CN112337480B - PtCo nano alloy modified Co 3 O 4 -SiO 2 Flower-like multistage composite material and preparation method thereof - Google Patents
PtCo nano alloy modified Co 3 O 4 -SiO 2 Flower-like multistage composite material and preparation method thereof Download PDFInfo
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- 229910004298 SiO 2 Inorganic materials 0.000 title claims abstract description 145
- 229910020599 Co 3 O 4 Inorganic materials 0.000 title claims abstract description 98
- 239000002131 composite material Substances 0.000 title claims abstract description 76
- 229910002837 PtCo Inorganic materials 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 50
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 18
- 239000000956 alloy Substances 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000002105 nanoparticle Substances 0.000 claims abstract description 9
- 238000005054 agglomeration Methods 0.000 claims abstract description 6
- 230000002776 aggregation Effects 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims description 86
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 68
- 239000008367 deionised water Substances 0.000 claims description 64
- 229910021641 deionized water Inorganic materials 0.000 claims description 64
- 238000006243 chemical reaction Methods 0.000 claims description 62
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 59
- 239000000047 product Substances 0.000 claims description 43
- 238000001035 drying Methods 0.000 claims description 41
- 229910052710 silicon Inorganic materials 0.000 claims description 41
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 38
- 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 38
- 239000010703 silicon Substances 0.000 claims description 38
- 238000005303 weighing Methods 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 35
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 33
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 33
- 238000001816 cooling Methods 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- 238000001291 vacuum drying Methods 0.000 claims description 24
- 238000004140 cleaning Methods 0.000 claims description 23
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 23
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 23
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 23
- -1 polytetrafluoroethylene Polymers 0.000 claims description 22
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 22
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 22
- 239000002244 precipitate Substances 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 12
- 238000005520 cutting process Methods 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 12
- 239000005457 ice water Substances 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 239000002114 nanocomposite Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- STXKJSYMVDTOSJ-UHFFFAOYSA-M chlorocopper hexahydrate Chemical compound [Cu]Cl.O.O.O.O.O.O STXKJSYMVDTOSJ-UHFFFAOYSA-M 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 239000006249 magnetic particle Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 238000005245 sintering Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
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- 102000020897 Formins Human genes 0.000 description 21
- 108091022623 Formins Proteins 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 20
- 238000007789 sealing Methods 0.000 description 20
- 238000003786 synthesis reaction Methods 0.000 description 20
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 12
- 238000012512 characterization method Methods 0.000 description 11
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- 238000001132 ultrasonic dispersion Methods 0.000 description 9
- 238000009826 distribution Methods 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 239000002064 nanoplatelet Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Silicon Compounds (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a PtCo nano alloy modified Co 3 O 4 ‑SiO 2 Flower-like multi-stage composite material and its preparation method are provided. The preparation method comprises the following steps: (1) Co (Co) 3 O 4 ‑SiO 2 Preparing a composite material; (2) PtCo/Co 3 O 4 ‑SiO 2 Preparation of the composite material. PtCo/Co with three-dimensional flower-like structure prepared by the method 3 O 4 ‑SiO 2 The composite material has very high CO catalytic oxidation activity, excellent high thermal stability and no obvious agglomeration and sintering of PtCo nano particles after being circularly catalyzed for 20 times in the temperature range of 100-400 ℃. The method has the advantages of novel process, universal preparation conditions, stable product morphology, high purity, convenient and concise product treatment, and suitability for medium-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of composite materials, and relates to PtCo nano alloy modified Co 3 O 4 -SiO 2 Flower-like multi-stage composite material and its preparation method are provided.
Background
Many industrial catalytic reactions, such as oxidation, combustion, hydrogenation and reduction of CO, need to be carried out at a reaction temperature above 300 ℃, so that designing a catalyst which can resist high temperature and has high catalytic performance is of great importance to industrial production. At present, the nanocomposite containing Pt is widely studied to catalyze CO oxidation, and particularly Pt nanoparticles dispersed on a carrier with high specific surface area can effectively improve the utilization rate of active atoms so as to realize high catalytic activity. Unfortunately, pt nanoparticles are extremely susceptible to agglomeration and sintering in order to reduce surface energy in high temperature environments, resulting in catalyst failure. To solve this problem, the carrier is stableSurface introduction of atomically dispersed Pt 2+ Due to the existence of a certain chemical bond, pt and a carrier can exist stably, so that the agglomeration and sintering problem of Pt nano particles in a high-temperature environment is solved. In addition, how to increase the activity of catalyzing the oxidation of CO at normal temperature is also a difficult problem. It is an important challenge to design a highly active Pt-containing catalyst with high cycling stability over a relatively large temperature range.
For decades, two-dimensional nanostructures have attracted attention in the catalytic field due to unique structural features, in which non-noble metal nanoplatelets of atomic thickness, particularly ultrathin nanoplatelets with defects, are considered an excellent high catalytic performance material because of the large number of catalytically active sites. However, two-dimensional nanostructures have limited their practical use to a great extent because they are not easily maintained in structural stability at high temperatures. SiO (SiO) 2 The active component is used as a carrier and a core-shell structure in a heterogeneous catalytic reaction system to stabilize the active component, wherein the carrier is not capable of effectively inhibiting agglomeration and sintering of the active substance in a high-temperature environment, and the core-shell structure can lead the active substance and a catalytic substrate to be insufficiently contacted to reduce the catalytic activity. Therefore, in order to further increase the stability of the active material without affecting the original catalytic activity, the active material is uniformly embedded in SiO 2 The surface of the nanoplatelets.
Disclosure of Invention
The invention aims to provide PtCo nano alloy modified Co 3 O 4 -SiO 2 The preparation method of the flower-shaped multistage composite material has the characteristics of convenience in cleaning, simplicity in operation, energy conservation, high efficiency, easiness in control and the like.
In order to achieve the above object, the technical scheme of the present invention is as follows:
PtCo nano alloy modified Co 3 O 4 -SiO 2 The preparation method of the flower-shaped multistage composite material comprises the following steps:
(1)Co 3 O 4 -SiO 2 of composite materialPreparing;
(2)PtCo/Co 3 O 4 -SiO 2 preparation of the composite material.
The Co is 3 O 4 -SiO 2 The preparation of the composite material comprises the following steps:
(1) Separately weighing copper chloride hexahydrate (CuCl) 2 ·6H 2 O) and cobalt chloride hexahydrate (CoCl) 2 ·6H 2 O) dissolving in a solvent to prepare a copper chloride solution and a cobalt chloride solution;
(2) Pretreating a silicon wafer to obtain a treated silicon wafer;
(3) Adding CuCl into a high-temperature reaction kettle 2 Solution and CoCl 2 Adding urea powder and the treated silicon wafer into the solution, stirring and dissolving;
(4) Heating the high-temperature reaction kettle and preserving heat;
(5) Cooling the high-temperature reaction kettle to room temperature, centrifugally separating a product in the reaction kettle, alternately and sequentially cleaning with deionized water and absolute ethyl alcohol, and then drying in a vacuum drying oven to obtain a dried product;
(6) Placing the dried product obtained in the step (5) into a tube furnace, heating up and calcining at high temperature in air atmosphere, and cooling to room temperature to obtain Co 3 O 4 -SiO 2 A composite material.
The Co is 3 O 4 -SiO 2 The solvent in the step (1) is deionized water.
The Co is 3 O 4 -SiO 2 The purity of the cobalt chloride hexahydrate in the step (1) is not lower than the chemical purity.
The Co is 3 O 4 -SiO 2 The purity of the copper chloride hexahydrate in the step (1) is not lower than the chemical purity.
The Co is 3 O 4 -SiO 2 The preparation method of the composite material comprises the step (1) that the concentration of the copper chloride solution is 5mmol/L-20mmol/L.
The Co is 3 O 4 -SiO 2 A method for producing a composite material, said steps(1) The concentration of the cobalt chloride solution is 5mmol/L-20mmol/L.
The Co is 3 O 4 -SiO 2 The preparation method of the composite material comprises the following steps of: cutting the silicon wafer into square small pieces with the length of not more than 1cm and the length of 1cm, sequentially and alternately ultrasonically washing the square small pieces with ethanol and acetone until the solution is clear, ultrasonically treating the square small pieces with deionized water for three times, and then storing the square small pieces in deionized water for later use.
The Co is 3 O 4 -SiO 2 A method for preparing a composite material, wherein in the step (3), cuCl 2 Solution and CoCl 2 The volume ratio of the solution is 1:3.
The Co is 3 O 4 -SiO 2 And (3) a preparation method of the composite material, wherein the drying time in the step (5) is 24 hours.
The Co is 3 O 4 -SiO 2 The drying temperature in the step (5) is 50-80 ℃.
The Co is 3 O 4 -SiO 2 The preparation method of the composite material comprises the step (6) of calcining at 200-500 ℃.
The Co is 3 O 4 -SiO 2 The preparation method of the composite material comprises the step (6) of calcining for 5 hours.
The PtCo/Co 3 O 4 -SiO 2 The preparation of the composite material comprises the following steps:
(1) Separately weighing hexachloroplatinic acid (H) 2 PtCl 6 ·6H 2 O) and sodium borohydride (NaBH) 4 ) Dissolving in solvent to obtain H 2 PtCl 6 Aqueous solution and NaBH 4 The water solution is ready for use;
(2) Weighing Co 3 O 4 -SiO 2 Dissolving the composite material in deionized water, uniformly dispersing by ultrasonic waves, adding polyvinylpyrrolidone (PVP), and dissolving by ultrasonic waves;
(3) Adding H 2 PtCl 6 The solution is evenly dispersed by ultrasonic, then is put into an ice water bath, stirred and added with NaBH 4 An aqueous solution;
(4) After reaction precipitation, centrifugally extracting and precipitatingWashing the precipitate with deionized water and absolute ethanol alternately, and vacuum drying to obtain dry Pt/Co 3 O 4 -SiO 2 ；
(5) The Pt/Co after drying in the step (4) is processed 3 O 4 -SiO 2 Transferring to a tube furnace, heating in hydrogen atmosphere, heating at constant temperature, and cooling to room temperature to obtain PtCo/Co 3 O 4 -SiO 2 A composite material.
The PtCo/Co 3 O 4 -SiO 2 A method for producing a composite material, wherein chloroplatinic acid hexahydrate (H) in the step (1) 2 PtCl 6 ·6H 2 O) mass purity is not lower than 37%.
The PtCo/Co 3 O 4 -SiO 2 The solvent in the step (1) is deionized water.
The PtCo/Co 3 O 4 -SiO 2 The purity of the sodium borohydride in the step (1) is not lower than the chemical purity.
The PtCo/Co 3 O 4 -SiO 2 The stirring in the step (3) is polytetrafluoroethylene magnetic stirring.
The PtCo/Co 3 O 4 -SiO 2 A preparation method of a composite material, wherein in the step (3), naBH is adopted 4 The aqueous solution is prepared in situ.
The PtCo/Co 3 O 4 -SiO 2 A preparation method of a composite material, wherein in the step (3), naBH is adopted 4 The refrigerating temperature of the aqueous solution is-14 ℃ to-4 ℃.
The PtCo/Co 3 O 4 -SiO 2 The preparation method of the composite material comprises the step (4) of drying at 50-80 ℃.
The PtCo/Co 3 O 4 -SiO 2 The preparation method of the composite material comprises the step (4) of drying for 10-12 h.
The PtCo/Co 3 O 4 -SiO 2 The preparation method of the composite material comprises the step (5) of reducing atmosphere of hydrogen gas to 5% (saturated by argon).
The PtCo/Co 3 O 4 -SiO 2 The preparation method of the composite material comprises the step (5) of heating at the temperature rate of 10 ℃ for min -1 。
The PtCo/Co 3 O 4 -SiO 2 The preparation method of the composite material comprises the following steps of (5) and (2) maintaining the temperature at 350-450 ℃.
The PtCo/Co 3 O 4 -SiO 2 The preparation method of the composite material comprises the step (5) of keeping the temperature for 1h.
PtCo nano alloy modified Co prepared according to the method 3 O 4 -SiO 2 Flower-like multi-stage composite material, ptCo nano alloy is uniformly loaded on three-dimensional flower-like Co formed by assembling two-dimensional films 3 O 4 -SiO 2 On the nano composite, the dispersibility among the nanospheres is good and no agglomeration exists.
By adopting the scheme, the invention has the beneficial effects that:
the method has certain universality for preparing the three-dimensional nano-composite and the high-activity Pt-containing nano-composite; the preparation method is simple to operate, and raw materials are easy to obtain; the product prepared by the method has high activity CO oxidation performance, has ultrahigh thermal stability, has little activity reduction after continuous catalysis at a constant temperature and cyclic catalysis at a high temperature, can be used as a high-performance CO catalytic oxidation material, and has wide development prospect and application space; the method has the advantages of simple process, energy conservation, high efficiency, easy control of reaction conditions, stable product morphology, convenient and concise product treatment, and suitability for medium-scale industrial production.
The invention provides a PtCo nano alloy modified Co 3 O 4 -SiO 2 The preparation method of the flower-like multistage composite material has the advantages of nano alloy and surface active lattice oxygen in the CO catalytic oxidation reaction. And the material also contains Co 3 O 4 -SiO 2 The ultra-high thermal stability of the nano flower-shaped structure can keep the activity not to be reduced in high-temperature cyclic catalysis and long-time continuous catalysis. So the material is inThe method has important application prospect in the fields of CO catalytic oxidation and the like.
Drawings
FIG. 1 is a laboratory prepared Co 3 O 4 -SiO 2 SEM images at different fold; wherein:
a is Co in example 1 3 O 4 -SiO 2 SEM photographs of the product obtained at a magnification of 10 μm;
b is Co in example 1 3 O 4 -SiO 2 SEM photographs of the product obtained at a magnification of 2 μm;
c is Co in example 1 3 O 4 -SiO 2 SEM photographs of the product obtained at a magnification of 1 μm.
FIG. 2 shows a laboratory prepared PtCo/Co 3 O 4 -SiO 2 A TEM photograph of (C) and a particle size distribution diagram of PtCo alloy; wherein:
a is PtCo/Co in example 1 3 O 4 -SiO 2 TEM pictures of the product obtained at a magnification of 20 μm;
b is PtCo/Co in example 1 3 O 4 -SiO 2 Particle size distribution of the PtCo alloy.
FIG. 3 shows a laboratory prepared PtCo/Co 3 O 4 -SiO 2 SEM images of (a) and corresponding Si, co and Pt element distribution diagrams; wherein:
a is PtCo/Co in example 1 3 O 4 -SiO 2 SEM photographs of the nanoflower-like multi-stage material;
b is PtCo/Co in example 1 3 O 4 -SiO 2 Corresponding Si element distribution diagram of SEM image of nanometer flower-like multi-stage material;
c is PtCo/Co in example 1 3 O 4 -SiO 2 Corresponding Co element distribution diagram of SEM image of nanometer flower-like multi-stage material;
d is PtCo/Co in example 1 3 O 4 -SiO 2 Corresponding Pt element profile of SEM images of nanoflower-like multi-stage materials.
FIG. 4 is Co in example 1 3 O 4 -SiO 2 、Pt/Co 3 O 4 -SiO 2 、PtCo/Co 3 O 4 -SiO 2 Is a EDS map of (C).
FIG. 5 is Co in example 1 3 O 4 -SiO 2 、Pt/Co 3 O 4 -SiO 2 、PtCo/Co 3 O 4 -SiO 2 Is a XRD pattern of (C).
Detailed Description
The invention will be described in further detail below with reference to the embodiments shown in the drawings.
Example 1
1)Co 3 O 4 -SiO 2 The synthesis steps of the composite material are as follows:
the first step: separately weighing CuCl with certain mass 2 ·6H 2 O and CoCl 2 ·6H 2 O, configured as CuCl at a concentration of 5mM 2 Aqueous solution and 5mM CoCl 2 An aqueous solution. The preparation method comprises the steps of preprocessing a silicon wafer, cutting the silicon wafer into square small pieces with the length of 1cm and the length of 1cm, alternately ultrasonically washing the square small pieces with ethanol and acetone until the solution is clear, ultrasonically treating the square small pieces with deionized water for three times, and storing the square small pieces in deionized water for later use.
And a second step of: 5mL of CuCl was added to a 30mL polytetrafluoroethylene high temperature reactor with a pipette 2 Aqueous solution and 15mL of CoCl 2 200mg of urea and a piece of treated silicon wafer are added into the aqueous solution, and stirring and dissolution are carried out.
And a third step of: sealing the reaction kettle, placing in an electrothermal constant temperature blast drying oven at 1 deg.C for min -1 The temperature rise rate of (2) was increased from room temperature to 140℃and incubated at 140℃for 8h.
Fourth step: and (3) naturally cooling the reaction system to room temperature, transferring and collecting the product in the reaction kettle into a centrifuge tube, centrifugally extracting precipitate, alternately cleaning with deionized water and absolute ethyl alcohol, and then drying in a vacuum drying oven for 24 hours.
Fifth step: pouring the dried product into a magnetic boat, transferring to a tube furnace in air atmosphere at 10deg.C for min -1 The temperature rise rate of (2) is increased from room temperature to 400 ℃, and the mixture is heated for 5 hours at constant temperature. After cooling to room temperature, taking out, sealing and preserving for subsequent experimentsAnd (3) using.
2)PtCo/Co 3 O 4 -SiO 2 The synthesis steps of the composite material are as follows:
the first step: respectively weighing H with certain mass 2 PtCl 6 ·6H 2 O and NaBH 4 H configured to a concentration of 5mM 2 PtCl 6 Aqueous solution and 10mM NaBH 4 An aqueous solution.
And a second step of: weighing 2mg of the prepared Co 3 O 4 -SiO 2 Into a beaker containing 19mL of deionized water, 200mg of polyvinylpyrrolidone (PVP) was added after uniform ultrasonic dispersion, and dissolved by ultrasonic.
And a third step of: 1mL of H was added to the reaction system 2 PtCl 6 The aqueous solution is placed in an ice-water bath after being evenly dispersed by ultrasonic treatment for 2 hours, polytetrafluoroethylene magnons are added for stirring, and 2mL of freshly prepared chilled NaBH is added 4 An aqueous solution.
Fourth step: after reaction precipitation at normal temperature, centrifugally extracting precipitate Pt/Co 3 O 4 -SiO 2 . Alternately cleaning with deionized water and absolute ethyl alcohol, and then drying in a vacuum drying oven for 24 hours.
Fifth step: introducing the dried product into a magnetic boat, spreading, transferring to a tube furnace at 5%H 2 (argon saturation) atmosphere at 10 ℃ C. Min -1 The temperature rise rate of (2) was increased from room temperature to 400 ℃, heated at constant temperature for 1h, then cooled to room temperature, and stored in a sealed condition for further characterization of the test.
FIGS. 1 (A-C) are Co obtained at different magnifications in example 1 3 O 4 -SiO 2 Emission scanning electron microscopy SEM of the composite, co can be seen 3 O 4 -SiO 2 The compound is a uniformly dispersed three-dimensional flower-like structure.
FIG. 2 (A, B) shows the PtCo/Co produced 3 O 4 -SiO 2 A TEM photograph of (C) and a particle size distribution diagram of PtCo alloy. It can be seen that PtCo nanoparticles are already supported on Co 3 O 4 -SiO 2 The particle size of PtCo particles is about 3nm on the surface.
FIG. 3 (A, B, C),D) Shows PtCo/Co 3 O 4 -SiO 2 The SEM image of the (C) and corresponding Si, co and Pt element distribution patterns can obviously observe that the distribution of the three elements of Si, co and Pt basically accords with the shape outline of the compound in the A image, and clearly shows that the Si content is the most, the Co is centered and the Pt content is the least.
The characterization of FIG. 4 shows Co 3 O 4 -SiO 2 、Pt/Co 3 O 4 -SiO 2 、PtCo/Co 3 O 4 -SiO 2 EDS spectra of the three materials can clearly show Co 3 O 4 -SiO 2 The nanocomposite contains three elements O, si and Co. Pt/Co formed after Pt nanoparticles are supported 3 O 4 -SiO 2 Four elements of O, si, co and Pt can be detected, and PtCo/Co obtained after the alloy is partially reduced 3 O 4 -SiO 2 EDS energy spectrum and Pt/Co of (C) 3 O 4 -SiO 2 The complex is similar.
FIG. 5 characterization shows Co 3 O 4 -SiO 2 、Pt/Co 3 O 4 -SiO 2 、PtCo/Co 3 O 4 -SiO 2 XRD patterns of three materials, pt/Co 3 O 4 -SiO 2 Except Co 3 O 4 The diffraction peaks are three diffraction peaks at 39.7 degrees, 46.2 degrees and 67.4 degrees, and are respectively corresponding to (111), (200) and (220) crystal faces of Pt and PtCo/Co by comparison of standard cards 3 O 4 -SiO 2 Except Co 3 O 4 The three diffraction peaks outside the diffraction peaks were located at 40.3 °, 46.8 ° and 68.0 °, respectively, shifted to the right with respect to the diffraction peak of Pt in curve b and all of these three peaks were located in the middle of the standard peaks of Pt (JCPDF No. 65-6828) and Co (JCPDF No. 15-0806), indicating the presence of PtCo alloy.
Example 2
1)Co 3 O 4 -SiO 2 The synthesis steps of the composite material are as follows:
the first step: separately weighing CuCl with certain mass 2 ·6H 2 O and CoCl 2 ·6H 2 O is configured as CuCl with a concentration of 5mM 2 Aqueous solution and 5mM CoCl 2 An aqueous solution. The preparation method comprises the steps of preprocessing a silicon wafer, cutting the silicon wafer into square small pieces with the length of 1cm and the length of 1cm, alternately ultrasonically washing the square small pieces with ethanol and acetone until the solution is clear, ultrasonically treating the square small pieces with deionized water for three times, and storing the square small pieces in deionized water for later use.
And a second step of: 5mL of CuCl was added to a 30mL polytetrafluoroethylene high temperature reactor with a pipette 2 Aqueous solution and 15mL of CoCl 2 200mg of urea and a piece of treated silicon wafer are added into the aqueous solution, and stirring and dissolution are carried out.
And a third step of: sealing the reaction kettle, placing in an electrothermal constant temperature blast drying oven at 1 deg.C for min -1 The temperature rise rate of (C) was increased from room temperature and incubated at 130℃at 140℃at 150℃for 8 hours.
Fourth step: and (3) naturally cooling the reaction system to room temperature, transferring and collecting the product in the reaction kettle into a centrifuge tube, centrifugally extracting precipitate, alternately cleaning with deionized water and absolute ethyl alcohol, and then drying in a vacuum drying oven for 24 hours.
Fifth step: pouring the dried product into a magnetic boat, transferring to a tube furnace in air atmosphere at 10deg.C for min -1 The temperature rise rate of (2) is increased from room temperature to 400 ℃, and the mixture is heated for 5 hours at constant temperature. And after cooling to room temperature, taking out, sealing and preserving for subsequent experiments.
2)PtCo/Co 3 O 4 -SiO 2 The synthesis steps of the composite material are as follows:
the first step: respectively weighing H with certain mass 2 PtCl 6 ·6H 2 O and NaBH 4 H configured to a concentration of 5mM 2 PtCl 6 Aqueous solution and 10mM NaBH 4 An aqueous solution.
And a second step of: weighing 2mg of the prepared Co 3 O 4 -SiO 2 Into a beaker containing 19mL of deionized water, 200mg of polyvinylpyrrolidone (PVP) was added after uniform ultrasonic dispersion, and dissolved by ultrasonic.
And a third step of: 1mL of H was added to the reaction system 2 PtCl 6 The aqueous solution is placed in an ice-water bath after being evenly dispersed by ultrasonic treatment for 2 hours, polytetrafluoroethylene magnetons are added for stirring, and 2mL of freshly prepared refrigerated food is addedNaBH 4 An aqueous solution.
Fourth step: after reaction precipitation at normal temperature, centrifugally extracting precipitate Pt/Co 3 O 4 -SiO 2 . Alternately cleaning with deionized water and absolute ethyl alcohol, and then drying in a vacuum drying oven for 24 hours.
Fifth step: introducing the dried product into a magnetic boat, spreading, transferring to a tube furnace at 5%H 2 (argon saturation) atmosphere at 10 ℃ C. Min -1 The temperature rise rate of (2) was increased from room temperature to 400 ℃, heated at constant temperature for 1h, then cooled to room temperature, and stored in a sealed condition for further characterization of the test.
Example 3
1)Co 3 O 4 -SiO 2 The synthesis steps of the composite material are as follows:
the first step: separately weighing CuCl with certain mass 2 ·6H 2 O and CoCl 2 ·6H 2 O, configured as CuCl at a concentration of 5mM 2 Aqueous solution and 5mM CoCl 2 An aqueous solution. The preparation method comprises the steps of preprocessing a silicon wafer, cutting the silicon wafer into square small pieces with the length of 1cm and the length of 1cm, alternately ultrasonically washing the square small pieces with ethanol and acetone until the solution is clear, ultrasonically treating the square small pieces with deionized water for three times, and storing the square small pieces in deionized water for later use.
And a second step of: 5mL of CuCl was added to a 30mL polytetrafluoroethylene high temperature reactor with a pipette 2 Aqueous solution and 15mL of CoCl 2 Adding 300-500 mg of urea and a piece of treated silicon wafer into the aqueous solution, stirring and dissolving.
And a third step of: sealing the reaction kettle, placing in an electrothermal constant temperature blast drying oven at 1 deg.C for min -1 The temperature rise rate of (2) was increased from room temperature to 140℃and incubated at 140℃for 8h.
Fourth step: and (3) naturally cooling the reaction system to room temperature, transferring and collecting the product in the reaction kettle into a centrifuge tube, centrifugally extracting precipitate, alternately cleaning with deionized water and absolute ethyl alcohol, and then drying in a vacuum drying oven for 24 hours.
Fifth step: pouring the dried product into a magnetic boat, transferring to a tube furnace in air atmosphere at 10deg.C for min -1 Is increased from room temperatureHeating to 400 ℃ for 5 hours at constant temperature. And after cooling to room temperature, taking out, sealing and preserving for subsequent experiments.
2)PtCo/Co 3 O 4 -SiO 2 The synthesis steps of the composite material are as follows:
the first step: respectively weighing H with certain mass 2 PtCl 6 ·6H 2 O and NaBH 4 H configured to a concentration of 5mM 2 PtCl 6 Aqueous solution and 10mM NaBH 4 An aqueous solution.
And a second step of: weighing 2mg of the prepared Co 3 O 4 -SiO 2 Into a beaker containing 19mL of deionized water, 200mg of polyvinylpyrrolidone (PVP) was added after uniform ultrasonic dispersion, and dissolved by ultrasonic.
And a third step of: 1mL of H was added to the reaction system 2 PtCl 6 The aqueous solution is placed in an ice-water bath after being evenly dispersed by ultrasonic treatment for 2 hours, polytetrafluoroethylene magnons are added for stirring, and 2mL of freshly prepared chilled NaBH is added 4 An aqueous solution.
Fourth step: after reaction precipitation at normal temperature, centrifugally extracting precipitate Pt/Co 3 O 4 -SiO 2 . Alternately cleaning with deionized water and absolute ethyl alcohol, and then drying in a vacuum drying oven for 24 hours.
Fifth step: introducing the dried product into a magnetic boat, spreading, transferring to a tube furnace at 5%H 2 (argon saturation) atmosphere at 10 ℃ C. Min -1 The temperature rise rate of (2) was increased from room temperature to 400 ℃, heated at constant temperature for 1h, then cooled to room temperature, and stored in a sealed condition for further characterization of the test.
Example 4
1)Co 3 O 4 -SiO 2 The synthesis steps of the composite material are as follows:
the first step: separately weighing CuCl with certain mass 2 ·6H 2 O and CoCl 2 ·6H 2 O, configured as CuCl at a concentration of 5mM 2 Aqueous solution and 5mM CoCl 2 An aqueous solution. Pretreating silicon wafer, cutting into square pieces of 1cm, alternately ultrasonic washing with ethanol and acetone until the solution is clear, ultrasonic treating with deionized water for three times, and storing in a containerAnd (5) adding deionized water for standby.
And a second step of: 5mL of CuCl was added to a 30mL polytetrafluoroethylene high temperature reactor with a pipette 2 Aqueous solution and 15mL of CoCl 2 200mg of urea and a piece of treated silicon wafer are added into the aqueous solution, and stirring and dissolution are carried out.
And a third step of: sealing the reaction kettle, placing in an electrothermal constant temperature blast drying oven at 1 deg.C for min -1 The temperature rise rate of (2) was increased from room temperature to 140℃and incubated at 140℃for 8h.
Fourth step: and (3) naturally cooling the reaction system to room temperature, transferring and collecting the product in the reaction kettle into a centrifuge tube, centrifugally extracting precipitate, alternately cleaning with deionized water and absolute ethyl alcohol, and then drying in a vacuum drying oven for 24 hours.
Fifth step: pouring the dried product into a magnetic boat, transferring to a tube furnace in air atmosphere at 10deg.C for min -1 The temperature rising rate of the furnace is increased from room temperature to 200-500 ℃, and the furnace is heated for 5h at constant temperature. And after cooling to room temperature, taking out, sealing and preserving for subsequent experiments.
2)PtCo/Co 3 O 4 -SiO 2 The synthesis steps of the composite material are as follows:
the first step: respectively weighing H with certain mass 2 PtCl 6 ·6H 2 O and NaBH 4 H configured to a concentration of 5mM 2 PtCl 6 Aqueous solution and 10mM NaBH 4 An aqueous solution.
And a second step of: weighing 2mg of the prepared Co 3 O 4 -SiO 2 Into a beaker containing 19mL of deionized water, 200mg of polyvinylpyrrolidone (PVP) was added after uniform ultrasonic dispersion, and dissolved by ultrasonic.
And a third step of: 1mL of H was added to the reaction system 2 PtCl 6 The aqueous solution is placed in an ice-water bath after being evenly dispersed by ultrasonic treatment for 2 hours, polytetrafluoroethylene magnons are added for stirring, and 2mL of freshly prepared chilled NaBH is added 4 An aqueous solution.
Fourth step: after reaction precipitation at normal temperature, centrifugally extracting precipitate Pt/Co 3 O 4 -SiO 2 . With deionized water and anhydrous waterEthanol is alternately washed, and then dried in a vacuum drying oven for 24 hours.
Fifth step: introducing the dried product into a magnetic boat, spreading, transferring to a tube furnace at 5%H 2 (argon saturation) atmosphere at 10 ℃ C. Min -1 The temperature rise rate of (2) was increased from room temperature to 400 ℃, heated at constant temperature for 1h, then cooled to room temperature, and stored in a sealed condition for further characterization of the test.
Example 5
1)Co 3 O 4 -SiO 2 The synthesis steps of the composite material are as follows:
the first step: separately weighing CuCl with certain mass 2 ·6H 2 O and CoCl 2 ·6H 2 O, configured as CuCl at a concentration of 5mM 2 Aqueous solution and 5mM CoCl 2 An aqueous solution. The preparation method comprises the steps of preprocessing a silicon wafer, cutting the silicon wafer into square small pieces with the length of 1cm and the length of 1cm, alternately ultrasonically washing the square small pieces with ethanol and acetone until the solution is clear, ultrasonically treating the square small pieces with deionized water for three times, and storing the square small pieces in deionized water for later use.
And a second step of: 5mL of CuCl was added to a 30mL polytetrafluoroethylene high temperature reactor with a pipette 2 Aqueous solution and 15mL of CoCl 2 200mg of urea and a piece of treated silicon wafer are added into the aqueous solution, and stirring and dissolution are carried out.
And a third step of: sealing the reaction kettle, placing in an electrothermal constant temperature blast drying oven at 1 deg.C for min -1 The temperature rise rate of (2) was increased from room temperature to 140℃and incubated at 140℃for 8h.
Fourth step: and (3) naturally cooling the reaction system to room temperature, transferring and collecting the product in the reaction kettle into a centrifuge tube, centrifugally extracting precipitate, alternately cleaning with deionized water and absolute ethyl alcohol, and then drying in a vacuum drying oven for 24 hours.
Fifth step: pouring the dried product into a magnetic boat, transferring to a tube furnace in air atmosphere at 10deg.C for min -1 The temperature rise rate of (2) is increased from room temperature to 400 ℃, and the mixture is heated for 5 hours at constant temperature. And after cooling to room temperature, taking out, sealing and preserving for subsequent experiments.
2)PtCo/Co 3 O 4 -SiO 2 The synthesis steps of the composite material are as follows:
the first step: respectively weighing H with certain mass 2 PtCl 6 ·6H 2 O and NaBH 4 H at a concentration of 5 to 20mM 2 PtCl 6 Aqueous solution and 10mM NaBH 4 An aqueous solution.
And a second step of: weighing 2mg of the prepared Co 3 O 4 -SiO 2 Into a beaker containing 19mL of deionized water, 200mg of polyvinylpyrrolidone (PVP) was added after uniform ultrasonic dispersion, and dissolved by ultrasonic.
And a third step of: 1mL of H was added to the reaction system 2 PtCl 6 The aqueous solution is placed in an ice-water bath after being evenly dispersed by ultrasonic treatment for 2 hours, polytetrafluoroethylene magnons are added for stirring, and 2mL of freshly prepared chilled NaBH is added 4 An aqueous solution.
Fourth step: after reaction precipitation at normal temperature, centrifugally extracting precipitate Pt/Co 3 O 4 -SiO 2 . Alternately cleaning with deionized water and absolute ethyl alcohol, and then drying in a vacuum drying oven for 24 hours.
Fifth step: introducing the dried product into a magnetic boat, spreading, transferring to a tube furnace at 5%H 2 (argon saturation) atmosphere at 10 ℃ C. Min -1 The temperature rise rate of (2) was increased from room temperature to 400 ℃, heated at constant temperature for 1h, then cooled to room temperature, and stored in a sealed condition for further characterization of the test.
Example 6
1)Co 3 O 4 -SiO 2 The synthesis steps of the composite material are as follows:
the first step: separately weighing CuCl with certain mass 2 ·6H 2 O and CoCl 2 ·6H 2 O, configured as CuCl with a concentration of 5-20 mM 2 Aqueous solution and 5-20 mM CoCl 2 An aqueous solution. The preparation method comprises the steps of preprocessing a silicon wafer, cutting the silicon wafer into square small pieces with the length of 1cm and the length of 1cm, alternately ultrasonically washing the square small pieces with ethanol and acetone until the solution is clear, ultrasonically treating the square small pieces with deionized water for three times, and storing the square small pieces in deionized water for later use.
And a second step of: 5mL of CuCl was added to a 30mL polytetrafluoroethylene high temperature reactor with a pipette 2 Aqueous solution and 15mL of CoCl 2 Water-soluble200mg of urea and a piece of treated silicon wafer are added into the solution, and stirring and dissolution are carried out.
And a third step of: sealing the reaction kettle, placing in an electrothermal constant temperature blast drying oven at 1 deg.C for min -1 The temperature rise rate of (2) was increased from room temperature to 140℃and incubated at 140℃for 8h.
Fourth step: and (3) naturally cooling the reaction system to room temperature, transferring and collecting the product in the reaction kettle into a centrifuge tube, centrifugally extracting precipitate, alternately cleaning with deionized water and absolute ethyl alcohol, and then drying in a vacuum drying oven for 24 hours.
Fifth step: pouring the dried product into a magnetic boat, transferring to a tube furnace in air atmosphere at 10deg.C for min -1 The temperature rise rate of (2) is increased from room temperature to 400 ℃, and the mixture is heated for 5 hours at constant temperature. And after cooling to room temperature, taking out, sealing and preserving for subsequent experiments.
2)PtCo/Co 3 O 4 -SiO 2 The synthesis steps of the composite material are as follows:
the first step: respectively weighing H with certain mass 2 PtCl 6 ·6H 2 O and NaBH 4 H configured to a concentration of 5mM 2 PtCl 6 Aqueous solution and 10mM NaBH 4 An aqueous solution.
And a second step of: weighing 2mg of the prepared Co 3 O 4 -SiO 2 Into a beaker containing 19mL of deionized water, 200mg of polyvinylpyrrolidone (PVP) was added after uniform ultrasonic dispersion, and dissolved by ultrasonic.
And a third step of: 1mL of H was added to the reaction system 2 PtCl 6 The aqueous solution is placed in an ice-water bath after being evenly dispersed by ultrasonic treatment for 2 hours, polytetrafluoroethylene magnons are added for stirring, and 2mL of freshly prepared chilled NaBH is added 4 An aqueous solution.
Fourth step: after reaction precipitation at normal temperature, centrifugally extracting precipitate Pt/Co 3 O 4 -SiO 2 . Alternately cleaning with deionized water and absolute ethyl alcohol, and then drying in a vacuum drying oven for 24 hours.
Fifth step: introducing the dried product into a magnetic boat, spreading, transferring to a tube furnace at 5%H 2 (argon saturation)And) in an atmosphere at 10 ℃ min -1 The temperature rise rate of (2) was increased from room temperature to 400 ℃, heated at constant temperature for 1h, then cooled to room temperature, and stored in a sealed condition for further characterization of the test.
Example 7
1)Co 3 O 4 -SiO 2 The synthesis steps of the composite material are as follows:
the first step: separately weighing CuCl with certain mass 2 ·6H 2 O and CoCl 2 ·6H 2 O, configured as CuCl at a concentration of 5mM 2 Aqueous solution and 5mM CoCl 2 An aqueous solution. The preparation method comprises the steps of preprocessing a silicon wafer, cutting the silicon wafer into square small pieces with the length of 1cm and the length of 1cm, alternately ultrasonically washing the square small pieces with ethanol and acetone until the solution is clear, ultrasonically treating the square small pieces with deionized water for three times, and storing the square small pieces in deionized water for later use.
And a second step of: 5mL of CuCl was added to a 30mL polytetrafluoroethylene high temperature reactor with a pipette 2 Aqueous solution and 15mL of CoCl 2 200mg of urea and a piece of treated silicon wafer are added into the aqueous solution, and stirring and dissolution are carried out.
And a third step of: sealing the reaction kettle, placing in an electrothermal constant temperature blast drying oven at 1 deg.C for min -1 The temperature rise rate of (2) was increased from room temperature to 140℃and incubated at 140℃for 8h.
Fourth step: and (3) naturally cooling the reaction system to room temperature, transferring and collecting the product in the reaction kettle into a centrifuge tube, centrifugally extracting precipitate, alternately cleaning with deionized water and absolute ethyl alcohol, and then drying in a vacuum drying oven for 24 hours.
Fifth step: pouring the dried product into a magnetic boat, transferring to a tube furnace in air atmosphere at 10deg.C for min -1 The temperature rise rate of (2) is increased from room temperature to 400 ℃, and the mixture is heated for 5 hours at constant temperature. And after cooling to room temperature, taking out, sealing and preserving for subsequent experiments.
2)PtCo/Co 3 O 4 -SiO 2 The synthesis steps of the composite material are as follows:
the first step: respectively weighing H with certain mass 2 PtCl 6 ·6H 2 O and NaBH 4 H configured to a concentration of 5mM 2 PtCl 6 Aqueous solutionAnd 10mM NaBH 4 An aqueous solution.
And a second step of: weighing 2mg of the prepared Co 3 O 4 -SiO 2 Into a beaker containing 19mL of deionized water, 200mg of polyvinylpyrrolidone (PVP) was added after uniform ultrasonic dispersion, and dissolved by ultrasonic.
And a third step of: 1mL of H was added to the reaction system 2 PtCl 6 The aqueous solution is placed in an ice-water bath after being evenly dispersed by ultrasonic treatment for 2 hours, polytetrafluoroethylene magnons are added for stirring, and 1-10 mL of freshly prepared chilled NaBH is added 4 An aqueous solution.
Fourth step: after reaction precipitation at normal temperature, centrifugally extracting precipitate Pt/Co 3 O 4 -SiO 2 . Alternately cleaning with deionized water and absolute ethyl alcohol, and then drying in a vacuum drying oven for 24 hours.
Fifth step: introducing the dried product into a magnetic boat, spreading, transferring to a tube furnace at 5%H 2 (argon saturation) atmosphere at 10 ℃ C. Min -1 The temperature rise rate of (2) was increased from room temperature to 400 ℃, heated at constant temperature for 1h, then cooled to room temperature, and stored in a sealed condition for further characterization of the test.
Example 8
1)Co 3 O 4 -SiO 2 The synthesis steps of the composite material are as follows:
the first step: separately weighing CuCl with certain mass 2 ·6H 2 O and CoCl 2 ·6H 2 O, configured as CuCl at a concentration of 5mM 2 Aqueous solution and 5mM CoCl 2 An aqueous solution. The preparation method comprises the steps of preprocessing a silicon wafer, cutting the silicon wafer into square small pieces with the length of 1cm and the length of 1cm, alternately ultrasonically washing the square small pieces with ethanol and acetone until the solution is clear, ultrasonically treating the square small pieces with deionized water for three times, and storing the square small pieces in deionized water for later use.
And a second step of: 5mL of CuCl was added to a 30mL polytetrafluoroethylene high temperature reactor with a pipette 2 Aqueous solution and 15mL of CoCl 2 200mg of urea and a piece of treated silicon wafer are added into the aqueous solution, and stirring and dissolution are carried out.
And a third step of: sealing the reaction kettle, placing in an electrothermal constant temperature blast drying oven at 1 deg.C for min -1 The temperature rise rate of (2) was increased from room temperature to 140℃and incubated at 140℃for 8h.
Fourth step: and (3) naturally cooling the reaction system to room temperature, transferring and collecting the product in the reaction kettle into a centrifuge tube, centrifugally extracting precipitate, alternately cleaning with deionized water and absolute ethyl alcohol, and then drying in a vacuum drying oven for 24 hours.
Fifth step: pouring the dried product into a magnetic boat, transferring to a tube furnace in air atmosphere at 10deg.C for min -1 The temperature rise rate of (2) is increased from room temperature to 400 ℃, and the mixture is heated for 5 hours at constant temperature. And after cooling to room temperature, taking out, sealing and preserving for subsequent experiments.
2)PtCo/Co 3 O 4 -SiO 2 The synthesis steps of the composite material are as follows:
the first step: respectively weighing H with certain mass 2 PtCl 6 ·6H 2 O and NaBH 4 H configured to a concentration of 5mM 2 PtCl 6 Aqueous solution and 10mM NaBH 4 An aqueous solution.
And a second step of: weighing 2mg of the prepared Co 3 O 4 -SiO 2 Into a beaker containing 19mL of deionized water, 200mg of polyvinylpyrrolidone (PVP) was added after uniform ultrasonic dispersion, and dissolved by ultrasonic.
And a third step of: 1mL of H was added to the reaction system 2 PtCl 6 The aqueous solution is placed in an ice-water bath after being evenly dispersed by ultrasonic treatment for 2 hours, polytetrafluoroethylene magnons are added for stirring, and 2mL of freshly prepared chilled NaBH is added 4 An aqueous solution.
Fourth step: after reaction precipitation at normal temperature, centrifugally extracting precipitate Pt/Co 3 O 4 -SiO 2 . Alternately cleaning with deionized water and absolute ethyl alcohol, and then drying in a vacuum drying oven for 24 hours.
Fifth step: introducing the dried product into a magnetic boat, spreading, transferring to a tube furnace at 5%H 2 (argon saturation) atmosphere at 10 ℃ C. Min -1 The temperature rise rate of (2) is increased from room temperature to 200-500 ℃, the temperature is heated for 1h at constant temperature, then the temperature is cooled to room temperature, and the mixture is stored in a sealed mode so as to further characterize the test.
Example 9
1)Co 3 O 4 -SiO 2 The synthesis steps of the composite material are as follows:
the first step: separately weighing CuCl with certain mass 2 ·6H 2 O and CoCl 2 ·6H 2 O, configured as CuCl at a concentration of 5mM 2 Aqueous solution and 5mM CoCl 2 An aqueous solution. The preparation method comprises the steps of preprocessing a silicon wafer, cutting the silicon wafer into square small pieces with the length of 1cm and the length of 1cm, alternately ultrasonically washing the square small pieces with ethanol and acetone until the solution is clear, ultrasonically treating the square small pieces with deionized water for three times, and storing the square small pieces in deionized water for later use.
And a second step of: 5mL of CuCl was added to a 30mL polytetrafluoroethylene high temperature reactor with a pipette 2 Aqueous solution and 15mL of CoCl 2 200mg of urea and a piece of treated silicon wafer are added into the aqueous solution, and stirring and dissolution are carried out.
And a third step of: sealing the reaction kettle, placing in an electrothermal constant temperature blast drying oven at 1 deg.C for min -1 The temperature rise rate of (2) was increased from room temperature to 140℃and incubated at 140℃for 8h.
Fourth step: and (3) naturally cooling the reaction system to room temperature, transferring and collecting the product in the reaction kettle into a centrifuge tube, centrifugally extracting precipitate, alternately cleaning with deionized water and absolute ethyl alcohol, and then drying in a vacuum drying oven for 24 hours.
Fifth step: pouring the dried product into a magnetic boat, transferring to a tube furnace in air atmosphere at 10deg.C for min -1 The temperature rise rate of (2) is increased from room temperature to 400 ℃, and the mixture is heated for 5 hours at constant temperature. And after cooling to room temperature, taking out, sealing and preserving for subsequent experiments.
2)PtCo/Co 3 O 4 -SiO 2 The synthesis steps of the composite material are as follows:
the first step: respectively weighing H with certain mass 2 PtCl 6 ·6H 2 O and NaBH 4 H configured to a concentration of 5mM 2 PtCl 6 Aqueous solution and 10mM NaBH 4 An aqueous solution.
And a second step of: weighing 2mg of the prepared Co 3 O 4 -SiO 2 Added to a beaker containing 19mL of deionized water and sonicatedAfter uniform dispersion, 200-500 mg of polyvinylpyrrolidone (PVP) is added for ultrasonic dissolution.
And a third step of: 1mL of H was added to the reaction system 2 PtCl 6 The aqueous solution is placed in an ice-water bath after being evenly dispersed by ultrasonic treatment for 2 hours, polytetrafluoroethylene magnons are added for stirring, and 2mL of freshly prepared chilled NaBH is added 4 An aqueous solution.
Fourth step: after reaction precipitation at normal temperature, centrifugally extracting precipitate Pt/Co 3 O 4 -SiO 2 . Alternately cleaning with deionized water and absolute ethyl alcohol, and then drying in a vacuum drying oven for 24 hours.
Fifth step: introducing the dried product into a magnetic boat, spreading, transferring to a tube furnace at 5%H 2 (argon saturation) atmosphere at 10 ℃ C. Min -1 The temperature rise rate of (2) was increased from room temperature to 400 ℃, heated at constant temperature for 1h, then cooled to room temperature, and stored in a sealed condition for further characterization of the test.
Example 10
1)Co 3 O 4 -SiO 2 The synthesis steps of the composite material are as follows:
the first step: separately weighing CuCl with certain mass 2 ·6H 2 O and CoCl 2 ·6H 2 O, configured as CuCl at a concentration of 5mM 2 Aqueous solution and 5mM CoCl 2 An aqueous solution. The preparation method comprises the steps of preprocessing a silicon wafer, cutting the silicon wafer into square small pieces with the length of 1cm and the length of 1cm, alternately ultrasonically washing the square small pieces with ethanol and acetone until the solution is clear, ultrasonically treating the square small pieces with deionized water for three times, and storing the square small pieces in deionized water for later use.
And a second step of: 5mL of CuCl was added to a 30mL polytetrafluoroethylene high temperature reactor with a pipette 2 Aqueous solution and 15mL of CoCl 2 200mg of urea and a piece of treated silicon wafer are added into the aqueous solution, and stirring and dissolution are carried out.
And a third step of: sealing the reaction kettle, placing in an electrothermal constant temperature blast drying oven at 1 deg.C for min -1 The temperature rise rate of (2) is increased from room temperature to 140 ℃, and the temperature is kept for 8 hours under the condition of 120-200 ℃.
Fourth step: and (3) naturally cooling the reaction system to room temperature, transferring and collecting the product in the reaction kettle into a centrifuge tube, centrifugally extracting precipitate, alternately cleaning with deionized water and absolute ethyl alcohol, and then drying in a vacuum drying oven for 24 hours.
Fifth step: pouring the dried product into a magnetic boat, transferring to a tube furnace in air atmosphere at 10deg.C for min -1 The temperature rise rate of (2) is increased from room temperature to 400 ℃, and the mixture is heated for 5 hours at constant temperature. And after cooling to room temperature, taking out, sealing and preserving for subsequent experiments.
2)PtCo/Co 3 O 4 -SiO 2 The synthesis steps of the composite material are as follows:
the first step: respectively weighing H with certain mass 2 PtCl 6 ·6H 2 O and NaBH 4 H configured to a concentration of 5mM 2 PtCl 6 Aqueous solution and 10mM NaBH 4 An aqueous solution.
And a second step of: weighing 2mg of the prepared Co 3 O 4 -SiO 2 Into a beaker containing 19mL of deionized water, 200mg of polyvinylpyrrolidone (PVP) was added after uniform ultrasonic dispersion, and dissolved by ultrasonic.
And a third step of: 1mL of H was added to the reaction system 2 PtCl 6 The aqueous solution is placed in an ice-water bath after being evenly dispersed by ultrasonic treatment for 2 hours, polytetrafluoroethylene magnons are added for stirring, and 2mL of freshly prepared chilled NaBH is added 4 An aqueous solution.
Fourth step: after reaction precipitation at normal temperature, centrifugally extracting precipitate Pt/Co 3 O 4 -SiO 2 . Alternately cleaning with deionized water and absolute ethyl alcohol, and then drying in a vacuum drying oven for 24 hours.
Fifth step: introducing the dried product into a magnetic boat, spreading, transferring to a tube furnace at 5%H 2 (argon saturation) atmosphere at 10 ℃ C. Min -1 The temperature rise rate of (2) was increased from room temperature to 400 ℃, heated at constant temperature for 1h, then cooled to room temperature, and stored in a sealed condition for further characterization of the test.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the embodiments herein, and modifications made without departing from the scope of the invention are within the scope of the invention.
Claims (13)
1. PtCo nano alloy modified Co 3 O 4 -SiO 2 The preparation method of the flower-shaped multistage composite material is characterized by comprising the following steps of: the method comprises the following steps:
(1)Co 3 O 4 -SiO 2 preparing a composite material;
(2)PtCo/Co 3 O 4 -SiO 2 preparing a composite material; the Co is 3 O 4 -SiO 2 The preparation of the composite material comprises the following steps:
(1) Respectively weighing copper chloride hexahydrate and cobalt chloride hexahydrate, and dissolving the copper chloride hexahydrate and the cobalt chloride hexahydrate in a solvent to prepare a copper chloride solution and a cobalt chloride solution;
(2) Pretreating a silicon wafer to obtain a treated silicon wafer;
(3) Adding CuCl into a high-temperature reaction kettle 2 Solution and CoCl 2 Adding urea powder and the treated silicon wafer into the solution, stirring and dissolving;
(4) Heating the high-temperature reaction kettle and preserving heat;
(5) Cooling the high-temperature reaction kettle to room temperature, centrifugally separating a product in the reaction kettle, alternately and sequentially cleaning with deionized water and absolute ethyl alcohol, and then drying in a vacuum drying oven to obtain a dried product;
(6) Placing the dried product obtained in the step (5) into a tube furnace, heating up and calcining at high temperature in air atmosphere, and cooling to room temperature to obtain Co 3 O 4 -SiO 2 A composite material;
the PtCo/Co 3 O 4 -SiO 2 The preparation of the composite material comprises the following steps:
(1) Respectively weighing hexa-water chloroplatinic acid and sodium borohydride, and dissolving in a solvent to prepare H 2 PtCl 6 Aqueous solution and NaBH 4 The water solution is ready for use;
(2) Weighing Co 3 O 4 -SiO 2 Dissolving the composite material in deionized water, uniformly dispersing by ultrasonic waves, adding polyvinylpyrrolidone, and dissolving by ultrasonic waves;
(3) Adding H 2 PtCl 6 The solution is evenly dispersed by ultrasonic, then is put into an ice water bath, stirred and added with NaBH 4 An aqueous solution;
(4) After reaction precipitation, centrifugally extracting precipitate, sequentially and alternately cleaning with deionized water and absolute ethyl alcohol, and vacuum drying to obtain dry Pt/Co 3 O 4 -SiO 2 ；
(5) The Pt/Co after drying in the step (4) is processed 3 O 4 -SiO 2 Transferring to a tube furnace, heating in hydrogen atmosphere, heating at constant temperature, and cooling to room temperature to obtain PtCo/Co 3 O 4 -SiO 2 A composite material.
2. The PtCo nanoalloy modified Co of claim 1 3 O 4 -SiO 2 The preparation method of the flower-shaped multistage composite material is characterized by comprising the following steps of:
the solvent in the step (1) is deionized water;
the purity of the cobalt chloride hexahydrate in the step (1) is not lower than the chemical purity;
the purity of the hexahydrated copper chloride in the step (1) is not lower than the chemical purity.
3. The PtCo nanoalloy modified Co of claim 1 3 O 4 -SiO 2 The preparation method of the flower-shaped multistage composite material is characterized by comprising the following steps of: the concentration of the copper chloride solution in the step (1) is 5mmol/L-20mmol/L; the concentration of the cobalt chloride solution in the step (1) is 5mmol/L-20mmol/L.
4. The PtCo nanoalloy modified Co of claim 1 3 O 4 -SiO 2 The preparation method of the flower-shaped multistage composite material is characterized by comprising the following steps of: the pretreatment of the silicon wafer in the step (2) is as follows: cutting silicon wafer into square small pieces with a length of not more than 1cm and 1cm, and sequentially and alternately ultrasonic washing with ethanol and acetone to dissolveClarifying the solution, then ultrasonically treating the solution with deionized water for three times, and then storing the solution in deionized water for later use.
5. The PtCo nanoalloy modified Co of claim 1 3 O 4 -SiO 2 The preparation method of the flower-shaped multistage composite material is characterized by comprising the following steps of: cuCl in the step (3) 2 Solution and CoCl 2 The volume ratio of the solution is 1:3.
6. The PtCo nanoalloy modified Co of claim 1 3 O 4 -SiO 2 The preparation method of the flower-shaped multistage composite material is characterized by comprising the following steps of: the drying time in the step (5) is 24 hours; the drying temperature in the step (5) is 50-80 ℃.
7. The PtCo nanoalloy modified Co of claim 1 3 O 4 -SiO 2 The preparation method of the flower-shaped multistage composite material is characterized by comprising the following steps of: the calcination temperature in the step (6) is 200-500 ℃; the calcination time in the step (6) is 5 hours.
8. The PtCo nanoalloy modified Co of claim 7 3 O 4 -SiO 2 The preparation method of the flower-shaped multistage composite material is characterized by comprising the following steps of: the mass purity of the hexa-water chloroplatinic acid in the step (1) is not lower than 37%; the solvent in the step (1) is deionized water; the purity of the sodium borohydride in the step (1) is not lower than the chemical purity.
9. The PtCo nanoalloy modified Co of claim 7 3 O 4 -SiO 2 The preparation method of the flower-shaped multistage composite material is characterized by comprising the following steps of: stirring in the step (3) is stirring by polytetrafluoroethylene magnetic particles; the NaBH of the step (3) 4 The aqueous solution is prepared in situ; the NaBH of the step (3) 4 The refrigerating temperature of the aqueous solution is-14 ℃ to-4 ℃.
10. PtCo sodium according to claim 7Rice alloy modified Co 3 O 4 -SiO 2 The preparation method of the flower-shaped multistage composite material is characterized by comprising the following steps of: the drying temperature in the step (4) is 50-80 ℃; and (3) drying in the step (4) for 10-12 hours.
11. The PtCo nanoalloy modified Co of claim 7 3 O 4 -SiO 2 The preparation method of the flower-shaped multistage composite material is characterized by comprising the following steps of: the hydrogen reducing atmosphere in the step (5) is saturated by 5% argon; the temperature rising rate in the step (5) is 10 ℃ min -1 The method comprises the steps of carrying out a first treatment on the surface of the The heat preservation temperature in the step (5) is 350-450 ℃; and (3) the heat preservation time in the step (5) is 1h.
12. PtCo nano alloy modified Co prepared by the preparation method according to any one of claims 1 to 11 3 O 4 -SiO 2 The flower-like multistage composite material is characterized in that: comprises the following components: ptCo nanoparticles and three-dimensional flower-like Co 3 O 4 -SiO 2 A nanocomposite.
13. The PtCo nanoalloy modified Co of claim 12 3 O 4 -SiO 2 The flower-like multistage composite material is characterized in that: the PtCo nano particles are uniformly loaded on the three-dimensional flower-shaped Co 3 O 4 -SiO 2 On the nanocomposite; the nanoparticles have good dispersibility and no agglomeration.
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