CN108666583B - Preparation method and application of high-bonding-degree nanometer WC-based binary composite material - Google Patents
Preparation method and application of high-bonding-degree nanometer WC-based binary composite material Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000011218 binary composite Substances 0.000 title abstract description 6
- 239000002131 composite material Substances 0.000 claims abstract description 72
- 229910002847 PtSn Inorganic materials 0.000 claims abstract description 57
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 47
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 46
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 27
- 239000010937 tungsten Substances 0.000 claims abstract description 27
- 238000001354 calcination Methods 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 20
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 15
- 239000001119 stannous chloride Substances 0.000 claims abstract description 15
- 235000011150 stannous chloride Nutrition 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000446 fuel Substances 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 239000010411 electrocatalyst Substances 0.000 claims abstract description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 4
- 238000005245 sintering Methods 0.000 claims abstract description 4
- 230000003213 activating effect Effects 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 30
- 230000035484 reaction time Effects 0.000 claims description 9
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical group [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 8
- 238000003763 carbonization Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- 238000010000 carbonizing Methods 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- 238000011065 in-situ storage Methods 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910052718 tin Inorganic materials 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000011246 composite particle Substances 0.000 description 4
- 238000010335 hydrothermal treatment Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910002056 binary alloy Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000001360 synchronised effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002848 Pt–Ru Inorganic materials 0.000 description 1
- 229910002846 Pt–Sn Inorganic materials 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- CFQCIHVMOFOCGH-UHFFFAOYSA-N platinum ruthenium Chemical compound [Ru].[Pt] CFQCIHVMOFOCGH-UHFFFAOYSA-N 0.000 description 1
- FHMDYDAXYDRBGZ-UHFFFAOYSA-N platinum tin Chemical compound [Sn].[Pt] FHMDYDAXYDRBGZ-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
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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
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- H01M4/00—Electrodes
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- H01M4/90—Selection of catalytic material
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- H01M4/921—Alloys or mixtures with metallic elements
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- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
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Abstract
A preparation method and application of a high-bonding-degree nanometer WC-based binary composite material are disclosed, wherein the preparation method comprises the following steps: 1) adding a tungsten source, a stannous chloride solution and oxalic acid into deionized water, and uniformly stirring to obtain a mixed solution; 2) carrying out hydrothermal reaction on the mixed solution to obtain precursor particles; 3) calcining the precursor particles to obtain a calcined powder material; 4) uniformly mixing the calcined powder material with high-purity white tin powder, tabletting, and calcining again in a nitrogen atmosphere to obtain a block-shaped sintered material; 5) the block sintering material is subjected to H temperature programming-gas-solid reaction2Carbonizing the mixture in a mixed atmosphere of CO to obtain a WC-Sn composite material; 6) slowly dissolving and activating the WC-Sn composite material in hydrochloric acid; 7) and adding a chloroplatinic acid solution into the WC-Sn composite material to replace platinum to obtain the PtSn/WC composite material. The PtSn/WC composite material can be used as an electrocatalyst to be applied to a methanol fuel cell, and can obviously improve the catalytic efficiency and prolong the service life of the catalyst.
Description
(I) technical field
The invention relates to a preparation method of a high-binding-degree nanometer WC-based binary composite material and application of the high-binding-degree nanometer WC-based binary composite material as an electrocatalyst in a methanol fuel cell.
(II) background of the invention
In recent years, tungsten carbide (WC) has attracted much attention for its wide range of applications, and has been widely studied as a non-noble metal catalyst support with excellent performance, particularly in the field of catalysis. For example, WC is often introduced as a carrier in the preparation process of a platinum-based catalyst of an anode of a direct alcohol fuel cell, because WC is a special material with high hardness, corrosion resistance and strong stability, and has an outer-layer electronic structure similar to that of platinum so as to show platinum-like catalytic performance. Therefore, the performance of the composite material combining the WC and the Pt is greatly improved under the synergistic catalysis of the WC and the Pt.
However, the preparation of highly active tungsten carbide composites still faces a number of challenges. On one hand, the preparation of the WC carrier is influenced by high-temperature agglomeration in the carbonization process and relatively large specific gravity of the WC carrier, so that the obtained material is small in specific surface area, large in particles and uneven in distribution. These disadvantages lead to the problem that noble metals are not well dispersed on the surface of WC during the preparation of the supported catalyst, the binding ability between the components is not strong, and the catalytic activity is difficult to have substantial breakthrough. On the other hand, although WC has good conductivity, its electron transport ability is still low to some extent. Therefore, in view of these disadvantages, how to effectively improve the performance of the catalyst as a whole will be the focus of attention of researchers.
Research shows that Pt is the most effective univalent metal catalyst for methanol electrocatalytic oxidation at present, and compared with other monometallics, platinum has good activity and stability, but cannot meet practical application due to the poisoning effect and high price of carbon monoxide (CO) similar substances. In order to find a methanol oxidation catalyst with high electrocatalytic activity and good stability, more Pt-Ru (platinum-ruthenium) and Pt-Sn (platinum-tin) binary composite catalysts are researched, because both Ru and Sn have a promoting effect. The addition of Ru may promote the oxidation of alcohol on the one hand and enable the oxidation of alcohol to occur more easily on the other hand, and the effect of Sn may be to influence the catalytic activity through an electronic effect to realize the improvement of catalytic performance and poisoning resistance.
The PtSn/C, PtSn/WC composite catalyst shows good catalytic activity and stability. However, the existing PtSn/WC catalyst is mainly in a supported type, and the preparation of the composite material is mainly completed by loading binary component particles on a substrate or preparing binary alloy PtSn and then loading the binary alloy PtSn on the substrate. The commonly used PtSn loaded composite material is mostly finished by a gas-phase reduction method and a chemical reduction method, the process is relatively complex, and the standardized control of the cost and the process is relatively difficult. Therefore, the composite catalyst with controllable preparation conditions, good PtSn dispersibility and strong binding force with a WC substrate is a key and important way for remarkably improving the catalytic activity and stability of the PtSn nano-catalyst. It is assumed that if part of the components can be prepared simultaneously, and the preparation steps are reduced, the production time and the production cost can be greatly reduced.
So far, reports on the preparation of the composite material by a similar synchronous method are not seen.
Disclosure of the invention
The first purpose of the invention is to provide a preparation method of a nano PtSn/WC composite material, in the preparation method, Sn is obtained by synchronous reduction in the step of carbonizing to generate nano WC particles, Pt particles are obtained by replacing Sn metal, the amount of carried platinum is controllable, the whole preparation step is simple, and the cost is low.
The second purpose of the invention is to provide a nano PtSn/WC composite material, which has the advantages of stable combination of all components, high catalytic activity, good thermal stability and strong anti-poisoning capability.
The third purpose of the invention is to provide the application of the nano PtSn/WC composite material as an electrocatalyst in a methanol fuel cell.
The technical scheme of the invention is specifically explained as follows:
the invention provides a preparation method of a nano PtSn/WC composite catalyst, which comprises the following steps:
(1) mixing a tungsten source and 15-20 mM stannous chloride solution according to the mass ratio of W/Sn of 4: 0.15-1.5, adding oxalic acid serving as a reducing agent into deionized water, and uniformly stirring to obtain a mixed solution of a tungsten source and stannous chloride, wherein the total mass fraction of the tungsten source and the stannous chloride is 3-5 wt%, and the adding amount of the oxalic acid is 0.2-0.5 g/15mL based on the volume of the deionized water;
(2) transferring the mixed solution obtained in the step (1) into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 8-14 h at 160-220 ℃ to obtain precursor particles;
(3) calcining the precursor particles obtained in the step (2) at the temperature of 300-600 ℃ to obtain a calcined powder material, wherein the calcination is carried out to remove volatile impurities in the precursor;
(4) uniformly mixing the calcined powder material obtained in the step (3) with high-purity white tin powder (99.99%), tabletting, wherein the mass fraction of the high-purity white tin powder is not more than 20% (preferably 10-20%), and calcining again at 600 ℃ under the nitrogen atmosphere at 300-;
(5) the block sintering material is subjected to H temperature programming-gas-solid reaction2And CO, and the temperature programming-gas-solid reaction method comprises the following steps: heating to 800-1000 ℃ at a speed of 1-10 ℃/min, keeping for 1-5 hours, and obtaining a tungsten carbide-tin composite material (WC-Sn) after carbonization is completed;
(6) slowly dissolving and activating the WC-Sn composite material obtained in the step (5) under 0.5-2M hydrochloric acid for 0.5-2h, and washing and drying the activated WC-Sn composite material by deionized water after activation;
(7) and (3) adding a chloroplatinic acid solution into the WC-Sn composite material treated in the step (6) to replace platinum, filtering, cleaning and drying after the reaction is finished to obtain the PtSn/WC composite material, wherein the platinum carrying amount can be finely regulated and controlled, and can be controlled by regulating the amount of chloroplatinic acid.
In step (1) of the present invention, the tungsten source is sodium tungstate, ammonium metatungstate or tungsten chloride, preferably sodium tungstate. The mass ratio of W/Sn is preferably 4: 0.25 to 1. The total mass fraction of the tungsten source and the stannous chloride in the mixed solution is preferably 3.5-4.5 wt%. The mass of the oxalic acid is preferably 0.3-0.4 g/15mL in terms of the volume of the deionized water.
In the step (2) of the present invention, it is preferable that the prepared mixed solution is sufficiently dispersed by ultrasonic treatment and then transferred to a hydrothermal reaction kettle to perform a hydrothermal reaction. Wherein the preferred hydrothermal reaction temperature is 180-200 ℃, and the preferred hydrothermal reaction time is 10-12 h.
In the step (3), in order to remove volatile impurities in the precursor, a product obtained after hydrothermal treatment is calcined, wherein the calcination temperature is preferably 400-600 ℃, more preferably 450-550 ℃, and further preferably 500 ℃; the calcination time is preferably 1 to 4 hours, more preferably 1.5 to 3.5 hours, and still more preferably 2 hours.
In the step (4), after tabletting, calcining again in a nitrogen atmosphere at the calcining temperature of preferably 400-600 ℃, more preferably 450-550 ℃, and further preferably 500 ℃; the calcination time is preferably 1 to 4 hours, more preferably 1.5 to 3.5 hours, and still more preferably 2 hours.
In the step (5), the WC-Sn composite material is prepared by carbonizing the particles by a temperature programming-gas-solid reaction method. The carbonization step is carried out in a high temperature tubular reactor, preferably hydrogen (H)2) And carbon monoxide (CO) in a reaction atmosphere in which H is2And CO, preferably in a volume ratio of 1: 1 to 5. The programmed heating-gas-solid reaction method is preferably as follows: heating to 850-950 ℃ at a programmed heating rate of 3-7 ℃/min and keeping for 2-4 h; most preferably 5 ℃/min, and the temperature is raised to 900 ℃ and kept for 3h, and the WC-Sn composite material is obtained after the carbonization and the temperature reduction.
In the step (6), the obtained WC-Sn needs to be slowly dissolved and activated under 0.5-1.5M hydrochloric acid, and the concentration of the hydrochloric acid is preferably 0.8-1.2M, and more preferably 1M. The treatment time is preferably 0.5 to 1.5h, more preferably 1 h. The volume usage of the hydrochloric acid is 5-10 mL/g based on the mass of the WC-Sn composite material.
In the step (7) of the invention, the WC-Sn composite material can be prepared by metal replacement in the solution without high-temperature gas reduction, reducing agent reduction and the like required by the conventional platinum-carrying, so that the raw materials and the energy consumption are saved. According to the invention, the concentration of the chloroplatinic acid solution is preferably 1-10 mmol/L, and more preferably 5 mmol/L. The dosage of the chloroplatinic acid is preferably 5-20% of the mass of the tungsten carbide/tin (WC-Sn) composite material, and more preferably 10% of the mass of the Pt. Specifically, the platinum-carrying reaction temperature is 20-80 ℃, and more preferably 50 ℃; the reaction time is 8-16 h, and more preferably 12 h.
The PtSn/WC composite material prepared by the invention comprises microsphere particles with the diameter of about 2-5 mu m, wherein the microsphere particles consist of tungsten carbide-platinum tin nanoparticles with the diameter of about 50-100 nm.
The invention further provides application of the PtSn/WC composite material as an electrocatalyst in a methanol fuel cell. The result shows that the PtSn/WC composite catalyst can obviously improve the catalytic efficiency and prolong the service life of the catalyst.
In the PtSn/WC composite material provided by the invention, Sn plays a dual role. Firstly, Sn is used as one of binary components of the composite material, is not loaded on a carrier at the later stage but is introduced in the preparation of a precursor, and the metal can be reduced in the formation process of tungsten carbide particles so as to be compounded with WC in situ; secondly, because Sn has stronger metal reducibility, the PtSn/WC composite binary metal catalyst is skillfully obtained by simply replacing Pt metal in situ by fully utilizing the advantages of the active component. In addition, as Sn has a lower melting point (231.89 ℃), Sn is easy to liquefy after being reduced at high temperature and is melted into WC particles in a metal liquid form, the dispersity of Sn and the binding force between Sn and WC particles can be better enhanced, the dispersion of platinum particles in the preparation of the platinum-carrying catalyst is facilitated, and the catalytic activity and the stability of the catalyst are greatly improved. Therefore, the PtSn/WC composite material prepared in situ has strong bonding force among the components, good conductivity and stability, excellent electrochemical performance, simple and easy preparation process and low cost, and can be used as a fuel cell electrode catalytic material.
Compared with the prior art, the invention has the beneficial effects that:
the in-situ preparation of the PtSn/WC composite material is beneficial to the improvement of the binding force and the thermal stability among the components.
The coexistence of WC and Sn in the PtSn/WC composite catalyst enhances the stability and anti-poisoning ability of the platinum-supported catalyst.
And 3, in-situ reduction of Sn in the PtSn/WC composite material, the Pt particles are obtained by in-situ replacement of Sn, so that the complicated steps in the conventional Pt and Sn loading and consumption of raw materials such as reducing agents are saved, the steps are simple, and the cost is effectively reduced.
And 4, the PtSn/WC composite material can regulate and control the loading amount of tin and platinum by controlling the content of Sn in the precursor solution and the addition amount of a chloroplatinic acid solution in a later period.
5, the PtSn/WC composite material as an electrocatalyst can be widely applied to important fields of fuel cells and the like, and the catalytic performance is obviously improved.
(IV) description of the drawings
FIG. 1 is an SEM image of the PtSn/WC composite material of example 1 at a magnification of 6000.
FIG. 2 is a SEM image of the PtSn/WC composite material of example 1 at a magnification of 50000.
FIG. 3 is an SEM image of the PtSn/WC composite material of example 4 at a magnification of 10000.
FIG. 4 is an SEM image of the PtSn/WC composite material of example 4 at a magnification of 30000.
FIG. 5 is a graph showing the catalytic activity of the PtSn/WC composite material in examples 1, 4 and 5 on methanol. In FIG. 5, the abscissa is the working electrode potential/V (SCE, with a saturated calomel electrode as a reference electrode), the ordinate is the platinum mass current/(mA/mgPt), and the curves are PtSn/WC and the carbon-supported platinum nanocrystal catalyst (platinum content 20 wt%) produced by Heson, China, respectively. The solution at the time of measurement was a mixed aqueous solution of methanol (0.5M) and sulfuric acid (0.5M) at a sweep rate of 50 mV/s.
FIG. 6 is a graph showing the catalytic activity of the PtSn/WC composite material in examples 1, 4 and 5 on methanol. In FIG. 6, the abscissa represents time (S) and the ordinate represents mass current/(mA/mgPt). The curves are for PtSn/WC and for the carbon supported platinum nanocrystal catalyst (platinum content 20 wt%) from Heson corporation of China, respectively. The solution at the time of measurement was a mixed aqueous solution of methanol (0.5M) and sulfuric acid (0.5M), the sweep rate was 50mV/s, and the potential was set at 0.7V.
(V) specific embodiment:
the following specific examples illustrate the technical solutions of the present invention, but the scope of the present invention is not limited thereto:
example 1:
(1) taking sodium tungstate as a tungsten source, and mixing the tungsten source and the tungsten source according to the mass ratio of W/Sn of 4: 1 adding sodium tungstate and a 17.7mM stannous chloride solution into 15mL of deionized water to prepare a solution with the total mass fraction of the sodium tungstate and the stannous chloride being 4.5 wt%, and then adding 0.375g of oxalic acid. And transferring the obtained mixed solution to a hydrothermal reaction kettle for hydrothermal reaction for 12 hours at the temperature of 200 ℃ after ultrasonic treatment. Calcining the product obtained after hydrothermal treatment at 550 ℃ for 2h to obtain a calcined powder material, uniformly mixing the calcined powder material with high-purity white tin powder (the purity is 99.99 percent), tabletting (the mass percent of the tin powder is 15 percent), and tabletting in nitrogenAnd calcining for 2 hours again at 550 ℃ in the atmosphere to obtain the block-shaped sintered material. Putting part of the block-shaped sintered material into a tube furnace to be heated in CO to H2(volume ratio is 5:1) under the mixed atmosphere, raising the temperature to 900 ℃ by a program at a speed of 5 ℃/min, preserving the heat for 3h, and carbonizing at high temperature to obtain the WC-Sn sample. The obtained WC-Sn was slowly dissolved and activated for 1h under 1M hydrochloric acid (0.5 mL). Adding 5mmol/L chloroplatinic acid solution into a WC-Sn sample according to the platinum loading amount of 10 wt%, standing at the constant temperature of 50 ℃ for 12h, filtering, cleaning and drying to obtain the nano PtSn/WC composite material.
FIG. 1 is an SEM image of the PtSn/WC composite material prepared, and it can be seen from FIG. 1 that the PtSn/WC composite material is approximately loose spheres with a diameter of about 4 μm. However, as is evident from fig. 2, the sphere is composed of a plurality of loose nano tungsten carbide-platinum tin composite particles, and the dispersion is very uniform, and the average particle size is about 60 nm.
Example 2:
procedure analogous to example 1, but with a W/Sn mass ratio of 4: 0.5, preparing a solution with the total mass fraction of sodium tungstate and stannous chloride being 3.8 wt%, adding 0.4g of oxalic acid, and obtaining the PtSn/WC composite material by the same steps. The composite material is a loose sphere with the diameter of about 2 mu m, and the sphere is composed of high-dispersion tungsten carbide-platinum tin composite particles, and the average particle size is about 50 nm.
Example 3:
procedure analogous to example 1, but with a W/Sn mass ratio of 4: 0.25, preparing a solution with the total mass fraction of sodium tungstate and stannous chloride being 3.5 wt%, adding 0.3g of oxalic acid, and obtaining the PtSn/WC composite material by the same steps.
Example 4:
the procedure of example 1 was followed in the same manner except that the tungsten source was changed to ammonium metatungstate and the stannous chloride solution concentration was changed to 15mM, to obtain a PtSn/WC composite material.
FIG. 3 is an SEM image of the prepared PtSn/WC composite material, and it can be seen from FIG. 3 that the WC composite material is approximately a sphere with a mesoporous structure having a diameter of about 5 μm. However, the enlarged surface of the sphere shown in fig. 4 can clearly observe that the sphere is composed of a plurality of nano tungsten carbide-platinum tin composite particles with uneven sizes and irregular shapes, and the mesopores are developed.
Example 5:
the procedure of example 1 was followed in the same manner except that the tungsten source was changed to tungsten chloride and the stannous chloride solution concentration was 20mM to obtain a PtSn/WC composite material. The composite material is a loose sphere with a diameter of about 5 μm, and the sphere is composed of tungsten carbide-platinum tin composite particles with a surface of about 100 nm.
Example 6:
similar to the procedure of example 1, but the hydrothermal reaction temperature was 180 ℃ and the reaction time was 12 hours, but the calcination treatment temperature of the product obtained after hydrothermal treatment was 550 ℃ and the treatment time was 1.5 hours, and the calcination temperature of the product obtained after tabletting was 550 ℃ and the reaction time was 1.5 hours. The rest steps are the same, and the PtSn/WC composite material is obtained.
Example 7:
similar to the procedure of example 1, but the hydrothermal reaction temperature was 200 ℃ and the reaction time was 10 hours, but the calcination treatment temperature of the product obtained after hydrothermal treatment was 450 ℃ and the treatment time was 3.5 hours, and the calcination temperature was 450 ℃ and the time was 3.5 hours again after tabletting. The rest steps are the same, and the PtSn/WC composite material is obtained.
Example 8:
the procedure of example 1 was followed, but the WC-Sn material obtained after carbonization had an activated hydrochloric acid concentration of 0.8M and an activation time of 1.5 h. The rest steps are the same, and the PtSn/WC composite material is obtained.
Example 9:
the procedure of example 1 was followed, but the WC-Sn material obtained after carbonization had an activated hydrochloric acid concentration of 1.2M and an activation time of 0.5 h. The rest steps are the same, and the PtSn/WC composite material is obtained.
Example 10:
similar to the procedure of example 1, except that the amount of platinum supported was changed to 20 wt%, the chloroplatinic acid concentration was changed to 10mmol/L, the reaction temperature was changed to 80 deg.C, the reaction time was changed to 16h, and the other steps were the same, to obtain a PtSn/WC composite material.
Example 11:
similar to the process of example 1, but the platinum loading amount was changed to 5 wt%, the chloroplatinic acid concentration was changed to 1mmol/L, the reaction temperature was changed to 20 deg.C, the reaction time was changed to 8 hours, and the other steps were the same, to obtain the PtSn/WC composite material.
Example 12: application examples
The PtSn/WC composite catalyst prepared by the method (examples 1, 4 and 5) is in 0.5M CH3OH+0.5 M H2SO4The electrocatalytic methanol oxidation performance characterization was performed in solution and compared to a commercial platinum-on-carbon catalyst (20%). FIG. 5 is a comparison of the performance of PtSn/WC in examples (1, 4, 5) versus commercial Pt/C catalysts for methanol oxidation. The results show that the PtSn/WC composite catalysts prepared in examples 1 and 4 have negative potential shift on the initial potential of methanol oxidation, which indicates that the reaction is more favorable to occur at lower potential, and the oxidation peak current density is obviously improved compared with that of commercial platinum carbon. Therefore, the preparation method provided by the invention is beneficial to the overall improvement of the performance of the composite material.
In addition, fig. 6 is a CA characterization diagram of catalytic activity of the PtSn/WC catalyst on methanol, and after the current is stabilized, the PtSn/WC prepared in each example shows better activity, which indicates better stability.
Claims (10)
1. A preparation method of a nano PtSn/WC composite catalyst comprises the following steps:
(1) mixing a tungsten source and 15-20 mM stannous chloride solution according to the mass ratio of W/Sn of 4: 0.15-1.5, adding oxalic acid serving as a reducing agent into deionized water, and uniformly stirring to obtain a mixed solution of a tungsten source and stannous chloride, wherein the total mass fraction of the tungsten source and the stannous chloride is 3-5 wt%, and the adding amount of the oxalic acid is 0.2-0.5 g/15mL based on the volume of the deionized water;
(2) transferring the mixed solution obtained in the step (1) into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 8-14 h at 160-220 ℃ to obtain precursor particles;
(3) calcining the precursor particles obtained in the step (2) at the temperature of 300-600 ℃ to obtain a calcined powder material;
(4) uniformly mixing the calcined powder material obtained in the step (3) with high-purity white tin powder, tabletting, wherein the mass fraction of the high-purity white tin powder is not more than 20%, and calcining again at the temperature of 600 ℃ under the nitrogen atmosphere to obtain a block sintering material;
(5) the block sintering material is subjected to H temperature programming-gas-solid reaction2And CO, and the temperature programming-gas-solid reaction method comprises the following steps: heating to 800-1000 ℃ at a speed of 1-10 ℃/min, keeping for 1-5 hours, and obtaining the tungsten carbide-tin composite material after carbonization;
(6) slowly dissolving and activating the tungsten carbide-tin composite material obtained in the step (5) under 0.5-2M hydrochloric acid for 0.5-2h, washing with deionized water after activation is finished, and drying;
(7) and (4) adding a chloroplatinic acid solution into the tungsten carbide-tin composite material treated in the step (6) to replace platinum, and filtering, cleaning and drying after the reaction to obtain the PtSn/WC composite material.
2. The method of claim 1, wherein: in the step (1), the tungsten source is sodium tungstate, ammonium metatungstate or tungsten chloride; the mass ratio of W/Sn is 4: 0.25 to 1; the total mass fraction of the tungsten source and the stannous chloride in the mixed solution is 3.5-4.5 wt%; the mass of the oxalic acid is 0.3-0.4 g/15mL calculated by the volume of the deionized water.
3. The method of claim 1, wherein: in the step (2), the mixed solution obtained in the step (1) is fully dispersed through ultrasonic treatment and then transferred to a hydrothermal reaction kettle for hydrothermal reaction; the hydrothermal reaction temperature is 180-200 ℃, and the hydrothermal reaction time is 10-12 h.
4. The method of claim 1, wherein: in the step (3), the calcining temperature is 400-600 ℃, and the calcining time is 1-4 h.
5. The method of claim 1, wherein: in the step (4), the calcining temperature is 400-600 ℃, and the calcining time is 1-4 h.
6. The method of claim 1, wherein: in step (5), H2And CO in a mixed atmosphere, H2And CO in an atmosphere volume ratio of 1: 1-5; the temperature programming-gas-solid reaction method comprises the following steps: heating to 850-950 ℃ at a programmed heating rate of 3-7 ℃/min and keeping for 2-4 h.
7. The method of claim 1, wherein: in the step (6), the hydrochloric acid has a concentration of 0.5-1.5M, and is dissolved and activated for 0.5-1.5h, wherein the volume consumption of the hydrochloric acid is 5-10 mL/g based on the mass of the tungsten carbide-tin composite material.
8. The method of claim 1, wherein: in the step (7), the concentration of the chloroplatinic acid solution is 1-10 mmol/L, the dosage of the chloroplatinic acid is 5-20% of the mass of the tungsten carbide-tin composite material in terms of the mass of Pt, the reaction temperature of the platinum-carrying is 20-80 ℃, and the reaction time is 8-16 h.
9. The PtSn/WC composite material produced by the production method according to claim 1.
10. Use of the PtSn/WC composite material of claim 9 as an electrocatalyst in a methanol fuel cell.
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