of the alloy nanowires.
FIG. 3 shows a one-dimensional hollow ternary Pt prepared in example 23Ni2Pd0.5TEM and HRTEM images of the alloy nanowires.
FIG. 4 shows a one-dimensional hollow ternary Pt prepared in example 33Ni2Rh0.5TEM and HRTEM images of the alloy nanowires.
FIG. 5 shows a one-dimensional hollow Pt prepared in example 43Ni2Ru0.5TEM and HRTEM images of the alloy nanowires.
Figure 6 is a comparison of oxygen reduction polarization curves and mass activity for example 1 and commercial Pt/C catalysts at the same Pt loading.
FIG. 7 is a comparison of the stability of example 1 and commercial Pt/C catalysts.
FIG. 8 is a comparison of cell performance of example 1 and commercial Pt/C.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention provides a preparation method of a one-dimensional porous low-platinum nanowire, which comprises the following steps:
(1) preparing a one-dimensional platinum-containing alloy nanowire: dissolving platinum metal salt and one or more transition metal salts in a solvent to obtain a precursor solution, mixing the precursor solution with a surfactant and a reducing agent under stirring, and carrying out oxidation-reduction reaction at a certain temperature to synthesize a one-dimensional platinum-containing alloy nanowire; under the action of a reducing agent, platinum metal salt and transition metal salt are reduced into platinum and transition metal alloy, and under the guiding action of a surfactant, the one-dimensional platinum-containing alloy nanowire is obtained.
(2) Preparing a one-dimensional porous platinum-containing alloy nanowire: and (2) corroding the one-dimensional platinum-containing alloy nanowire obtained in the step (1) by an acid corrosion method to remove part of transition metal in the alloy nanowire, so as to obtain the one-dimensional porous platinum-containing alloy nanowire. Part of transition metal in the alloy nanowire is corroded and removed by an acid corrosion method, and relatively inert platinum is reserved, so that the one-dimensional porous platinum-containing alloy nanowire is formed, and the platinum proportion in the porous platinum-containing alloy nanowire is increased by 20-50% compared with the platinum proportion of a solid platinum-containing alloy nanowire before corrosion.
In some embodiments, the platinum metal salt is platinum acetylacetonate, chloroplatinic acid, potassium chloroplatinate, or diaminetetrachloroplatinum, the transition metal salt is iron acetylacetonate, cobalt acetylacetonate, nickel acetylacetonate, copper acetylacetonate, palladium acetylacetonate, ferric nitrate, ferric acetate, cobalt nitrate, copper nitrate, palladium chloride, cobalt acetate, copper chloride, niobium chloride, lead nitrate, tin oxide, molybdenum chloride, or tantalum chloride, the concentration range of the platinum metal salt in the precursor solution is 0.1-10 mg/m L, and the concentration range of the transition metal salt in the precursor solution is 0.1-10 mg/m L.
In some embodiments, the platinum alloy comprises a binary Pt alloy of Pt with any one of Fe, Co, Ni, Cu, Sn, Pd, Nb, Mo, Pb, or Ta or a ternary or multicomponent Pt alloy of two or more thereof.
In the step (1), the reducing agent is used for reducing platinum metal salt and transition metal salt into platinum and transition metal alloy, and the surfactant is used as a guiding agent for obtaining the one-dimensional platinum-containing alloy nanowire. In some embodiments, the surfactant of step (1) is one or more of polyvinylpyrrolidone, dodecyltrimethylammonium chloride, and hexadecyltrimethylammonium bromide; the reducing agent is one or more of formaldehyde, ascorbic acid, glucose and sucrose; the solvent is deionized water, alcohols, a mixture of the alcohols and ketone, a mixture of the alcohols and ester, oleylamine, octadecene or oleic acid; the reaction temperature of the oxidation-reduction reaction is 150-230 ℃; the reaction time is 1-15 h.
In some embodiments, the mixing under stirring conditions is specifically: mixing for 0.5-3 hr under magnetic stirring or ultrasonic condition, wherein the reaction vessel is a normal or high pressure reaction kettle, high temperature glass bottle, glassware or flask lined with polytetrafluoroethylene or stainless steel cylinder.
The one-dimensional porous platinum-containing alloy nanowire prepared by the method can also be loaded on a carrier, and in some embodiments, the specific method comprises the following steps: and (3) adding the one-dimensional porous platinum-containing alloy nanowire obtained in the step (2) and a carrier into a solvent, and uniformly mixing under a stirring condition to obtain the supported one-dimensional porous platinum-containing alloy nanowire.
In some embodiments, the solvent is water, ethanol, isopropanol, acetone, or cyclohexane; the carrier is a carbon material, nitride, carbide or phosphide; the carbon material is XC-72R carbon black, carbon nano tubes, carbon nano fibers or graphene.
In some embodiments, the one-dimensional porous platinum-containing alloy nanowires have been found to have better catalytic performance when used as an active component of a catalyst of an electrode material when the loading of the nanowires on a carrier is 1-60 wt%.
In some embodiments, when the carrier is a carbon material, the carbon material is a pretreated carbon material carrier, and the pretreated carbon material has better hydrophilicity and electrical conductivity, the pretreatment method of the carbon material carrier comprises the steps of weighing 1-20g of the carbon material, adding the carbon material into a 100-500m L beaker, injecting acetone or cyclohexane with the volume of 3/5 of the beaker, stirring for 0.5-24h at room temperature, filtering and washing, then drying in vacuum at 60-100 ℃, roasting the dried carbon material for 1-6h at 300-550 ℃ under the protection of high-purity argon or nitrogen atmosphere, and then roasting in HNO at 550 DEG C3And H2SO4(the molar percentage is 3:1-1:5, the solution concentration is 1-6 mol/L) heating and refluxing the mixed solution for 3-12h, keeping the temperature at 60-90 ℃, finally centrifuging or filtering the solution, washing the solution with deionized water to be neutral, and drying the solution in an oven at 60-90 ℃ for 2-24h in vacuum to obtain the pretreated carbon material carrier.
The invention also provides a one-dimensional porous platinum-containing alloy nanowire (the structure is similar to a pearl necklace), which comprises the one-dimensional platinum-containing alloy nanowire and a plurality of hollow sphere structures penetrating through the nanowire, wherein the sphere structures are approximate spheres, the length of the nanowire is 0.3-3 mu m, the diameter of each hollow sphere structure is 3-15nm, the platinum content in the alloy nanowire is improved by 20-50% compared with that of a solid platinum alloy nanowire due to corrosion of part of transition metal, the alloy is an alloy of platinum and one or more transition metals, and in some embodiments, the transition metal is Fe, Co, Ni, Cu, Sn, Pd, N, Mo, Pb or Ta.
In order to improve the catalytic performance of the alloy nanowire used as an electrode material catalyst, the alloy nanowire can also be loaded on the surface of a carrier, and in some embodiments, the carrier is a carbon material, a nitride, a carbide or a phosphide; the carbon material is XC-72R carbon black, carbon nano tubes, carbon nano fibers or graphene.
In some embodiments, the alloy nanowires can be loaded on the surface of the carrier by the following method: and adding the one-dimensional porous platinum-containing alloy nanowire and a carrier into a solvent, and uniformly mixing under a stirring condition to obtain the supported one-dimensional porous platinum-containing alloy nanowire.
The invention provides a catalyst which can be used as an electrode material based on a one-dimensional porous platinum-containing alloy nanowire, the surface of the electrode material is coated with the catalyst, and the active component of the catalyst is the one-dimensional porous platinum-containing alloy nanowire; the loading amount of platinum in the electrode material is 1-500 mu g/cm2。
In some embodiments, the electrode material is obtained by the following method: and mixing the one-dimensional porous platinum-containing alloy nanowire with an alcohol solution containing a binder, dispersing to prepare slurry, coating the slurry on the surface of a working electrode substrate, and drying to obtain the electrode material based on the one-dimensional porous platinum-containing alloy nanowire.
In some embodiments, the adhesive is polytetrafluoroethylene emulsion, fluorocarbon resin emulsion or perfluorosulfonic acid resin emulsion, and the mass percentage of the adhesive used is 0.5-20 wt% of the total amount of the one-dimensional porous platinum-containing nanowires and the dry polymer resin calculated by the dry polymer resin; the alcohol is absolute ethyl alcohol, methanol, isopropanol or ethylene glycol; the working electrode substrate is glassy carbon, foamed nickel, a titanium sheet, a titanium mesh, a platinized titanium sheet, a platinum sheet or a platinum mesh; the drying mode comprises natural air drying, radiation drying under an infrared lamp or drying in an oven.
The one-dimensional porous platinum-containing alloy nanowire provided by the invention can also be used as a catalyst of a battery material, such as an active component of a catalyst loaded on the surface of a proton exchange membrane of a single cell. The invention provides a one-dimensional porous structure based on theThe battery material comprises a proton exchange membrane, wherein catalysts are loaded on two sides of the proton exchange membrane, and active components of the catalysts are the one-dimensional porous platinum-containing alloy nanowires; the loading amount of platinum in the battery material is 0.1-0.5 mg/cm2。
The invention discloses a one-dimensional porous low-platinum alloy nanowire catalyst and a preparation method thereof. The preparation method of the catalyst comprises the following steps: firstly, preparing a one-dimensional platinum-based alloy nanowire rich in transition metal components, and finally obtaining the porous low-platinum nanowire catalyst with a one-dimensional structure through the acid corrosion action. The catalyst can be used as a cathode catalyst of various energy conversion technologies, and has high electrocatalytic activity and stability; in addition, the membrane electrode prepared by using the catalyst as a cathode catalyst also has better cell performance. The catalyst can greatly reduce the use amount of noble metal in the catalysis process, and can greatly reduce the application cost of the fuel cell. The method has the characteristics of high yield, simple synthesis process, high catalytic activity, high efficiency and the like, and is suitable for large-scale industrial production.
The following are examples:
example 1:
is a porous platinum-containing alloy nanowire which is one-dimensional porous binary Pt3Ni2The nanowire, wherein the platinum content is 83.3%, is obtained according to the following preparation method:
(1) preparation of one-dimensional solid platinum alloy nanowire
In a fume hood, a 100 ml beaker was taken and platinum acetylacetonate (Pt (acac))210mg), Nickel acetylacetonate (Ni (acac)24.84mg) and dodecyl trimethyl ammonium bromide (CTAB,100mg) are added into 10m L oleylamine solution, mixed and stirred evenly, ultrasonic treatment is carried out for 2 hours, thus obtaining light yellow transparent solution, the solution is transferred into a 50ml flask, oil bath heating is carried out, the temperature of an oil bath kettle is raised to 180 ℃ within 30 minutes, reaction is carried out for 3 hours under the temperature, natural cooling is carried out, reactants are centrifuged, 10000 r/min is carried out for 5 minutes, and cyclohexane/absolute ethyl alcohol (volume ratio is 1:3) is used for mixingCleaning the reactant by the synthetic solution, and continuing centrifuging; repeating the process for 3 times, and naturally drying the obtained product to obtain one-dimensional Pt3Ni2Solid nanowires.
(2) 30 ml of glacial acetic acid were added to a 100 ml beaker, and 30 mg of Pt were added3Ni2And (4) solid nanowires, performing ultrasonic treatment for 30 minutes, uniformly mixing, and sealing the beaker by using a sealing film. And (3) putting the sealed beaker into an oil bath kettle, reacting for 3 hours at the temperature of 80 ℃, and naturally cooling. Washing the sample with deionized water for 3 times to obtain one-dimensional hollow Pt3Ni2Nanowire with a platinum content of 93%.
(3) Structural morphology characterization and performance test of catalyst
(A) Structural morphology characterization and component analysis of the catalyst:
the structure and the microscopic surface appearance of the product nanowire are observed by adopting a Scanning Electron Microscope (SEM) and a Transmission Electron Microscope (TEM), and the specific element contents of different products are determined by adopting inductively coupled plasma emission spectroscopy (ICP-OES). FIG. 1 shows one-dimensional solid binary Pt prepared in example 13Ni2SEM and TEM images of nanowires. FIG. 2 shows one-dimensional hollow binary Pt prepared in example 13Ni2TEM and HRTEM images of the alloy nanowires. As can be seen, the solid alloy nanowire consists of a plurality of solid spheres connected in series with the nanowire, the length of the nanowire is 0.3-2 microns, and the diameter of the solid sphere structure is 8-15 nm. After the etching treatment, it can be seen that the length and diameter of the nanowires are not significantly changed. The one-dimensional hollow platinum-containing alloy nano structure is formed by connecting a nanowire in series with a plurality of (hollow) spherical structures, the length of the nanowire is 0.3-2 microns, and the diameter of each (hollow) spherical structure is 8-15 nm. (B) And (3) testing the catalytic performance of cathode oxygen reduction: 0.1M HClO saturated in oxygen4In the scanning, the scanning speed is set to 10mV/s, and the polarization curve scanning is carried out by adopting the electrode rotating speed of 1600 rpm. Using a three-electrode system at 0.1MHClO4In the solution, uninterrupted cyclic voltammetric scans were performed at a sweep rate of 50mV/s, ranging from 0.6 to 1.05V vs. RHE, and the value of the electrochemical activity specific surface area (ECSA) of the catalyst was recorded every 2000 cycles of the scan.
As described aboveIn the examples, the electrode catalytic material was obtained as follows: 1. firstly, loading a nanowire catalyst on the surface of carbon powder, and specifically implementing the process as follows: weighing 20mg of hollow nanowire catalyst, putting the hollow nanowire catalyst into a 50ml beaker, adding 10ml of cyclohexane, and carrying out ultrasonic treatment for 30 min; adding 80mg carbon powder (XC-72R) into the mixed solution, continuing to perform ultrasonic treatment for 30min, performing centrifugal filtration, washing with mixed solution of cyclohexane and ethanol (volume ratio of 1:3) for 3 times, and drying in an oven at 50 deg.C for 12 h. 2. And (2) taking 5mg of the prepared supported alloy nanowire catalyst, wherein the loading capacity of the alloy nanowire on the carrier is 20%, putting the alloy nanowire catalyst into a 10ml beaker, adding 2ml of nafion (0.25 wt%) ethanol mixed solution, and carrying out ultrasonic treatment for 30min to obtain catalyst slurry. 10 microliter of the slurry was applied to the surface of a platinum-carbon electrode (diameter 5mm, area 0.196 cm)2) Naturally drying to prepare an electrode catalytic material for later use, wherein the platinum loading in the electrode material is 25.5 mu g/cm2。
Figure 6 is an oxygen reduction polarization curve for example 1 and a commercial Pt/C catalyst at the same Pt loading. FIG. 7 is a comparison of the stability of example 1 and commercial Pt/C catalysts. It can be seen that the catalytic activity of the catalyst, whether it is a solid or hollow catalyst, is far superior to that of the platinum-carbon catalyst, 5.1 and 12.1 times that of the platinum-carbon catalyst, respectively.
The testing methods of the catalyst related to the invention for the oxygen reduction performance of the cathode and the stability of the catalyst are the same as the testing methods except for special description.
Example 2:
one-dimensional porous ternary Pt3Ni2Pd0.5Nanowires, in which the platinum content is 77.4%, were used as catalysts for the electrode material. The preparation method comprises the following steps:
the preparation and testing methods were completely the same as in example 1 except that palladium acetylacetonate (2.35mg) was added during the above synthesis, the supported alloy nanowires had a supported alloy nanowire catalyst loading of 22% on the support, and the electrode material prepared in this example had a platinum loading of 21.6 μ g/cm2. The catalyst obtained in this example had an oxygen reduction performance 6.8 times that of the commercial Pt/C catalyst.
FIG. 3 shows a one-dimensional hollow ternary Pt prepared in example 23Ni2Pd0.5TEM and HRTEM images of the alloy nanowires. It can be seen that the one-dimensional hollow ternary Pt3Ni2Pd0.5The alloy nanowire consists of a nanowire and a plurality of hollow sphere structures penetrating through the nanowire, wherein the length of the nanowire is 0.3-3 microns, and the diameter of each hollow sphere structure is 5-15 nm.
Example 3:
one-dimensional porous ternary Pt3Ni2Ir0.5Nanowires, with a platinum content of 77.6%, were used as catalysts for the electrode material. The preparation method comprises the following steps:
the preparation and testing methods were completely the same as in example 1 except that iridium acetylacetonate (1.4mg) was added during the synthesis, the loading of the alloy nanowire catalyst on the carrier in the supported alloy nanowire was 20%, and the platinum loading in the electrode material prepared in this example was 21.8 μ g/cm2. The catalyst obtained in this example had an oxygen reduction performance 9.3 times that of the commercial Pt/C catalyst.
FIG. 4 shows a one-dimensional hollow ternary Pt prepared in example 33Ni2Rh0.5TEM and HRTEM images of the alloy nanowires. It can be seen that the one-dimensional hollow ternary Pt3Ni2Rh0.5The alloy nanowire consists of a nanowire and a plurality of hollow sphere structures penetrating through the nanowire, the length of the nanowire is 0.5-2.5 mu m, and the diameter of each hollow sphere structure is 5-12 nm.
Example 4:
one-dimensional porous ternary Pt3Ni2Ru0.5A nanowire having a platinum content of 77.7%. Which is used as a catalyst for electrode materials. The preparation method comprises the following steps:
the preparation and testing methods were completely the same as in example 1 except that ruthenium acetylacetonate (1.7mg) was added during the synthesis, the loading of the alloy nanowire catalyst on the support in the supported alloy nanowire was 20%, and the platinum loading in the electrode material prepared in this example was 21.2 μ g/cm2. Oxygen reduction of the catalyst obtained in this exampleThe performance was 9.8 times that of the commercial Pt/C catalyst.
FIG. 5 shows a one-dimensional hollow Pt prepared in example 43Ni2Ru0.5TEM and HRTEM images of the alloy nanowires. It can be seen that the one-dimensional hollow ternary Pt3Ni2Ru0.5The alloy nanowire consists of a nanowire and a plurality of hollow sphere structures penetrating through the nanowire, wherein the length of the nanowire is 0.3-2 microns, and the diameter of each hollow sphere structure is 5-15 nm.
Example 5:
supported one-dimensional porous binary Pt3Ni2Nanowires, Pt3Ni2and/C, which is used as a catalyst for the electrode material. The preparation method comprises the following steps:
one-dimensional porous binary Pt prepared in the example3Ni2The nanowires are exactly the same as in example 1. A100 ml beaker was taken and 20mg of Pt was weighed3Ni2Nanowires were added to a beaker along with 80mg of commercial XC-72R carbon powder (carbopol) and 50ml of cyclohexane, stirred magnetically for 12h, and filtered. Washing with deionized water for 3 times, oven drying the obtained filter cake in a 60 deg.C oven, grinding into powder to obtain Pt with mass fraction of 16.7%3Ni2a/C catalyst. The loading amount of the alloy nanowire catalyst on the carrier in the supported alloy nanowire is 20%, and the platinum loading amount in the electrode material prepared in the example is 25.5 mu g/cm2。
The catalyst prepared in this example had an oxygen reduction performance 12.1 times that of the commercial Pt/C catalyst.
Example 6:
supported one-dimensional porous ternary Pt3Ni2Ru0.5Nanowire (Pt)3Ni2Ru0.5/C) wherein the platinum content was 77.7%, which was used as a catalyst for an electrode material. The preparation method comprises the following steps:
except for the use of Pt in the loading process described above3Ni2Ru0.5Replacement of Pt3Ni2(20mg) except that the preparation and test methods are completely the same as those of example 5, the alloy nano in the supported alloy nanowireThe loading of the catalyst on the support was 20%, and the platinum loading in the electrode material prepared in this example was 21.2. mu.g/cm2. The catalyst obtained in this example had an oxygen reduction performance 8.1 times that of the commercial Pt/C catalyst.
Example 7:
a single cell, which comprises a proton exchange membrane, wherein two sides of the proton exchange membrane are loaded with load type one-dimensional porous binary Pt3Ni2The load capacity of the alloy nanowire catalyst on the carrier in the load type alloy nanowire is 16.6%. The cells were prepared and tested for cell performance as follows:
the performance of the fuel cell as a catalyst for the cathode was tested on a fuel cell testing system (Arbin Instruments, USA). The preparation method of the slurry for spraying the catalyst comprises the following steps: the weighed supported one-dimensional porous alloy nanowire catalyst prepared in the example 1, isopropanol and Nafion (5 wt%) were mixed and sonicated for 1 hour, wherein the alloy nanowire catalyst accounted for 75% of the total weight of the catalyst and Nafion (5 wt%). Then spraying catalyst on one side of a Nafion212(DuPont, USA) proton exchange membrane by adopting a spraying process to prepare a membrane electrode serving as a cathode, wherein the active surface area of the catalyst is 5cm-2Platinum loading of 0.15mgcm-2. The proton exchange membrane is firstly used with 0.5M H before use2SO4The solution was treated in a water bath at 80 ℃ for 12h and then rinsed 3-5 times with deionized water.
By a similar method, an anode catalyst slurry was prepared using a commercial JM Pt/C catalyst and sprayed on the other side of the Nafion212 membrane to form an anode catalyst layer with a platinum loading of 0.1mgcm-2。
In the same manner, a membrane electrode was prepared by spraying a commercial JM Pt/C catalyst on both sides of a Nafion212 membrane as a performance comparison membrane electrode of this example, the amount of platinum loading: cathode with platinum loading of 0.15mgcm-2(ii) a Anode, platinum loading 0.1mgcm-2Finally, two sheets of gas diffusion layer carbon paper (GD L) and the prepared MEA were hot pressed at 600 lbs, 120 ℃ for 5 minutes to assemble a single cell.
Fig. 8 is a comparison of the cell performance of commercial Pt/C of example 7 and it can be seen that the cell made in this example has a power density of 1.5 times that of commercial platinum carbon (JM Pt/C) and an output power at 0.6V of 1.7 times that of the commercial platinum carbon catalyst at the same platinum loading on the cathode.
From the above data, it can be seen that the one-dimensional porous platinum alloy nanowire catalyst prepared by the present invention shows better catalytic activity and stability than commercial Pt/C on both the oxygen reduction test of the cathode and the single cell test.
The commercial Pt/C catalysts mentioned in the present invention are all commercial JM Pt/C catalysts with a platinum content of 20%.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A preparation method of a one-dimensional porous low-platinum nanowire is characterized by comprising the following steps:
(1) preparing a precursor solution: the precursor solution comprises a solution obtained by dissolving a platinum metal salt and one or more transition metal salts in a first solvent, a surfactant and a reducing agent;
(2) preparing a one-dimensional platinum-containing alloy nanowire: the precursor solution is subjected to oxidation reduction reaction at a certain temperature to synthesize a one-dimensional platinum-containing alloy nanowire;
(3) preparing a one-dimensional porous platinum-containing alloy nanowire: and (3) corroding the one-dimensional platinum-containing alloy nanowire obtained in the step (2) by an acid corrosion method to remove part of transition metal in the alloy nanowire, so as to obtain the one-dimensional porous platinum-containing alloy nanowire.
2. The method according to claim 1, wherein the platinum metal salt in step (1) is platinum acetylacetonate, chloroplatinic acid, potassium chloroplatinate or diaminetetrachloroplatinum, the transition metal salt is iron acetylacetonate, cobalt acetylacetonate, nickel acetylacetonate, copper acetylacetonate, palladium acetylacetonate, ferric nitrate, ferric acetate, cobalt nitrate, copper nitrate, palladium chloride, cobalt acetate, copper chloride, niobium chloride, lead nitrate, tin oxide, molybdenum chloride or tantalum chloride, the concentration of the platinum metal salt in the precursor solution is in the range of 0.1 to 10mg/m L, and the concentration of the transition metal salt in the precursor solution is in the range of 0.1 to 10mg/m L.
3. The method according to claim 1, wherein the surfactant in step (1) is one or more of polyvinylpyrrolidone, dodecyltrimethylammonium chloride and hexadecyltrimethylammonium bromide; the reducing agent is one or more of formaldehyde, ascorbic acid, glucose and sucrose; the first solvent is deionized water, alcohols, a mixture of the alcohols and ketones, a mixture of the alcohols and esters, oleylamine, octadecene or oleic acid.
4. The method according to claim 1, wherein the redox reaction in the step (2) is carried out at a reaction temperature of 150 to 230 ℃; the reaction time is 1-15 h.
5. The method of claim 1, further comprising the steps of:
(4) and (4) mixing the one-dimensional porous platinum-containing alloy nanowire obtained in the step (3) with a carrier and a second solvent to obtain the loaded one-dimensional porous platinum-containing alloy nanowire.
6. The method of claim 5, wherein the second solvent is water, ethanol, acetone, or cyclohexane; the carrier is a carbon material, nitride, carbide or phosphide; the carbon material is XC-72R carbon black, carbon nano tubes, carbon nano fibers or graphene.
7. A one-dimensional porous platinum-containing alloy nanowire is characterized by comprising the one-dimensional platinum-containing alloy nanowire and a plurality of hollow sphere structures penetrating through the nanowire, wherein the length of the nanowire is 0.3-3 mu m, the diameter of each hollow sphere structure is 3-15nm, the platinum content in the alloy nanowire is 40-95%, the alloy is an alloy of platinum and one or more transition metals, and the transition metals are Fe, Co, Ni, Cu, Sn, Pd, Nb, Mo, Pb or Ta.
8. The one-dimensional porous platinum-containing alloy nanowire of claim 7, which is loaded on the surface of a carrier, wherein the carrier is a carbon material, a nitride, a carbide or a phosphide; the carbon material is XC-72R carbon black, carbon nano tubes, carbon nano fibers or graphene.
9. An electrode material based on the one-dimensional porous platinum-containing alloy nanowires according to claim 7 or 8, wherein the surface of the electrode material is coated with a catalyst, and the active component of the catalyst is the one-dimensional porous platinum-containing alloy nanowires according to claim 6 or 7; the loading amount of platinum in the electrode material is 1-500 mu g/cm2。
10. A cell material based on the one-dimensional porous platinum-containing alloy nanowires of claim 7 or 8, wherein the cell material comprises a proton exchange membrane, a catalyst is supported on two sides of the proton exchange membrane, and the active component of the catalyst is the one-dimensional porous platinum-containing alloy nanowires of claim 7 or 8; the loading amount of platinum in the battery material is 0.1-0.5 mg/cm2。
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