CN111229214B - Preparation method for regulating and controlling size of platinum-ruthenium alloy nanoparticles - Google Patents
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Abstract
本发明涉及材料化学技术领域，具体公开了一种调控铂钌合金纳米颗粒尺寸的制备方法，包括二氧化硅光子晶体模板制备和碳前驱体溶液的制备，将铂前驱体和钌前驱体溶解于THF和CHCl3中得混合溶液；准备嵌段共聚物、碳前驱体溶液、原硅酸四乙酯和质子酸溶液，依次加入混合溶液中，搅拌得透明溶液；将透明溶液加入到二氧化硅光子晶体模板中，干燥后升温固化得红棕色固体；将红棕色固体煅烧，得灰色固体；将灰色固体采用强碱或强酸刻蚀，后过滤干燥，采用本专利中的技术方案利用不同嵌段共聚物，其PPO端分子量的大小不同，从而连接了不同数量的铂钌前驱体，从而精准调控铂钌合金纳米颗粒尺寸。
The invention relates to the technical field of material chemistry, and specifically discloses a preparation method for regulating the size of platinum-ruthenium alloy nanoparticles, including the preparation of a silicon dioxide photonic crystal template and the preparation of a carbon precursor solution. A mixed solution was obtained in THF and CHCl 3 ; the block copolymer, carbon precursor solution, tetraethyl orthosilicate and protonic acid solution were prepared, added to the mixed solution in turn, and stirred to obtain a transparent solution; the transparent solution was added to the silica In the photonic crystal template, the reddish-brown solid is obtained by heating and curing after drying; the reddish-brown solid is calcined to obtain a gray solid; the gray solid is etched with strong alkali or strong acid, and then filtered and dried, and the technical scheme in this patent is used to utilize different blocks The copolymers have different molecular weights at the PPO end, thus connecting different amounts of platinum-ruthenium precursors, so as to precisely control the size of platinum-ruthenium alloy nanoparticles.
Description
Technical Field
The invention relates to the technical field of material chemistry, in particular to a preparation method for regulating and controlling the size of platinum-ruthenium alloy nanoparticles.
Background
A great deal of research shows that the catalytic activity of the Pt alloy is closely related to the element composition and the alloy size, and the smaller the size is, the narrower the distribution is, and the more uniform the particle composition is, the better the catalytic activity is. At present, among various methods capable of achieving controllable alloy particle size, a common method includes reduction of alloy nanoparticles in a solution directly on a commercial carbon material (activated carbon, Vulcan carbon, etc.), or preparation of a monodisperse alloy colloidal solution and then loading on the surface of the commercial carbon material by electrostatic adsorption.
However, these methods have several significant drawbacks: (1) the size of the platinum-ruthenium alloy nanoparticles is difficult to accurately regulate and control; (2) it is difficult to further reduce the size of the alloy particles, the migration, aggregation and growth of the alloy particles can be caused during the heat treatment in the current preparation process, and the uniformly dispersed alloy catalyst cannot be obtained. (3) The commonly used commercial carbon materials are composed of a disordered accumulation of carbon particles, the pores are complex and almost all consist of micropores below 2nm, resulting in a very large mass transfer resistance during the reaction, and a low utilization of the pores and active sites resulting in a poor catalytic activity of the catalyst as a whole.
Based on the problems, the application provides a preparation method of the ordered mesoporous carbon supported platinum-ruthenium alloy nanoparticle catalyst, which can accurately regulate and control the size of the alloy nanoparticles, has the advantages of uniform particle dispersion, high methanol oxidation activity and high stability.
Disclosure of Invention
The invention provides a preparation method of an ordered mesoporous carbon supported platinum-ruthenium alloy nanoparticle catalyst, which can accurately regulate and control the size of alloy nanoparticles, has the advantages of uniform particle dispersion, high methanol oxidation activity and high stability.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method for regulating and controlling the size of platinum-ruthenium alloy nanoparticles comprises the preparation of a silicon dioxide photonic crystal template and the preparation of a carbon precursor solution, and is characterized in that: the method comprises the following steps:
step 1: dissolving a platinum precursor and a ruthenium precursor in a mass ratio of 1 (1-5) in THF (tetrahydrofuran) and CHCl 3 Obtaining a mixed solution;
step 2: preparing a block copolymer, a carbon precursor solution and tetraethyl orthosilicate in a mass ratio of 1 (0.3-5) (0.1-3), and a protonic acid solution with a substance amount of 0-15 mmol, sequentially adding the protonic acid solution into the mixed solution obtained in the step (1), and stirring to obtain a red transparent solution;
and step 3: adding the red transparent solution obtained in the step (2) into a silicon dioxide photonic crystal template, drying, and heating and curing to obtain a reddish brown solid;
and 4, step 4: calcining the reddish brown solid in the step 3 at 500-800 ℃ to obtain a gray solid;
and 5: and 4, etching the gray solid obtained in the step 4 by using strong alkali or strong acid, filtering and drying to obtain the ordered mesoporous carbon-supported PtRu alloy nanoparticle catalyst.
The technical principle and the effect of the technical scheme are as follows:
1. according to the scheme, a hydrophobic chain end (PPO end) of a block copolymer and a metal precursor are assembled to form a core of a micelle, a hydrophilic terminal (PEO end) is connected with the carbon precursor to form an outer layer of the micelle, a carbon skeleton is formed by the PEO end in a high-temperature carbonization process, the PPO end is decomposed at high temperature and volatilized to form a mesoporous channel, residual metal atoms in the same micelle form alloy particles at a mesoporous channel pore wall, and the alloy particles are difficult to migrate and agglomerate in the high-temperature carbonization process due to the anchoring effect of carbon, so that the ordered mesoporous carbon-supported platinum-ruthenium alloy nanoparticle catalyst is obtained.
2. According to the scheme, the different molecular weights of the PPO ends of the block copolymers are skillfully utilized (namely, the different molecular weights of the PPO ends are realized by selecting different types of block copolymers), so that different numbers of platinum and ruthenium precursors are connected, and the accurate regulation and control of the size of the platinum and ruthenium alloy nanoparticles are realized.
3. The silicon dioxide photonic crystal template used in the scheme has communicated ordered macropores and mesoporous channels left after removal, so that a large surface area is formed, a large number of exposed active sites are provided, the reaction kinetics of the platinum-ruthenium alloy nanoparticle catalyst are enhanced, meanwhile, the three-dimensional ordered macroporous structure is favorable for electrolyte permeation, and compared with commercial PtRu/C or Pt/C, the silicon dioxide photonic crystal template has higher methanol oxidation activity and stability, and is suitable for large-scale industrial application.
Further, in the step 1, the platinum precursor is one of platinum acetylacetonate, platinum tetraammine bicarbonate and platinum tetrachlorodiammine, and the ruthenium precursor is one of ruthenium acetylacetonate, ruthenium triphenylphosphine chloride and ruthenium pentaammine dichloride.
Has the advantages that: the organic metal salt is common organic metal salt and is easy to purchase.
Further, the block copolymer in the step 2 is one of F127, F68, F88 or F108.
Has the advantages that: the molecular weights of hydrophobic chain ends (PPO ends) of four block copolymers F127, F68, F88 and F108 are different, and platinum and ruthenium nanoparticles with different particle sizes are obtained by selecting different block copolymers.
Further, the protonic acid solution in the step 2 is one of a hydrochloric acid solution, a sulfuric acid solution and a nitric acid solution.
Has the advantages that: the hydrochloric acid solution, the sulfuric acid solution and the nitric acid solution are all commonly used protonic acid solutions and are easy to purchase.
Further, the temperature rise solidification in the step 3 is completed in two steps, the temperature is firstly raised to 90-115 ℃ and kept for 10-14 h, and then the temperature is raised to 120-140 ℃ and kept for 10-14 h.
Has the advantages that: the solidification is completed step by step, so that the formed solid mesostructure is more stable.
Further, the calcination in the step 4 is completed in two steps, the reddish brown solid is calcined at 200-400 ℃ for 2-4 h, and then calcined at 600-800 ℃ for 2-4 h.
Has the advantages that: the calcination is performed at 200-400 ℃ for 2-4 h mainly to burn off the block copolymer in the reddish brown solid, and the calcination is performed at 600-800 ℃ for 2-4 h to graphitize the carbon precursor so as to improve the conductivity.
Further, in the step 5, etching is performed at 60-70 ℃.
Has the advantages that: the etching can be rapidly finished at the temperature of 60-70 ℃, and the etching speed is improved.
Further, the specific method for preparing the silicon dioxide photonic crystal template comprises the steps of mixing deionized water and ethanol in a volume ratio of 1:6, adding an ammonia water solution into the mixture, and stirring to obtain a mixed solution; adding tetraethyl orthosilicate with the volume ratio of 1:1 to the water into the mixed solution to obtain a milky white solution; adding tetraethyl orthosilicate and ethanol into the milky white solution, continuously stirring, and then obtaining the silicon dioxide photonic crystal template through centrifugal washing and evaporation.
Has the beneficial effects that: the method in the scheme is adopted to obtain the silicon dioxide photonic crystal template for preparing the catalyst.
Further, the preparation method of the carbon precursor comprises the steps of liquefying phenol at the temperature of 30-80 ℃, adding a NaOH aqueous solution and a formalin solution to form a mixture, keeping the mixture at the temperature of 30-90 ℃ for 0.5-3 hours to obtain a carbon precursor aqueous solution, dehydrating the carbon precursor aqueous solution, and adding the dehydrated carbon precursor aqueous solution into a tetrahydrofuran solution to form the carbon precursor solution.
Has the advantages that: and (3) dehydrating the prepared carbon precursor aqueous solution, and then adding the dehydrated carbon precursor aqueous solution into a tetrahydrofuran solution to form the carbon precursor solution which is an anhydrous solution.
Further, after filtering and washing to be neutral in the step 5, drying treatment is carried out.
Has the advantages that: the ordered mesoporous carbon-supported PtRu alloy nanoparticle catalyst prepared in the way has higher purity.
Drawings
FIG. 1 is a TEM image of a PtRu alloy nanoparticle catalyst prepared in example 1 of the present invention;
fig. 2 is a statistical diagram of the particle size distribution of the PtRu alloy nanoparticle catalyst prepared in example 1 of the present invention;
FIG. 3 is a TEM image of a PtRu alloy nanoparticle catalyst prepared in example 2 of the present invention;
fig. 4 is a statistical chart of the particle size distribution of the PtRu alloy nanoparticle catalyst prepared in example 2 of the present invention;
FIG. 5 is a TEM image of a PtRu alloy nanoparticle catalyst prepared in example 3 of the present invention;
fig. 6 is a statistical view of the particle size distribution of the PtRu alloy nanoparticle catalyst prepared in example 3 of the present invention;
FIG. 7 is a TEM image of a PtRu alloy nanoparticle catalyst prepared in example 4 of the present invention;
fig. 8 is a statistical view of the particle size distribution of the PtRu alloy nanoparticle catalyst prepared in example 4 of the present invention;
fig. 9 is an XRD pattern of the PtRu alloy nanoparticle catalyst prepared in example 1 of the present invention;
FIG. 10 shows the cyclic voltammograms of methanol oxidation for the PtRu alloy nanoparticle catalyst prepared in example 1 of the present invention, and commercial Pt/C catalysts and commercial PtRu/C catalysts.
Detailed Description
The following is further detailed by way of specific embodiments:
the preparation work includes: preparing hard template silicon dioxide photonic crystals and preparing a carbon precursor solution.
The preparation method of the hard template silicon dioxide photonic crystal comprises the following specific steps:
deionized water and ethanol in a volume ratio of 1:6 were mixed in a round-bottomed flask, and an aqueous ammonia solution in a volume ratio of 1:0.5 to water was added thereto, and the resulting solution was continuously stirred at 30 ℃ for 30 minutes. And then adding tetraethyl orthosilicate with the volume ratio of 1:1 to the water into the mixed solution, and continuing stirring for 12 hours to obtain a milky white solution.
And (2) mixing tetraethyl orthosilicate and ethanol in a volume ratio of 1:1, transferring the mixture into a constant-pressure dropping funnel, slowly dropping the mixed solution into the milky white solution at a rate of one drop per 3 seconds, further continuously stirring for 12 hours, finally centrifugally washing the obtained product with the mixed solution of water and ethanol at a rotating speed of 7000r for 7 minutes, dispersing the product in the ethanol solution after washing for three times, and forming the hard template silicon dioxide photonic crystal after natural sedimentation and ethanol evaporation.
In addition, the preparation method of the carbon precursor solution comprises the following specific steps:
phenol was added to the flask and placed in a 45 ℃ water bath to be liquefied, and then an aqueous NaOH (20 wt%) solution and a formalin solution (37 wt%) were continuously added thereto, and then the mixture was maintained at 70 ℃ for 1h, thereby obtaining a low molecular weight carbon precursor solution.
After cooling the low molecular weight carbon precursor solution to room temperature, the pH of the carbon precursor solution was further adjusted to neutral (pH 7.0) using an HCl solution, and the solution was placed in a vacuum oven to remove water from the solution at a temperature lower than 52 ℃ to obtain a carbon precursor powder, which was dissolved in a tetrahydrofuran solution to form a carbon precursor solution (containing no water) having a concentration of 20 wt%.
Example 1
A preparation method for regulating and controlling the size of platinum-ruthenium alloy nanoparticles comprises the following steps:
step 1: weighing platinum acetylacetonate and ruthenium acetylacetonate at a mass ratio of 1:1, and dissolving in Tetrahydrofuran (THF) and CHCl 3 And (4) obtaining a mixed solution.
Step 2: weighing the block copolymer F127, the carbon precursor solution and tetraethyl orthosilicate in a mass ratio of 1:1:1, preparing a hydrochloric acid solution with a substance concentration of 7mmol, sequentially adding the hydrochloric acid solution into the mixed solution obtained in the step 1, and stirring for 30-50 min to obtain a red transparent solution.
And step 3: and (3) pouring the red transparent solution obtained in the step (2) into a silicon dioxide photonic crystal template, then placing the silicon dioxide photonic crystal template in a vacuum oven at the temperature of 30 ℃ for vacuum drying for 24h, raising the temperature to 110 ℃ for keeping for 11h, further raising the temperature to 130 ℃, and continuing to keep for 12h to obtain the cured reddish brown solid.
And 4, step 4: transferring the reddish brown solid obtained in the step 3 into a tubular furnace, and performing temperature control for 1 ℃ min -1 Heating to 350 deg.C, calcining for 2 hr, and heating at 1 deg.C for min -1 The temperature rising rate is heated to 700 ℃, calcined for 3 hours, and then naturally cooled to room temperature to obtain gray solid.
And 5: transferring the gray solid obtained in the step 4 into a polytetrafluoroethylene high-pressure reaction kettle, and reactingThe reactor is filled with 2mol L of water -1 And (3) etching the solution at 60 ℃, then performing suction filtration, washing with water to neutrality (PH is 7), and performing vacuum drying to obtain the ordered mesoporous carbon supported PtRu alloy nanoparticle catalyst.
Examples 2 to 8
Examples 2 to 8 are the same as example 1, except that the platinum precursor, ruthenium precursor, protonic acid solution, block copolymer and process parameters used are different as shown in table 1.
TABLE 1
And (3) experimental detection:
1. TEM and particle size statistics
Detecting the platinum-ruthenium alloy particle catalyst prepared in the examples 1-8 by using a Transmission Electron Microscope (TEM), and randomly selecting 200 particles to detect the particle size distribution, wherein a TEM image and a particle size distribution statistical image of the PtRu alloy nanoparticle catalyst prepared in the example 1 are respectively shown in FIG. 1 and FIG. 2; a TEM image and a statistical view of the particle size distribution of the PtRu alloy nanoparticle catalyst prepared in example 2 are shown in fig. 3 and 4, respectively; a TEM image and a statistical view of the particle size distribution of the PtRu alloy nanoparticle catalyst prepared in example 3 are shown in fig. 5 and 6, respectively; a TEM image and a statistical view of the particle size distribution of the PtRu alloy nanoparticle catalyst obtained in example 4 are shown in fig. 7 and 8, respectively.
As can be observed by combining fig. 1 to 8, the catalyst particles formed by the preparation methods provided in embodiments 1 to 8 have good dispersibility and uniform particle size distribution, and the PtRu alloy particles are perfectly embedded in the mesoporous channels, and it can be found through an electron microscope photograph that the carbon carrier in the catalyst has a large pore and mesoporous structure and a large surface area, and a large number of exposed active sites are provided to enhance the reaction kinetics of the catalyst.
By randomly selecting 200 alloy nanoparticles, it is found that the average particle size of the nanoparticles in the catalyst prepared in example 1 is 1.52nm, the average particle size of the nanoparticles in the catalyst prepared in example 2 is 2.90nm, the average particle size of the nanoparticles in the catalyst prepared in example 3 is 3.90nm, and the average particle size of the nanoparticles in the catalyst prepared in example 4 is 4.41nm, so that the precise control of the size of the PtRu alloy particles can be realized by changing the molecular weight of the hydrophobic chain end of the block copolymer.
2、XRD
An X-ray diffractometer is used for detecting the platinum-ruthenium alloy nanoparticles prepared in the embodiments 1-8, taking the embodiment 1 as an example, the XRD spectrum of the platinum-ruthenium alloy nanoparticles is shown in fig. 9, and it can be observed from fig. 9 that the PtRu nanoparticle catalyst synthesized in the embodiment 1 has an obvious graphite (002) peak, which is formed in the high-temperature calcination process of the carbon carrier.
Meanwhile, the PtRu nanoparticle catalyst is observed to show an obvious Pt (111) peak at a position of 2 theta approximately equal to 41 degrees, and compared with a diffraction peak value of 111 crystal face 2 theta 39.66 degrees of pure Pt (JCPDS file No.04-0802), the positive shift is obviously generated, because Ru atoms enter a face-centered cubic lattice of Pt atoms to form a PtRu alloy when the PtRu nanoparticle catalyst is synthesized, and the catalyst prepared by the method is further proved to exist in an alloy form.
3. Comparative experiment:
comparative example 1: the Jonhson-Matthey company, UK, commercializes a Pt/C (60% by weight platinum) catalyst.
Comparative example 2: the company Jonhson-Matthey, UK, commercializes a PtRu/C (60% by mass platinum) catalyst.
The PtRu alloy nanoparticle catalysts obtained in examples 1-8 and comparative examples 1 and 2 are respectively prepared into working electrodes, graphite and silver/silver chloride (Ag/AgCl) electrodes are respectively used as auxiliary electrodes and reference electrodes, nitrogen is introduced into 0.1mol/L perchloric acid solution until saturation, and then the working electrodes are placed in N 2 In the middle of 50mv s -1 The sweep rate of the electrode is circularly swept for 60 circles in a potential interval of 0V to 1.2V, and the electrode is activated and then is saturated by nitrogen and has a height of 0.1mol/LA cyclic voltammogram test of methanol was carried out in a chloric acid solution +0.5mol/L methanol solution at a sweep rate of 50 mv/s.
Taking the test result of example 1 as an example, as shown in fig. 10, wherein curve a is the methanol oxidation cyclic voltammetry curve of the PtRu alloy nanoparticle catalyst obtained in example 1; curve B is the methanol oxidation cyclic voltammogram of a commercial Pt/C (60% platinum by mass) catalyst; and curve C is the methanol oxidation cyclic voltammetry curve for a commercial PtRu/C (60% platinum by mass) catalyst.
It can be observed from fig. 10 that the catalysts prepared by the preparation methods provided in examples 1 to 8 have better methanol oxidation activity than the conventional Pt/C and PtRu/C catalysts, and the peak current densities are 3.4 times and 4.9 times of those of the conventional Pt/C and PtRu catalysts, respectively.
The If/Ib ratio of the PtRu alloy nanoparticle catalyst prepared in the example 1 is as high as 2.51, and is far higher than that of commercial PtRu/C (1.08) and commercial Pt/C (0.68), so that the catalyst prepared by the preparation method provided in the examples 1-8 has more excellent anti-poisoning performance than that of the commercial catalyst.
The foregoing is merely an example of the present invention and common general knowledge of known specific structures and features of the embodiments is not described herein in any greater detail. It should be noted that, for those skilled in the art, without departing from the structure of the present invention, several changes 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.
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