CN113398951A - Intermetallic compound catalyst and method for preparing intermetallic compound catalyst by using bimetallic complex - Google Patents
Intermetallic compound catalyst and method for preparing intermetallic compound catalyst by using bimetallic complex Download PDFInfo
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- CN113398951A CN113398951A CN202110668739.XA CN202110668739A CN113398951A CN 113398951 A CN113398951 A CN 113398951A CN 202110668739 A CN202110668739 A CN 202110668739A CN 113398951 A CN113398951 A CN 113398951A
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- intermetallic compound
- compound catalyst
- carbon black
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- bimetallic complex
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- 229910000765 intermetallic Inorganic materials 0.000 title claims abstract description 58
- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 29
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000006229 carbon black Substances 0.000 claims abstract description 27
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims abstract description 17
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 16
- 239000012046 mixed solvent Substances 0.000 claims abstract description 13
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 12
- 239000011591 potassium Substances 0.000 claims abstract description 12
- -1 transition metal salt Chemical class 0.000 claims abstract description 12
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 238000004108 freeze drying Methods 0.000 claims abstract description 6
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims abstract description 4
- 238000001556 precipitation Methods 0.000 claims abstract description 4
- 238000011068 loading method Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 238000007710 freezing Methods 0.000 claims description 7
- 230000008014 freezing Effects 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 7
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 abstract description 18
- 238000000137 annealing Methods 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 4
- 150000003624 transition metals Chemical class 0.000 abstract description 3
- 238000005275 alloying Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 22
- 229910002837 PtCo Inorganic materials 0.000 description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 239000011943 nanocatalyst Substances 0.000 description 10
- 238000000634 powder X-ray diffraction Methods 0.000 description 10
- 239000010453 quartz Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000000446 fuel Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 229910002836 PtFe Inorganic materials 0.000 description 8
- 229910002844 PtNi Inorganic materials 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000011363 dried mixture Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- CMHKGULXIWIGBU-UHFFFAOYSA-N [Fe].[Pt] Chemical compound [Fe].[Pt] CMHKGULXIWIGBU-UHFFFAOYSA-N 0.000 description 4
- PCLURTMBFDTLSK-UHFFFAOYSA-N nickel platinum Chemical compound [Ni].[Pt] PCLURTMBFDTLSK-UHFFFAOYSA-N 0.000 description 4
- SKJKDBIPDZJBPK-UHFFFAOYSA-N platinum zinc Chemical compound [Zn].[Pt] SKJKDBIPDZJBPK-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 229920000554 ionomer Polymers 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- GNBVPFITFYNRCN-UHFFFAOYSA-M sodium thioglycolate Chemical compound [Na+].[O-]C(=O)CS GNBVPFITFYNRCN-UHFFFAOYSA-M 0.000 description 2
- 229940046307 sodium thioglycolate Drugs 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J23/8906—Iron and noble metals
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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Abstract
The invention provides a method for preparing an intermetallic compound catalyst by adopting a bimetallic complex, which comprises the following steps: s1) mixing thioacetic acid, sodium bicarbonate, potassium platinochloride and transition metal salt in an aqueous solution to obtain a bimetallic complex molecule separated out in a precipitation form; s2) removing moisture from the bimetal complex molecule; s3) mixing the bimetal complex molecule after water removal and carbon black in a mixed solvent of tertiary butanol and water, and freeze-drying to obtain a mixture of the bimetal complex molecule and the carbon black; s4) calcining the above mixture in a reducing atmosphere to obtain an intermetallic compound catalyst. The intermetallic compound catalyst prepared by the freeze-drying method can form high-load platinum load at low annealing temperature, and the atomic ratio of platinum to transition metal is clear 1: 1, the composition is controllable, the size distribution is uniform, and the atomic alloying degree is high. The method is simple to operate, has universality and is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to an intermetallic compound catalyst and a method for preparing the intermetallic compound catalyst by adopting a bimetallic complex.
Background
In the past three decades, proton exchange membrane fuel cells have been rapidly developed as a power source for electric vehicles, and understanding the basic principles of the relevant electrocatalysis process can provide ideas for designing efficient and stable proton exchange membrane fuel cell catalysts. At present, Pt is still a precious metal simple substance catalyst which is difficult to replace in a proton exchange membrane fuel cell catalyst, and in the process of designing a high-efficiency platinum-based proton exchange membrane fuel cell, the load of high-load platinum on a cathode catalyst is very important, because a great loss of power density can be observed in the proton exchange membrane fuel cell with low Pt load, and the existence of the high-load platinum on the catalyst can provide more available Pt surface area to reduce the local mass transfer resistance of oxygen at the interface between Pt/ionomer and ionomer/gas to meet the requirement of the high-power density fuel cell under high current density besides reducing the thickness of the membrane electrode of the fuel cell.
Recently, ordered platinum-based intermetallic compound fuel cell catalysts have attracted extensive research interest. Compared with disordered solid solution alloy, the intermetallic compound is formed by combining metal atoms in a specific proportion, has a long-range ordered crystal structure, can optimize Pt-O binding energy by the strain effect and the ligand effect brought by the unique structure, further improves the activity of oxygen reduction reaction, has stronger stability, inhibits the dissolution of transition metal elements, and shows excellent catalytic activity and stability.
Currently, the synthesis methods related to ordered platinum-based intermetallic compounds can be simply classified into a thermal annealing synthesis method and a liquid phase synthesis method. The liquid phase synthesis is only suitable for some alloy systems with low boiling points, and a surfactant and a reducing agent are additionally added in the synthesis, so that the operation is complicated and the method is not suitable for large-scale preparation; however, in the general thermal annealing method, two different metal precursors are directly impregnated on the carbon carrier by an impregnation method, which is simple, but lacks control on the uniformity of the size and the composition of the ordered platinum-based alloy nanoparticles. Particularly, when the metal loading is increased, the metal atoms have strong affinity, the particles are easy to agglomerate, and the agglomeration of the particles can finally cause the electrochemical active surface area of the catalyst to be reduced. Therefore, the synthesis of the ordered platinum-based intermetallic compound fuel cell catalyst with controllable composition and high noble metal platinum loading capacity is reported at present.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide an intermetallic compound catalyst and a method for preparing an intermetallic compound catalyst by using a bimetallic complex, and the prepared platinum-based intermetallic compound nanomaterial has controllable composition, uniform size and high universality.
In order to achieve the above objects, the present invention provides a method for preparing an intermetallic compound catalyst using a bimetallic complex, comprising the steps of:
s1) mixing thioacetic acid, sodium bicarbonate, potassium platinochloride and transition metal salt in an aqueous solution to obtain a bimetallic complex molecule separated out in a precipitation form;
s2) removing moisture from the bimetal complex molecule;
s3) mixing the bimetal complex molecule after water removal and carbon black in a mixed solvent of tertiary butanol and water, and freeze-drying to obtain a mixture of the bimetal complex molecule and the carbon black;
s4) calcining the above mixture in a reducing atmosphere to obtain an intermetallic compound catalyst.
Preferably, in the present invention, the step S1) is specifically:
dissolving sodium bicarbonate in aqueous solution of thioacetic acid, stirring to dissolve, sequentially adding potassium platinochloride and transition metal salt, and stirring at room temperature until precipitate is generated.
The stirring and dissolving time is preferably 5-20 min.
The stirring time at room temperature is preferably 24 h.
Stirring and dissolving to obtain a light yellow clear sodium thioglycolate solution, then sequentially adding potassium chloroplatinite and a transition metal salt aqueous solution into the clear solution, and continuing stirring at room temperature for 24 hours, wherein the sulfur and oxygen in the sodium thioglycolate are allowed to selectively combine platinum and transition metal at different sites due to two different binding groups, so that a bimetallic complex molecule precipitate is finally formed after reaction.
In a preferred embodiment of the present invention, the metal element in the bimetallic complex molecule includes any one of cobalt, iron, nickel and zinc, and platinum.
Preferably, the transition metal salt is selected from transition metal salts containing cobalt, iron, nickel or zinc, more preferably one or more of cobalt chloride hexahydrate, ferrous sulfate heptahydrate, nickel chloride hexahydrate and zinc sulfate heptahydrate.
Preferably, the moisture removal treatment is suction filtration and/or vacuum drying.
The step S2) is preferably specifically:
and (3) carrying out suction filtration on the bimetallic complex molecules, washing with water for three times, and then putting the bimetallic complex into a 65-DEG C vacuum drying oven for 4-10 h to remove residual moisture, thus obtaining the dewatered bimetallic complex.
The step S3) is preferably specifically:
and mixing the dehydrated bimetallic complex molecules and carbon black in a mixed solvent of tert-butyl alcohol and water, carrying out ultrasonic treatment for 1-2 hours, freezing for 20-30 min under liquid nitrogen, and then putting into a freeze dryer for drying for 36-64h to remove the solvent to obtain a mixture of the bimetallic complex molecules and the carbon black.
In the preferred mixed solvent of tertiary butanol and water, the mass fraction of tertiary butanol is 10% to 90%.
Considering that the bimetallic complex molecule does not have good hydrophilicity and simultaneously, in order to make the molecule adsorbed on the carbon black more uniformly, the mixed solution of tert-butyl alcohol and water is used as a solvent in the invention.
The carbon Black of the present invention is not particularly limited, and is generally commercially available, and Ketjen Black EC-300J (KJ300), Ketjen Black EC-600J (KJ600), BP2000 and/or Vulcan XC-72R (XC-72) are preferred.
Preferably, the reducing atmosphere comprises hydrogen and an inert gas. The inert gas is preferably argon.
In the invention, the calcination temperature is preferably 500-1100 ℃.
According to the invention, the temperature rise speed of the calcination is preferably 2-30 ℃/min.
According to the invention, the calcination time is preferably 2-40 h.
The invention provides the intermetallic compound catalyst prepared by the method, wherein the loading amount of Pt on carbon black in the catalyst is 30-60%.
Compared with the prior art, the invention provides a method for preparing an intermetallic compound catalyst by adopting a bimetallic complex, which comprises the following steps: s1) mixing thioacetic acid, sodium bicarbonate, potassium platinochloride and transition metal salt in an aqueous solution to obtain a bimetallic complex molecule separated out in a precipitation form; s2) removing moisture from the bimetal complex molecule; s3) mixing the bimetal complex molecule after water removal and carbon black in a mixed solvent of tertiary butanol and water, and freeze-drying to obtain a mixture of the bimetal complex molecule and the carbon black; s4) calcining the above mixture in a reducing atmosphere to obtain an intermetallic compound catalyst. The intermetallic compound catalyst prepared from the bimetallic complex by using a freeze-drying method can form a high-load platinum load at a low annealing temperature, and the atomic ratio of platinum to transition metal is clear 1: 1, the composition is controllable, the size distribution is uniform, and the atomic alloying degree is high. The method is simple to operate, has universality and is suitable for industrial production.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of an intermetallic compound PtCo nano-catalyst with a Pt loading of 30 wt% prepared in example 1 of the present invention;
FIG. 2 is a TEM photograph of a PtCo nano-catalyst with Pt loading of 30 wt% prepared in example 1 of the present invention;
FIG. 3 is an X-ray powder diffraction pattern of an intermetallic compound PtCo nano-catalyst with a Pt loading of 40 wt% prepared in example 2 of the present invention;
FIG. 4 is a TEM photograph of 40 wt% Pt loaded intermetallic compound PtCo nano-catalyst prepared in example 2 of the present invention;
FIG. 5 shows the X-ray powder diffraction pattern of the PtFe nano-catalyst of intermetallic compound with Pt loading of 30 wt% prepared in example 3 of the present invention;
FIG. 6 is a TEM photograph of 30 wt% Pt loading in PtFe nano-catalyst prepared in example 3 of the present invention;
FIG. 7 is an X-ray powder diffraction pattern of an intermetallic compound PtNi nano-catalyst with a Pt loading of 30 wt% prepared in example 4 of the present invention;
FIG. 8 is a TEM photograph of a PtNi nano-catalyst with Pt loading of 30 wt% prepared in example 4 of the present invention;
FIG. 9 shows the X-ray powder diffraction pattern of the PtZn nanocatalyst with 30 wt% Pt loading prepared in example 5 of the present invention;
fig. 10 is a transmission electron microscope photograph of the intermetallic compound PtZn nanocatalyst with a Pt loading of 30 wt% prepared in example 5 of the present invention.
Detailed Description
In order to further illustrate the present invention, the intermetallic compound catalyst and the method for preparing the intermetallic compound catalyst using the bimetallic complex according to the present invention will be described in detail with reference to the following examples.
Example 1
a. Dispersing 68 mu L of thioacetic acid solution into 30ml of water, then adding 85mg of sodium bicarbonate solution dissolved into 3ml of water, stirring for 5min at room temperature, sequentially adding 100mg of potassium chloroplatinite solution dissolved into 3ml of water and 57mg of cobalt chloride hexahydrate solution dissolved into 3ml of water, and continuously stirring for 24h at room temperature to obtain gray precipitate containing a platinum-cobalt bimetallic complex;
b. carrying out suction filtration and water washing on the aqueous solution containing the platinum-cobalt bimetallic complex molecules, repeating the steps for three times, and then putting the aqueous solution into a vacuum drying oven at 65 ℃ for drying for 6 hours;
c. dissolving the completely dried 28mg bimetallic complex molecule and 20mg carbon black XC-72 in a mixed solvent of 10ml tertiary butanol and 12ml water, performing ultrasound treatment in an ultrasonic machine for 1h, transferring the obtained uniform mixture into a centrifuge tube, freezing in liquid nitrogen for 20min, drying in a freeze dryer for 48h, and removing the solvent;
d. transferring the dried mixture of the carbon black and the platinum-cobalt bimetallic complex into a quartz crucible, putting the quartz crucible into a tubular furnace, raising the temperature of the tubular furnace to 550 ℃ at the heating rate of 5 ℃/min under the argon-hydrogen atmosphere (the volume ratio of argon to hydrogen is 95:5), preserving the temperature of the tubular furnace for 12h at 550 ℃, naturally cooling the temperature to room temperature, and keeping the pressure in the tubular furnace at normal pressure to obtain the PtCo intermetallic compound catalyst with the Pt loading of 30 wt%.
FIG. 1 is an X-ray powder diffraction pattern of 30 wt% PtCo intermetallic compound prepared in example 1 of the present invention, from which it can be seen that the X-ray diffraction pattern matches with XRD standard PDF card of PtCo, demonstrating the synthesis of ordered PtCo intermetallic compound phase;
fig. 2 is a transmission electron micrograph of 30 wt% PtCo intermetallic compound prepared in example 1 of the present invention, and it can be seen from fig. 2 that the size of the PtCo intermetallic compound prepared from the platinum-cobalt bimetallic complex is about 4 to 6nm and the distribution is uniform.
Example 2
a. Dispersing 68 mu L of thioacetic acid solution into 30ml of water, then adding 85mg of sodium bicarbonate solution dissolved into 3ml of water, stirring for 5min at room temperature, sequentially adding 100mg of potassium chloroplatinite solution dissolved into 3ml of water and 57mg of cobalt chloride hexahydrate solution dissolved into 3ml of water, and continuously stirring for 24h at room temperature to obtain gray precipitate containing a platinum-cobalt bimetallic complex;
b. carrying out suction filtration and water washing on the aqueous solution containing the platinum-cobalt bimetallic complex molecules, repeating the steps for three times, and then putting the aqueous solution into a vacuum drying oven at 65 ℃ for drying for 6 hours;
c. dissolving the completely dried 47.4mg of bimetallic complex molecule and 20mg of carbon black KJ300 into a mixed solvent of 10ml of tertiary butanol and 12ml of water, performing ultrasound treatment in an ultrasonic machine for 1h, transferring the obtained uniform mixture into a centrifugal tube, freezing in liquid nitrogen for 20min, drying in a freeze dryer for 48h, and removing the solvent;
d. transferring the dried mixture of the carbon black and the platinum-cobalt bimetallic complex into a quartz crucible, putting the quartz crucible into a tubular furnace, heating the tubular furnace to 600 ℃ at the heating rate of 5 ℃/min under the argon-hydrogen atmosphere (the volume ratio of argon to hydrogen is 95:5), preserving the heat for 8h at the temperature of 600 ℃, naturally cooling to room temperature, and keeping the normal pressure in the tubular furnace to obtain the PtCo intermetallic compound catalyst with the Pt loading of 40 wt%.
FIG. 3 is an X-ray powder diffraction pattern of 40 wt% PtCo intermetallic compound prepared in example 2 of the present invention, from which it can be seen that the X-ray diffraction pattern matches with XRD standard PDF card of PtCo, demonstrating the synthesis of ordered PtCo intermetallic compound phase;
FIG. 4 is a TEM photograph of 40 wt% PtCo intermetallic compound prepared in example 2 of the present invention, and it can be seen from FIG. 4 that the size of PtCo intermetallic compound increases with the particle size of about 6-10nm at higher annealing temperature (600 ℃ C.) and higher Pt loading (40 wt%) by using KJ300 carbon black having a higher specific surface area as a carrier.
Example 3
a. Dispersing 68 mu L of thioacetic acid solution into 30ml of water, then adding 85mg of sodium bicarbonate solution dissolved into 3ml of water, stirring for 5min at room temperature, sequentially adding 100mg of potassium chloroplatinite solution dissolved into 3ml of water and 67mg of ferrous sulfate heptahydrate solution dissolved into 3ml of water, and continuously stirring for 24h at room temperature to obtain a precipitate containing a platinum-iron bimetallic complex;
b. carrying out suction filtration and water washing on the aqueous solution containing the platinum-iron bimetallic complex molecules, repeating the steps for three times, and then putting the aqueous solution into a vacuum drying oven at 65 ℃ for drying for 6 hours;
c. dissolving the completely dried 27.6mg of bimetallic complex molecule and 20mg of carbon black XC-72 into a mixed solvent of 10ml of tertiary butanol and 12ml of water, performing ultrasound in an ultrasonic machine for 1h, transferring the obtained uniform mixture into a centrifuge tube, freezing in liquid nitrogen for 20min, drying on a freeze dryer for 48h, and removing the solvent;
d. transferring the dried mixture of the carbon black and the platinum-iron bimetallic complex into a quartz crucible, putting the quartz crucible into a tube furnace, heating the tube furnace to 700 ℃ at the heating rate of 5 ℃/min under the argon-hydrogen atmosphere (the volume ratio of argon to hydrogen is 95:5), preserving the heat for 4h at 700 ℃, naturally cooling to room temperature, and keeping the normal pressure in the tube furnace to obtain the PtFe intermetallic compound catalyst with the Pt loading of 30 wt%.
FIG. 5 is an X-ray powder diffraction pattern of 30 wt% PtFe intermetallic compound prepared in example 3 of the present invention, from which it can be seen that the X-ray diffraction pattern matches with XRD standard PDF card of PtFe, demonstrating the synthesis of ordered PtFe intermetallic compound phase;
fig. 6 is a transmission electron micrograph of a 30 wt% PtFe intermetallic compound prepared in example 3 of the present invention, and it can be seen from fig. 6 that the size of the PtFe intermetallic compound prepared from the platinum-iron bimetallic complex is mostly 7 to 9 nm.
Example 4
a. Dispersing 68 mu L of thioacetic acid solution into 30ml of water, then adding 85mg of sodium bicarbonate solution dissolved into 3ml of water, stirring for 5min at room temperature, sequentially adding 100mg of potassium chloroplatinite solution dissolved into 3ml of water and 57mg of nickel chloride hexahydrate solution dissolved into 3ml of water, and continuously stirring for 24h at room temperature to obtain a precipitate containing a platinum-nickel bimetallic complex;
b. carrying out suction filtration and water washing on the aqueous solution containing the platinum-nickel bimetallic complex molecules, repeating the steps for three times, and then putting the aqueous solution into a vacuum drying oven at 65 ℃ for drying for 6 hours;
c. mixing the completely dried 28mg bimetallic complex molecule and 20mg carbon black XC-72, dissolving into a mixed solvent of 10ml tertiary butanol and 12ml water, performing ultrasound in an ultrasonic machine for 1h, transferring the obtained uniform mixture into a centrifuge tube, freezing in liquid nitrogen for 20min, drying on a freeze dryer for 48h, and removing the solvent;
d. transferring the dried mixture of the carbon black and the platinum-nickel bimetallic complex into a quartz crucible, putting the quartz crucible into a tube furnace, heating the tube furnace to 600 ℃ at the heating rate of 5 ℃/min under the argon-hydrogen atmosphere (the volume ratio of argon to hydrogen is 95:5), preserving the temperature for 20h at 600 ℃, naturally cooling to room temperature, and keeping the normal pressure in the tube furnace to obtain the PtNi intermetallic compound catalyst with the Pt loading of 30 wt%.
FIG. 7 is an X-ray powder diffraction pattern of 30 wt% PtNi intermetallic compound prepared in example 3 of the present invention, from which it can be seen that the X-ray diffraction pattern matches with XRD standard PDF card of PtNi, demonstrating the synthesis of ordered PtNi intermetallic compound phase;
fig. 8 is a transmission electron micrograph of the PtNi intermetallic compound of 30 wt% prepared in example 4 of the present invention, and it can be seen from fig. 8 that the size of the PtNi intermetallic compound prepared by the platinum-nickel bimetallic complex is 6 to 10 nm.
Example 5
a. Dispersing 68 mu L of thioacetic acid solution into 30ml of water, then adding 85mg of sodium bicarbonate solution dissolved into 3ml of water, stirring for 5min at room temperature, sequentially adding 100mg of potassium chloroplatinite solution dissolved into 3ml of water and 68mg of zinc sulfate heptahydrate solution dissolved into 3ml of water, and continuously stirring for 24h at room temperature to obtain a precipitate containing a platinum-zinc bimetallic complex;
b. carrying out suction filtration and water washing on the aqueous solution containing the platinum-zinc bimetallic complex molecules, repeating the steps for three times, and then putting the aqueous solution into a vacuum drying oven at 65 ℃ for drying for 6 hours;
c. dissolving the completely dried 28.8mg of bimetallic complex molecule and 20mg of carbon black XC-72 into a mixed solvent of 10ml of tertiary butanol and 12ml of water, performing ultrasound treatment in an ultrasonic machine for 1h, transferring the obtained uniform mixture into a centrifuge tube, freezing in liquid nitrogen for 20min, drying in a freeze dryer for 48h, and removing the solvent;
d. transferring the dried mixture of the carbon black and the platinum-zinc bimetallic complex into a quartz crucible, putting the quartz crucible into a tube furnace, heating the tube furnace to 600 ℃ at the heating rate of 5 ℃/min under the argon-hydrogen atmosphere (the volume ratio of argon to hydrogen is 95:5), preserving the heat at 600 ℃ for 12h, naturally cooling to room temperature, and keeping the normal pressure in the tube furnace to obtain the PtZn intermetallic compound catalyst with the Pt loading of 30 wt%.
FIG. 9 is an X-ray powder diffraction pattern of 30 wt% PtZn intermetallic compound prepared in example 5 of the present invention, from which it can be seen that the X-ray diffraction pattern matches with XRD standard PDF card of PtZn, demonstrating that an ordered PtZn intermetallic compound phase is synthesized;
fig. 10 is a transmission electron micrograph of 30 wt% PtZn intermetallic compound prepared in example 5 of the present invention, and it is understood from fig. 10 that most of PtZn intermetallic compounds prepared by platinum-zinc bimetallic complex have a size of about 7 to 9nm and relatively uniform size distribution.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A method for preparing an intermetallic compound catalyst using a bimetallic complex, comprising the steps of:
s1) mixing thioacetic acid, sodium bicarbonate, potassium platinochloride and transition metal salt in an aqueous solution to obtain a bimetallic complex molecule separated out in a precipitation form;
s2) removing moisture from the bimetal complex molecule;
s3) mixing the bimetal complex molecule after water removal and carbon black in a mixed solvent of tertiary butanol and water, and freeze-drying to obtain a mixture of the bimetal complex molecule and the carbon black;
s4) calcining the above mixture in a reducing atmosphere to obtain an intermetallic compound catalyst.
2. The method of claim 1, wherein the transition metal salt is selected from transition metal salts containing cobalt, iron, nickel, or zinc.
3. The method of claim 2, wherein the transition metal salt is selected from one or more of cobalt chloride hexahydrate, ferrous sulfate heptahydrate, nickel chloride hexahydrate, and zinc sulfate heptahydrate.
4. The method according to claim 1, wherein the step S1) is specifically:
dissolving sodium bicarbonate in aqueous solution of thioacetic acid, stirring to dissolve, sequentially adding potassium platinochloride and transition metal salt, and stirring at room temperature until precipitate is generated.
5. The method according to claim 1, wherein the moisture removal treatment is suction filtration and/or vacuum drying.
6. The method according to claim 1, wherein the mass fraction of the tertiary butanol in the mixed solvent of tertiary butanol and water is 10% to 90%.
7. The method according to claim 1, wherein the step S3) is specifically:
and mixing the dehydrated bimetallic complex molecules and carbon black in a mixed solvent of tert-butyl alcohol and water, carrying out ultrasonic treatment for 1-2 hours, freezing for 20-30 min under liquid nitrogen, and then putting into a freeze dryer for drying for 36-64h to remove the solvent to obtain a mixture of the bimetallic complex molecules and the carbon black.
8. The method of claim 1, wherein the reducing atmosphere comprises hydrogen and an inert gas.
9. The method according to claim 1, wherein the temperature of the calcination is 500 to 1100 ℃;
the temperature rise speed of the calcination is 2-30 ℃/min;
the calcining time is 2-40 h.
10. An intermetallic compound catalyst prepared by the method of any one of claims 1 to 9, wherein the loading of Pt on carbon black is 30% to 60%.
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