CN110627030A - Platinum phosphide nano-catalyst, preparation method thereof and application thereof in electrocatalytic oxygen reduction - Google Patents

Platinum phosphide nano-catalyst, preparation method thereof and application thereof in electrocatalytic oxygen reduction Download PDF

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CN110627030A
CN110627030A CN201910888541.5A CN201910888541A CN110627030A CN 110627030 A CN110627030 A CN 110627030A CN 201910888541 A CN201910888541 A CN 201910888541A CN 110627030 A CN110627030 A CN 110627030A
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金明尚
郭瑞雲
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Xian Jiaotong University
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
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    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/08—Other phosphides

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Abstract

The invention provides a platinum phosphide nano-catalyst, a preparation method thereof and application thereof in electrocatalytic oxygen reduction, comprising the following steps: 1) dispersing a platinum catalyst in a solvent, and uniformly stirring to obtain a platinum catalyst dispersion liquid; 2) adding a phosphorus source into the platinum catalyst dispersion liquid, uniformly mixing, reacting at a certain temperature, and centrifuging and washing after the reaction is finished to obtain the platinum phosphide nano-catalyst. The method synthesizes the platinum phosphide nano-catalyst with a specific electronic structure by diffusing phosphorus atoms generated by decomposing a phosphorus source into the platinum catalyst at a certain temperature. The preparation method has the advantages of simple flow, low cost, good repeatability, no environmental pollution and convenient mass preparation, and the prepared platinum phosphide nano-catalyst shows far higher catalytic activity and stability than a commercial platinum/carbon catalyst in an electrocatalytic oxidation-reduction reaction, thereby having good application prospect.

Description

Platinum phosphide nano-catalyst, preparation method thereof and application thereof in electrocatalytic oxygen reduction
Technical Field
The invention belongs to the field of nano science, and particularly relates to a platinum phosphide nano catalyst, a preparation method thereof and application thereof in electrocatalytic oxygen reduction.
Background
The platinum catalyst shows excellent catalytic performance in the fields of energy, chemistry and petrochemical industry, and particularly plays a role in fuel cells, automobile exhaust purification, hydrogenation, dehydrogenation and other industrial catalytic reactions. However, due to the scarcity of platinum resources and the concentration in a few countries and regions, the price of platinum is expensive and the use cost is extremely high, which seriously hinders the large-scale application of platinum in modern industries. Therefore, the method for improving the catalytic performance of the platinum catalyst and reducing the platinum dosage becomes a great research hotspot of energy science at present, and has great significance for promoting economic development and saving resources.
Alloying platinum by introducing a second phase transition metal (such as palladium, gold, cobalt, nickel, copper, iron, lead, etc.) is a strategy for effectively improving the performance of the platinum catalyst. The method mainly improves the number of surface active sites of platinum or changes the binding energy of platinum with reactants, reactant intermediates and products by changing the electronic structure (5d empty rail) of platinum, thereby achieving the purposes of improving the catalytic activity of platinum and reducing the platinum dosage. However, the second phase transition metal component in the catalyst is easy to undergo corrosion dissolution and Ostwald ripening process (Nano Energy 2019,60,111-118) under the conditions of low pH value, high oxygen concentration, high humidity, different potentials and the like, so that the activity of the catalyst is damaged in the using process, the service life is shortened, and the process of commercial scale application of the catalyst is hindered. In addition, the platinum alloying technology is limited by its complicated preparation method and the use of expensive transition metals (such as gold and silver), so that it is not feasible to develop conditions in industry.
Recent research results show that compared with the modification of a platinum catalyst by adding a second phase metal element, the addition of a non-metal atom (such as H, B, N, C or P) into the metal catalyst has a larger influence on the electronic structure (nat. Comm.2014,5,5787, J.Mater. chem.A 2019,7,4714.), and further has better improvement on the catalytic performance. However, due to the strong bonding energy between platinum atoms and the large bonding energy (306.7 kJ/mol) (CRC press,2007), doping non-metal atoms into a platinum lattice to form PtX (X ═ H, B, N, C, P, or the like) remains a great challenge.
In recent years, transition metal phosphides (e.g., phosphorous compounds) have been usedNickel phosphide, cobalt phosphide, iron phosphide, rhodium phosphide, ruthenium phosphide and the like) has the advantages of low raw material cost (avoiding the use of second-phase transition metal), various preparation modes, high catalytic activity and stability and the like, and is widely applied to the research of electrocatalysis, energy storage, photocatalysis, chemical catalysis and the like. The porous surface oxidized cobalt phosphide nano-catalyst is reported to have good electrocatalytic oxygen reduction performance (J.Power Sources,2017,363,87-94), and the rhodium phosphide nano-catalyst shows high catalytic activity and stability in both electrocatalytic hydrogen evolution and oxygen evolution reactions (J.Am.chem.Soc.,2017,139, 5494-. The surface of the palladium catalyst can be rapidly modified by adding a phosphorus source to improve the selectivity of the palladium catalyst in the carbon monoxide catalytic reaction (patent CN107413359A), but the prepared catalyst is palladium-palladium phosphide with a core-shell structure, wherein the palladium phosphide is in an amorphous state, and the structure cannot be stably maintained in the catalytic reaction. In addition, although there have been many studies on metal phosphide, few studies on platinum phosphide nano-catalyst have been reported at present due to the limitations of difficult synthesis of platinum phosphide nano-crystal, harsh production conditions, complex preparation and few controllable factors. Such as PtP formation on a platinum catalyst core by Cramerikawa et al2A surface layer and is applied to a fuel cell (patent CN 102365775B). However, the catalyst prepared by the method can only be synthesized on a carrier material, has no universality, needs vacuum and high-temperature calcination and other conditions, has high process cost, and is not beneficial to industrial large-scale production. Therefore, developing a low-cost and efficient way to obtain a platinum phosphide nano-catalyst with excellent catalytic activity and stability is a great challenge while having great significance.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a platinum phosphide nano-catalyst, a preparation method thereof and application thereof in electrocatalytic oxygen reduction.
The invention is realized by the following technical scheme:
a preparation method of a platinum phosphide nano-catalyst comprises the following steps:
step 1, dispersing a platinum catalyst in a solvent to obtain a platinum catalyst dispersion liquid;
and 2, adding a phosphorus source into the platinum catalyst dispersion liquid obtained in the step 1, uniformly stirring, reacting at the temperature of 200-360 ℃ for 1-20h, and centrifuging and washing after the reaction is finished to obtain the platinum phosphide nano-catalyst.
Preferably, in step 1, the platinum catalyst is a platinum nanocrystal, a platinum-based alloy or a supported platinum-based catalyst.
Furthermore, the particle size of the platinum nanocrystal is 2-8 nm.
Further, the platinum-based alloy is an alloy of platinum cobalt, platinum nickel, platinum iron, platinum copper, platinum gold, platinum palladium, platinum cobalt nickel, platinum rhodium palladium or platinum iron manganese.
Further, the supported platinum-based catalyst is commercial platinum/carbon, platinum/alumina, platinum/silica, platinum/titania or platinum-supported molecular sieve.
Preferably, in step 1, the solvent is oleylamine, oleic acid, 1-octadecene, glycerol, formamide, quinoline, 1-chloronaphthalene, sulfolane, diphenyl ether or diphenyl sulfone.
Preferably, in step 2, the phosphorus source is white phosphorus, red phosphorus, phosphine, phosphate, phosphite, hypophosphite, tri-n-octylphosphine oxide or triphenylphosphine.
Preferably, in the step 1, the concentration of platinum in the platinum catalyst dispersion liquid is 0.01-10 mg/mL; the concentration of the amount of phosphorus species in the phosphorus source used in step 2 is lower than the concentration of the amount of platinum species in the platinum catalyst.
The platinum phosphide nano-catalyst prepared by the preparation method.
The application of the platinum phosphide nano-catalyst in electrocatalytic oxygen reduction is provided.
Compared with the prior art, the invention has the following beneficial technical effects:
in the invention, phosphorus atoms generated by decomposing a phosphorus source are diffused into the platinum catalyst lattice to prepare pure-phase platinum phosphide (with the molecular formula of Pt)2P) nanocrystalline catalysts, specific forThe determined electronic structure weakens the binding energy of the catalyst to the intermediate of the oxygen reduction reaction, and shows excellent activity of the electrocatalytic oxygen reduction reaction. Meanwhile, the surface of the catalyst is rich in stacking fault defects, and the catalyst has a large number of dangling bonds and rich platinum reaction active sites, so that the electrocatalysis performance is further improved. More importantly, the platinum phosphide nano-catalyst has a good crystal structure (face-centered cubic structure) and is a pure phase, so that the catalyst has structural stability superior to other amorphous structures or heterogeneous catalysts, shows excellent catalytic stability in electrocatalysis reaction, avoids great reduction of catalyst activity in the catalytic process, and has great application potential in the field of electrocatalysis.
In addition, the invention avoids the use of transition metal in the conventional platinum-based alloy catalyst, greatly reduces the manufacturing cost of the catalyst and further meets the requirement of industrial mass production. Compared with the existing platinum-based catalyst, the preparation method provided by the invention is simple, the raw materials are cheap, the production cost is low, and no environmental pollution is caused.
Further, the components of the catalyst can be regulated and controlled through reaction time, and the size of the catalyst can be accurately controlled through regulating and controlling the size of the original platinum catalyst.
The platinum phosphide nano-catalyst prepared by the invention is applied to electrocatalytic oxygen reduction reaction, has excellent catalytic activity and stability due to the characteristics of specific electronic structure, surface rich defect, stable structure in the reaction, good dispersibility and the like, and can meet the requirement of higher industrial application.
Drawings
FIG. 1 is a TEM photograph of Pt phosphide nanocatalyst prepared in the first example of the present invention, wherein the inset is an enlarged photograph of a single nanoparticle.
FIG. 2 is a TEM photograph of Pt phosphide nanocatalyst prepared in example II of the present invention, wherein the inset is an enlarged photograph of a single nanoparticle.
FIG. 3 is a TEM photograph of Pt phosphide nanocatalyst prepared in example III of the present invention, wherein the inset is an enlarged photograph of a single nanoparticle.
FIG. 4 is a TEM photograph of Pt phosphide nanocatalyst prepared in example IV of the present invention, wherein the inset is an enlarged photograph of a single nanoparticle.
FIG. 5 is a TEM photograph of Pt phosphide nanocatalyst prepared in example V of the present invention, wherein the inset is an enlarged photograph of a single nanoparticle.
FIG. 6 is a high-resolution TEM image of Pt phosphide nanocatalyst prepared in example V of the present invention, and the corresponding Fourier transform image is shown in the inset.
FIG. 7 is an X-ray diffraction spectrum of a platinum phosphide nanocatalyst prepared in example five of the present invention.
FIG. 8 is a TEM photograph of Pt phosphide nanocatalyst prepared in example six of the present invention.
FIG. 9 is a graph comparing the X-ray diffraction spectra of the Pt phosphide nano-catalyst prepared in example six and the Pt nano-particles as the raw material.
FIG. 10 is a TEM photograph of commercial carbon black loaded with Pt nano-catalyst prepared in example six of the present invention.
FIG. 11 is a graph comparing the electrocatalytic oxygen reduction reaction activity of the platinum phosphide nanocatalyst prepared in example six of the present invention and a commercial platinum/carbon catalyst.
FIG. 12 is a graph comparing the stability of electrocatalytic oxygen reduction reaction of the platinum phosphide nanocatalyst prepared in example six of the present invention and a commercial platinum/carbon catalyst.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The preparation method of the platinum phosphide nano-catalyst comprises the following steps:
step 1, dispersing a platinum catalyst in a solvent to obtain a platinum catalyst dispersion liquid;
and 2, adding a phosphorus source into the platinum catalyst dispersion liquid obtained in the step 1, uniformly stirring, heating for reaction, and centrifuging and washing after the reaction is finished to obtain the platinum phosphide nano-catalyst.
In step 1, the platinum catalyst is platinum nanocrystal, platinum-based alloy or a supported platinum-based catalyst. The platinum-based alloy is a platinum-based binary alloy such as platinum cobalt, platinum nickel, platinum iron, platinum copper, platinum gold, platinum palladium, etc., a platinum-based ternary alloy such as platinum cobalt nickel, platinum rhodium palladium, platinum iron manganese, etc., a platinum-based multicomponent alloy, etc. The supported platinum-based catalysts are commercial platinum/carbon, platinum/alumina, platinum/silica, platinum/titania or platinum-supported molecular sieves.
In the step 1, the solvent is oleylamine, oleic acid, 1-octadecene, glycerol, formamide, quinoline, 1-chloronaphthalene, sulfolane, diphenyl ether or diphenyl sulfone.
In step 2, the phosphorus source is a simple substance of phosphorus element and compounds with various valence states (inorganic substances of phosphorus such as white phosphorus, red phosphorus, phosphine, phosphate, phosphite, hypophosphite and the like, and organic phosphorus reagents such as tri-n-octylphosphine, tri-n-octylphosphine oxide, triphenylphosphine and the like).
In the step 1, the concentration of platinum in the platinum catalyst dispersion liquid is 0.01-10 mg/mL; the concentration of the amount of phosphorus species in the phosphorus source used in step 2 is lower than the concentration of the amount of platinum species in the platinum catalyst.
In the step 2, the reaction temperature is 200-.
Example one
The preparation method of the platinum phosphide nano-catalyst comprises the following steps:
1) ultrasonically dispersing 3.76mg of platinum nanocubes (with the average particle size of 8nm) in 10mL of oleylamine to obtain a stable platinum catalyst dispersion liquid, wherein the concentration of platinum is 0.376 mg/mL;
2) adding 1.6mL of tri-n-octylphosphine into the platinum catalyst dispersion liquid obtained in the step 1), and uniformly stirring to obtain a reaction precursor liquid;
3) heating and stirring the reaction precursor solution at 300 ℃, reacting for 1h, centrifuging and washing to obtain the platinum phosphide nano-catalyst. The phosphorus atom content in the catalyst is 4%, the morphology is still maintained as a nanocube, and the size is not obviously changed.
Example two
The preparation method of the platinum phosphide nano-catalyst comprises the following steps:
1) ultrasonically dispersing 3.76mg of platinum nanocubes (with the average particle size of 8nm) in 10mL of oleylamine to obtain a stable platinum catalyst dispersion liquid, wherein the concentration of platinum is 0.376 mg/mL;
2) adding 1.6mL of tri-n-octylphosphine into the platinum catalyst dispersion liquid obtained in the step 1), and uniformly stirring to obtain a reaction precursor liquid;
3) heating and stirring the reaction precursor solution at 300 ℃, reacting for 1.5h, centrifuging and washing to obtain the platinum phosphide nano-catalyst. The phosphorus atom content in the catalyst is 10%, and the shape gradually changes into a chamfered cube.
EXAMPLE III
The preparation method of the platinum phosphide nano-catalyst comprises the following steps:
1) ultrasonically dispersing 3.76mg of platinum nanocubes (with the average particle size of 8nm) in 10mL of oleylamine to obtain a stable platinum catalyst dispersion liquid, wherein the concentration of platinum is 0.376 mg/mL;
2) adding 1.6mL of tri-n-octylphosphine into the platinum catalyst dispersion liquid obtained in the step 1), and uniformly stirring to obtain a reaction precursor liquid;
3) heating and stirring the reaction precursor solution at 300 ℃, reacting for 2 hours, centrifuging and washing to obtain the platinum phosphide nano-catalyst. The content of phosphorus atoms in the catalyst is 16%, the catalyst particles become gradually round, and the corners disappear gradually.
Example four
The preparation method of the platinum phosphide nano-catalyst comprises the following steps:
1) ultrasonically dispersing 3.76mg of platinum nanocubes (with the average particle size of 8nm) in 10mL of oleylamine to obtain a stable platinum catalyst dispersion liquid, wherein the concentration of platinum is 0.376 mg/mL;
2) adding 1.6mL of tri-n-octylphosphine into the platinum catalyst dispersion liquid obtained in the step 1), and uniformly stirring to obtain a reaction precursor liquid;
3) heating and stirring the reaction precursor solution at 300 ℃, reacting for 2.5h, centrifuging and washing to obtain the platinum phosphide nano-catalyst. The phosphorus atom content in the catalyst is 21 percent, the morphology of the catalyst is changed into a nearly spherical shape, and the size of the catalyst is not obviously changed.
EXAMPLE five
The preparation method of the platinum phosphide nano-catalyst comprises the following steps:
1) ultrasonically dispersing 3.76mg of platinum nanocubes (with the average particle size of 8nm) in 10mL of oleylamine to obtain a stable platinum catalyst dispersion liquid, wherein the concentration of platinum is 0.376 mg/mL;
2) adding 1.6mL of tri-n-octylphosphine into the platinum catalyst dispersion liquid obtained in the step 1), and uniformly stirring to obtain a reaction precursor liquid;
3) heating and stirring the reaction precursor solution at 300 ℃, reacting for 3 hours, centrifuging and washing to obtain the platinum phosphide nano-catalyst. The phosphorus atom content in the catalyst is 33.3%, the particle morphology further becomes spherical, and the particle size is increased to 9.5 nm.
EXAMPLE six
The preparation method of the platinum phosphide nano-catalyst comprises the following steps:
1) ultrasonically dispersing 3.76mg of platinum nano particles (with the average particle size of 5nm) in 10mL of oleylamine to obtain a stable platinum catalyst dispersion liquid, wherein the concentration of platinum is 0.376 mg/mL;
2) adding 1.6mL of tri-n-octylphosphine into the platinum catalyst dispersion liquid obtained in the step 1), and uniformly stirring to obtain a reaction precursor liquid;
3) heating and stirring the reaction precursor solution at 300 ℃, reacting for 3 hours, centrifuging and washing to obtain the platinum phosphide nano-catalyst. The phosphorus atom content in the catalyst is 33.3%, the particle appearance is quasi-sphere, and the particle size is 6.2 nm.
EXAMPLE seven
The preparation method of the platinum phosphide nano-catalyst comprises the following steps:
1) ultrasonically dispersing 3.76mg of platinum nano particles (with the average particle size of 2nm) in 10mL of oleylamine to obtain a stable platinum catalyst dispersion liquid, wherein the concentration of platinum is 0.376 mg/mL;
2) adding 1.6mL of tri-n-octylphosphine into the platinum catalyst dispersion liquid obtained in the step 1), and uniformly stirring to obtain a reaction precursor liquid;
3) heating and stirring the reaction precursor solution at 300 ℃, reacting for 1.5h, centrifuging and washing to obtain the platinum phosphide nano-catalyst. The phosphorus atom content in the catalyst is 33.3%, the particle appearance is quasi-sphere, and the particle size is 2.5 nm.
Example eight
The preparation method of the platinum phosphide nano-catalyst comprises the following steps:
1) 3.71mg of a platinum-nickel alloy (composition PtNi)3) The nano catalyst is ultrasonically dispersed in 10mL of oleylamine to obtain stable platinum-nickel alloy nano catalyst dispersion liquid. Wherein the concentration of platinum atoms is 0.195 mg/mL;
2) adding 3mL of tri-n-octylphosphine into the platinum-nickel alloy catalyst dispersion liquid in the step 1), and uniformly stirring to obtain a reaction precursor liquid;
3) heating and stirring the reaction precursor solution at 200 ℃, reacting for 20 hours, centrifuging and washing to obtain the platinum-nickel-phosphorus alloy nano catalyst.
Example nine
The preparation method of the platinum phosphide nano-catalyst comprises the following steps:
1) 5mg of a platinum alloy (composition: Pt)50Au50) The nano catalyst is ultrasonically dispersed in 10mL of oleic acid to obtain stable platinum alloy nano catalyst dispersion liquid. Wherein the concentration of platinum atoms is 0.249 mg/mL;
2) adding 5.4mL of tri-n-octylphosphine into the platinum alloy catalyst dispersion liquid obtained in the step 1), and uniformly stirring to obtain a reaction precursor liquid;
3) heating and stirring the reaction precursor solution at 290 ℃, reacting for 8.5h, centrifuging and washing to obtain the platinum-gold-phosphorus alloy nano catalyst.
Example ten
The preparation method of the platinum phosphide nano-catalyst comprises the following steps:
1) 17mg of a platinum rhodium palladium alloy (composition: Pt)47Rh33Pd20) The nano catalyst is ultrasonically dispersed in 10mL of 1-octadecene to obtain stable platinum-rhodium-palladium alloy nano catalyst dispersion liquid. It is composed ofThe concentration of the platinum atom in the platinum alloy is 1.06 mg/mL;
2) adding 5mL of tri-n-octylphosphine into the platinum-rhodium-palladium alloy catalyst dispersion liquid in the step 1), and uniformly stirring to obtain reaction precursor liquid;
3) heating and stirring the reaction precursor solution at 280 ℃, reacting for 3.5h, centrifuging and washing to obtain the platinum-rhodium-palladium alloy nano catalyst.
EXAMPLE eleven
The preparation method of the platinum phosphide nano-catalyst comprises the following steps:
1) 50mg of a commercial platinum/carbon catalyst (loading 10%) was ultrasonically dispersed in 10mL of 1-octadecene to obtain a stable platinum/carbon catalyst dispersion. Wherein the concentration of platinum atoms is 0.5 mg/mL;
2) adding 2mL of tri-n-octylphosphine into the platinum/carbon catalyst dispersion liquid obtained in the step 1), and uniformly stirring to obtain a reaction precursor liquid;
3) heating and stirring the reaction precursor solution at 250 ℃, reacting for 6 hours, centrifuging and washing to obtain the platinum phosphide/carbon nano-catalyst.
Example twelve
The preparation method of the platinum phosphide nano-catalyst comprises the following steps:
1) 100mg of a commercial platinum/silica catalyst (loading 5%) was ultrasonically dispersed in 10mL of 1-octadecene to give a stable platinum/silica catalyst dispersion. Wherein the concentration of platinum atoms is 0.5 mg/mL;
2) adding 2mL of tri-n-octylphosphine into the platinum/silicon dioxide catalyst dispersion liquid obtained in the step 1), and uniformly stirring to obtain a reaction precursor liquid;
3) heating and stirring the reaction precursor solution at 260 ℃, reacting for 5 hours, centrifuging and washing to obtain the platinum phosphide/silicon dioxide nano catalyst.
EXAMPLE thirteen
The preparation method of the platinum phosphide nano-catalyst comprises the following steps:
1) ultrasonically dispersing 10mg of platinum-loaded molecular sieve catalyst (the loading amount is 1%) in 10mL of oleylamine to obtain a stable platinum-loaded molecular sieve catalyst dispersion liquid. Wherein the concentration of platinum atoms is 0.01 mg/mL;
2) adding 5mL of tri-n-octylphosphine into the platinum-loaded molecular sieve catalyst dispersion liquid obtained in the step 1), and uniformly stirring to obtain a reaction precursor liquid;
3) heating and stirring the reaction precursor solution at 320 ℃, reacting for 10 hours, centrifuging and washing to obtain the nano catalyst of the phosphorized platinum-loaded molecular sieve.
Example fourteen
The preparation method of the platinum phosphide nano-catalyst comprises the following steps:
1) 10mg of platinum nanoparticles (average particle size 5nm) were homogeneously mixed with 20mg of diphenyl sulfone;
2) adding 6mg of white phosphorus simple substance (dissolved in carbon disulfide) into the step 1), and uniformly stirring to obtain a reaction precursor;
3) heating and stirring the reaction precursor at 360 ℃, reacting for 4 hours, centrifuging and washing to obtain the platinum phosphide nano-catalyst.
Example fifteen
The preparation method of the platinum phosphide nano-catalyst comprises the following steps:
1) 100mg of platinum nanoparticles (average particle size of 5nm) were ultrasonically dispersed in 10mL of glycerin to obtain a stable platinum catalyst dispersion. Wherein the concentration of platinum atoms is 10 mg/mL;
2) adding 72mg of sodium hypophosphite into the platinum catalyst dispersion liquid obtained in the step 1), and uniformly stirring to obtain a reaction precursor liquid;
3) heating and stirring the reaction precursor solution at 260 ℃, reacting for 8.5h, centrifuging and washing to obtain the platinum phosphide nano-catalyst.
Application example
0.6mg of the platinum phosphide nanocatalyst prepared in example six was uniformly loaded on the surface of a commercial carbon material (Ketjen Black EC-300J, platinum loading 20%). Dispersing the loaded catalyst in 5mL of acetic acid, keeping the temperature at 70 ℃ for 12h to clean the surface of the catalyst, centrifuging, washing twice with an ethanol solution, drying in a 60 ℃ oven for 12h, and ultrasonically dispersing the catalyst in 2mL of a mixed solution (volume ratio is 4:1:0.02) of water, isopropanol and 5% nafion solution. 10 μ L (containing 3 μ g of platinum) of the dispersion was dropped on a glassy carbon electrode (area: 0.196 cm)2) And after being dried in the air, carrying out an electrocatalytic oxygen reduction reaction performance test on an Autolab PGSTAT302N electrochemical workstation. The test temperature is 25 ℃, a three-electrode system is adopted, and the reference electrode and the counter electrode are respectively Ag/AgCl and Pt foil electrodes. Cyclic voltammogram at N2Saturated 0.1M HClO4Obtained in solution with a sweep rate of 50 mV/s. Linear sweep voltammetry at O2The sweeping speed is 10mV/s, and the electrode rotating speed is 1600 rpm. Catalyst stability test at O2Saturated 0.1M HClO4The scanning is carried out in solution, the scanning cycle range is 0.6-1.1V (relative to the standard hydrogen electrode potential), the scanning speed is 100mV/s, and cyclic voltammetry and linear scanning voltammetry curves are recorded after the stability test.
Fig. 1-5 are transmission electron micrographs of the platinum phosphide nanocatalysts prepared in examples one-five, respectively, and show that as the reaction time increases, phosphorus atoms diffuse uniformly into the platinum catalyst lattice and the nanocrystal size increases. The appearance of the catalyst gradually evolves from a cube of the original platinum nano catalyst to be nearly spherical, and further proves that the platinum nano crystal evolves to the platinum phosphide nano crystal along with the diffusion of phosphorus atoms. Meanwhile, as the reaction proceeds, the content of phosphorus atoms in the platinum phosphide gradually increases, which also shows that the components of the platinum phosphide catalyst can be accurately controlled by regulating and controlling the reaction time.
FIG. 6 is a high resolution TEM image of the Pt phosphide nanocatalyst prepared in example five and its corresponding Fourier transform image, which shows that the Pt phosphide nanocatalyst is rich in a large number of stacking fault defects.
FIG. 7 is an X-ray diffraction pattern of the platinum phosphide nanocatalyst prepared in example five, and pure-phase platinum phosphide (molecular formula is Pt) can be determined by analyzing the diffraction pattern2P) generation of nanocrystals.
FIGS. 8 and 9 are a transmission electron micrograph and an X-ray diffraction spectrum, respectively, of a platinum phosphide nanocatalyst prepared in example six, having a catalyst particle size of 6.2nm, demonstrating small-sized pure-phase platinum phosphide (molecular formula Pt)2P) formation of nanocatalyst, indicating that the size of the platinum phosphide catalyst can beAnd (4) regulating and controlling the size of the platinum catalyst in the step one.
FIG. 10 is a TEM photograph of a small-sized Pt phosphide nanocatalyst prepared in example six and supported on commercial carbon black. It can be seen that the platinum phosphide nanoparticles are easy to uniformly load, and the catalytic performance research in subsequent application examples is facilitated.
Fig. 11 is a graph comparing the performance of the electrocatalytic oxygen reduction reaction of the platinum phosphide nanocatalyst of fig. 9 with that of the platinum catalyst before the phosphide. From the data in the figure, the area activity of the platinum phosphide nano-catalyst is 10.2 times that of the platinum catalyst, and the mass activity of the platinum phosphide nano-catalyst is 10.3 times that of the platinum catalyst, which shows that the platinum phosphide nano-catalyst has excellent catalytic activity.
FIG. 12 is a graph comparing the stability of electrocatalytic oxygen reduction reaction of the platinum phosphide nanocatalyst prepared in example six of the present invention and a commercial platinum/carbon catalyst. According to the data calculation in the figure, after 10,000 times and 30,000 times of cycle tests, the mass activity of the platinum phosphide nano-catalyst is respectively reduced by 6.8% and 9.1%. By way of comparison, the mass activity of the commercial platinum/carbon catalyst decreased by 22% and 55% after the same number of cycles. The loss of activity of the platinum phosphide nanocatalyst is far lower than that of the commercial platinum/carbon catalyst, which indicates that the catalyst has excellent catalytic stability.

Claims (10)

1. A preparation method of a platinum phosphide nano-catalyst is characterized by comprising the following steps:
step 1, dispersing a platinum catalyst in a solvent to obtain a platinum catalyst dispersion liquid;
and 2, adding a phosphorus source into the platinum catalyst dispersion liquid obtained in the step 1, uniformly stirring, reacting at the temperature of 200-360 ℃ for 1-20h, and centrifuging and washing after the reaction is finished to obtain the platinum phosphide nano-catalyst.
2. The method for preparing a platinum phosphide nano-catalyst according to claim 1, wherein in the step 1, the platinum catalyst is a platinum nanocrystal, a platinum-based alloy or a supported platinum-based catalyst.
3. The method of preparing a platinum phosphide nanocatalyst according to claim 2, wherein the particle size of the platinum nanocrystals is 2 to 8 nm.
4. The method for preparing a platinum phosphide nano-catalyst according to claim 2, wherein the platinum-based alloy is an alloy of platinum cobalt, platinum nickel, platinum iron, platinum copper, platinum gold, platinum palladium, platinum cobalt nickel, platinum rhodium palladium or platinum iron manganese.
5. The method of preparing a platinum phosphide nanocatalyst according to claim 2, wherein the supported platinum-based catalyst is commercial platinum/carbon, platinum/alumina, platinum/silica, platinum/titania or platinum-supported molecular sieve.
6. The method for preparing the platinum phosphide nanocatalyst according to claim 1, wherein in the step 1, the solvent is oleylamine, oleic acid, 1-octadecene, glycerol, formamide, quinoline, 1-chloronaphthalene, sulfolane, diphenyl ether or diphenyl sulfone.
7. The method for preparing a platinum phosphide nano-catalyst according to claim 1, wherein in the step 2, the phosphorus source is white phosphorus, red phosphorus, phosphine, phosphate, phosphite, hypophosphite, tri-n-octylphosphine oxide or triphenylphosphine.
8. The method for preparing a platinum phosphide nanocatalyst according to claim 1, wherein in the step 1, the concentration of platinum in the platinum catalyst dispersion liquid is 0.01-10 mg/mL; the concentration of the amount of phosphorus species in the phosphorus source used in step 2 is lower than the concentration of the amount of platinum species in the platinum catalyst.
9. The platinum phosphide nano-catalyst prepared by the preparation method of any one of claims 1 to 8.
10. Use of the platinum phosphide nanocatalyst of claim 9 in electrocatalytic oxygen reduction.
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