CN114797891A - Pt 3 Fe alloy particles, preparation and catalytic application thereof - Google Patents
Pt 3 Fe alloy particles, preparation and catalytic application thereof Download PDFInfo
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- 229910000640 Fe alloy Inorganic materials 0.000 title claims abstract description 76
- 239000002245 particle Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 230000003197 catalytic effect Effects 0.000 title description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 163
- 239000002105 nanoparticle Substances 0.000 claims abstract description 119
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 95
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 40
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000013078 crystal Substances 0.000 claims abstract description 18
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- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 12
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- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 10
- 230000009467 reduction Effects 0.000 claims abstract description 10
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 7
- YGUFXEJWPRRAEK-UHFFFAOYSA-N dodecyl(triethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OCC)(OCC)OCC YGUFXEJWPRRAEK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 6
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 claims description 2
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- 239000012071 phase Substances 0.000 claims 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
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- 239000007791 liquid phase Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 4
- 239000005977 Ethylene Substances 0.000 abstract description 4
- MBUJACWWYFPMDK-UHFFFAOYSA-N pentane-2,4-dione;platinum Chemical compound [Pt].CC(=O)CC(C)=O MBUJACWWYFPMDK-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 2
- 239000000377 silicon dioxide Substances 0.000 abstract 2
- DLAPQHBZCAAVPQ-UHFFFAOYSA-N iron;pentane-2,4-dione Chemical compound [Fe].CC(=O)CC(C)=O DLAPQHBZCAAVPQ-UHFFFAOYSA-N 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- 239000000956 alloy Substances 0.000 description 13
- CMHKGULXIWIGBU-UHFFFAOYSA-N [Fe].[Pt] Chemical compound [Fe].[Pt] CMHKGULXIWIGBU-UHFFFAOYSA-N 0.000 description 11
- 229910045601 alloy Inorganic materials 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 9
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- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 229910002836 PtFe Inorganic materials 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
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- 230000008859 change Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- VWVRASTUFJRTHW-UHFFFAOYSA-N 2-[3-(azetidin-3-yloxy)-4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound O=C(CN1C=C(C(OC2CNC2)=N1)C1=CN=C(NC2CC3=C(C2)C=CC=C3)N=C1)N1CCC2=C(C1)N=NN2 VWVRASTUFJRTHW-UHFFFAOYSA-N 0.000 description 2
- 239000012692 Fe precursor Substances 0.000 description 2
- 229910005335 FePt Inorganic materials 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
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- VEJOYRPGKZZTJW-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;platinum Chemical compound [Pt].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O VEJOYRPGKZZTJW-FDGPNNRMSA-N 0.000 description 1
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
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- 239000000843 powder Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
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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
- B01J23/70—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
- B01J23/8906—Iron and noble metals
-
- B01J35/40—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
- C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
Abstract
The invention discloses a Pt 3 A preparation method and a crystal phase modulation method of Fe alloy nano particles mainly relate to single Pt 3 The Fe alloy nano particles are from A1 phase to L1 phase under the premise of unchanging particle size and chemical composition 2 The phase of the phase is transformed. Firstly, preparing Pt in a CO atmosphere by taking acetylacetone platinum and acetylacetone iron as precursors and oleylamine as a solvent and a surfactant 3 Fe nanoparticles; then wrapping the Pt by silicon dioxide in a reverse microemulsion system consisting of cyclohexane, Igepal CO-520 and ammonia water 3 Fe alloy particles to form Pt 3 Pt with Fe particle as core and silicon dioxide as shell 3 Fe@SiO 2 Particles; final warp H 2 The high-temperature reduction of the mixed gas of the/He gas respectively obtains an A1 phase and an L1 phase 2 Phase Pt 3 Fe alloy nanoparticles. Prepared A1 phase and L1 2 Phase Pt 3 The Fe alloy nano particles have excellent acetylene catalytic hydrogenation activity and ethylene selectivity, and are closely related to the crystalline phase of the Fe alloy nano particles.
Description
Technical Field
The invention relates to a Pt 3 A preparation method of Fe nano particles.
The invention also relates to Pt 3 Fe@SiO 2 A method for preparing core-shell structure nano particles.
The invention also relates to Pt 3 Fe alloy nanoparticles A1 phase and L1 2 A method for modulating phase.
The invention also relates to the above Pt 3 And (3) catalytic application of Fe alloy nanoparticles.
Background
The size, morphology, chemical composition and crystal structure of the platinum-iron alloy nanoparticles are important factors affecting the performance thereof. Under normal conditions, Pt atoms and Fe atoms in the alloy are randomly distributed on lattice sites to form a disordered occupied crystalline phase structure (A1 phase); however, when Pt and Fe atoms occupy specific sites selectively in the unit cell, an ordered crystal phase structure is formed (L1) 0 And L1 2 Phase). The change of the crystal phase structure changes the arrangement mode of Pt and Fe atoms in the alloy and the electronic structure of the whole alloy particles, thereby obviously influencing the catalytic reaction performance of the alloy. For example: carried on SiO 2 Surface Pt 3 Fe. PtFe, and PtFe 3 Ordered alloys show higher selectivity for propylene in propane dehydrogenation reactions than metallic Pt, the difference in performance being in the modification of the Pt-Fe coordination structure and Pt electronic structure in ordered alloys (ChemCatchem 12(2020) 1325-1333). With Pt (acac) 2 And Fe (CO) 5 Is used as a precursor and is treated at high temperature to prepare a disordered PtFe/C (10.7nm) alloy catalyst and an ordered phase L1 2 -Pt 3 Fe/C (6.8nm) alloy catalyst. Ordered phase L1 2 -Pt 3 The Fe/C catalyst exhibits higher specific mass activity and more excellent stability in the oxygen reduction reaction than disordered phase PtFe/C and Pt/C catalysts because the highly ordered crystal structure can effectively suppress Fe loss (ACS appl. mater. interfaces 9(2017) 31806-31815). L1 with core-shell structure 0 -FePt @ Pt catalyst due to the order L1 0 Epitaxial growth of FePt alloy particles results in contraction of the spacing between the outer Pt atomic layers, thus improving the activity and stability of the oxygen reduction reaction (J.Am.chem.Soc.140(2018) 2926-2932). Up to now, disordered platinoid particles have been prevalentUsing highly toxic and explosive Fe (CO) 5 Is used as a precursor, and then is treated at high temperature to obtain the ordered-phase platinum-iron alloy nano particles. This not only leads to the complexity and danger of the chemical synthesis process, but also more importantly, the platinum-iron alloy particles inevitably cause the sintering of the nanoparticles and the segregation of the chemical composition during the high-temperature treatment process, thereby failing to realize the single crystal phase structure regulation. Therefore, the preparation of the platinum-iron alloy nanoparticles by using the harmless, cheap and easily-obtained metal salt precursor and the modulation of the crystal phase structure of the platinum-iron alloy nanoparticles under the condition of unchanged size and composition are still a great problem to be solved urgently in the field of material preparation. Platinum-iron alloy particles are packaged in porous SiO by utilizing nano space confinement effect 2 The interior of the shell layer can inhibit the migration and sintering of the platinum iron particles and can effectively block the element diffusion among the platinum iron alloy particles, thereby providing a new idea for adjusting the crystal phase structure of the platinum iron alloy particles and researching the structure-activity relationship between the crystal phase structure and the catalytic performance of the platinum iron alloy particles on the premise of not changing the chemical composition and the size morphology.
Disclosure of Invention
The invention aims to provide Pt 3 A preparation method of Fe nano particles.
Another object of the present invention is to provide a SiO 2 Wrapping Pt 3 Fe nanoparticles, preparation of Pt 3 Fe@SiO 2 A method for preparing core-shell structure nano particles.
Another object of the present invention is to utilize SiO 2 Spatially domain-limited modulation of individual Pt 3 The Fe alloy nano particle crystalline phase solves the problem that the alloy particles are easy to sinter in the high-temperature crystalline phase modulation process of the traditional alloy material to cause the change of the size, the appearance and the element composition.
Another object of the present invention is to provide the above Pt 3 The Fe alloy nano particles are applied to acetylene catalytic hydrogenation reaction.
The purpose of the invention is realized by the following technical scheme:
pt 3 The preparation method of the Fe nano-particles comprises the following process steps:
(1) dissolving a platinum precursor and an iron precursor in oleylamine at a temperature of between 50 and 100 ℃, wherein the concentration of platinum is between 3 and 16mmol/L, and the concentration of iron is between 1 and 5 mmol/L;
(2) taking 20-25mL of the solution prepared according to the step (1), and introducing carbon monoxide gas with the flow rate of 50-200 mL/min;
(3) heating the solution to 200-300 ℃, and reacting for 40-60 min; centrifugally separating the product, washing with ethanol to obtain Pt 3 Fe nanoparticles.
The platinum precursor is acetylacetone platinum, and the concentration is preferably 3-16 mmol/L.
The iron precursor is ferric acetylacetonate, and the concentration is preferably 1-5 mmol/L.
The flow rate of carbon monoxide introduced into the system is preferably 50-200 mL/min.
The reaction temperature is preferably 200 ℃ to 300 ℃.
The reaction time is preferably 40-60 min.
Pt 3 Fe@SiO 2 The preparation method of the core-shell structure nano material is characterized by comprising the following steps:
(1) with said Pt 3 Fe nanoparticles as a raw material, dispersing them in cyclohexane, Pt 3 The concentration of the Fe nano particles is 0.30-0.70g/L, and the ultrasonic treatment is carried out for 5-10 min;
(2) taking 30-210mL of the Pt 3 Adding 15-60g of Igepal CO-520 and 250-850mL of cyclohexane into the Fe nano particle dispersion, carrying out ultrasonic treatment on the mixed solution for 20-40min, and stirring;
(3) adding 2.0-8.0mL of concentrated ammonia water (the mass concentration is 25-28%) into the solution obtained in the step (2), and stirring;
(4) adding 20-150mL of cyclohexane solution of n-dodecyl triethoxysilane with the concentration of 17-19g/L and 10-120mL of cyclohexane solution of tetraethyl orthosilicate with the concentration of 48-52g/L into the solution obtained in the step (3), and reacting for 12-16h at the temperature of 25-35 ℃ under the stirring condition;
(5) adding 500mL of 100-one ethanol into the solution obtained after the reaction in the step (4), centrifugally separating the product, washing with ethanol, drying, and roasting at the temperature of 600 ℃ for 4-8h to obtain Pt 3 Fe@SiO 2 Core-shell structured nanoparticles.
The Pt 3 Fe nanoparticle dispersion liquid at a concentration of 0.3Preferably 0 to 0.70g/L, and the amount is preferably 30 to 210 mL.
The dosage of the Igepal CO-520 is preferably 15-60g, and the volume of cyclohexane is preferably 250-850 mL.
The adding amount of the strong ammonia water (the mass concentration is 25-28%) is preferably 2.0-8.0 mL.
The cyclohexane solution concentration of the n-dodecyl triethoxy silane is preferably 17-19g/L, the dosage is preferably 20-150mL, the cyclohexane solution concentration of tetraethyl orthosilicate is preferably 48-52g/L, and the dosage is preferably 10-120 mL.
The reaction temperature is preferably 25-35 ℃, and the reaction time is preferably 12-16 h.
The roasting condition is preferably 400-600 ℃ roasting for 4-8 h.
Modulated Pt 3 The method for preparing the Fe alloy nano particle crystalline phase comprises the following process steps: using said Pt 3 Fe@SiO 2 The core-shell structure nano-particle is a precursor, and the volume concentration of H is 2-15% at 400- 2 Reducing for 1-3h in the atmosphere of/He, cooling to 20-30 ℃ to obtain A1 phase Pt 3 Fe alloy nanoparticles; or by using said Pt 3 Fe@SiO 2 The core-shell structure nano-particle is a precursor, and the volume concentration of H is 2-15% at the temperature of 600-700 DEG C 2 Reducing in He atmosphere for 1-3h, cooling to 20-30 deg.C to obtain L1 2 Phase Pt 3 Fe alloy nanoparticles.
The A1 phase Pt 3 The crystal phase modulation temperature of the Fe alloy nanoparticles is preferably 400-500 ℃, and the reduction time is preferably 1-3 h.
The A1 phase Pt 3 The volume concentration of the Fe alloy nano particle crystalline phase modulation atmosphere is 2-15% H 2 The value of/He is preferred.
The L1 2 Phase Pt 3 The crystal phase modulation temperature of the Fe alloy nanoparticles is preferably 600-700 ℃, and the reduction time is preferably 1-3 h.
The L1 2 Phase Pt 3 The volume concentration of the Fe alloy nano particle crystalline phase modulation atmosphere is 2-15% H 2 The value of/He is preferred.
The nano-scale is observed by adopting a Hitachi HT7700 type transmission electron microscopeThe particle size and morphology, the test results are shown in figures 1, 2, 3 and 5, the prepared particles have regular shape and structure and uniform size, wherein Pt is 3 The average grain diameter of Fe is always kept at 7.2 +/-0.4 nm and SiO 2 The thickness is maintained at 7-12 nm. Characterization of Pt by Rigaku D/MAX-2500/PC X-ray powder diffractometer 3 The Fe alloy crystal phase and the characterization results are shown in FIG. 4 and FIG. 6, and the successful modulation of Pt is proved by referring to the shift of diffraction peak and comparing with the standard cards (JCPDS #89-2050 and JCPDS #65-2868) 3 The crystalline phases of the Fe alloy nano particles are A1 phase and L1 phase 2 And (4) phase(s). It is characterized by being in Pt 3 Under the premise of keeping the size and chemical composition of Fe particles unchanged, single Pt is realized 3 Fe particles from A1 phase to L1 phase 2 Modulation of the crystal structure of the phase.
A1 phase Pt 3 The Fe alloy nano particles are applied to acetylene catalytic hydrogenation reaction and comprise the following steps:
(1) by using the A1 phase Pt 3 Taking 50mg of Fe alloy nano particles, introducing C with the volume concentration of 1 percent at 180 DEG C 2 H 2 /2％H 2 The flow rate of the raw material gas for the reaction of the/He is 50mL/min, and the reaction time is 40 h;
(2) sampling is carried out every 20min after the reaction is started, and the composition of a reaction product is analyzed on line by adopting a gas chromatography.
The A1 phase Pt 3 The Fe alloy nano-particles are preferably used in an amount of 50 mg.
The reaction temperature is preferably 180 ℃.
The volume concentration of the reaction raw material gas is 1 percent C 2 H 2 /2％H 2 The flow rate is preferably 50mL/min per He.
L1 2 Phase Pt 3 The Fe alloy nano particles are applied to acetylene catalytic hydrogenation reaction and comprise the following steps:
(1) using said L1 2 Phase Pt 3 Taking 50mg of Fe alloy nano particles, introducing C with the volume concentration of 1 percent at 180 DEG C 2 H 2 /2％H 2 The flow rate of the raw material gas for the reaction of the/He is 50mL/min, and the reaction time is 40 h;
(2) sampling is carried out every 20min after the reaction is started, and the composition of a reaction product is analyzed on line by adopting a gas chromatography.
The L1 2 Phase Pt 3 The Fe alloy nano-particles are preferably used in an amount of 50 mg.
The reaction temperature is preferably 180 ℃.
The volume concentration of the reaction raw material gas is 1 percent C 2 H 2 /2％H 2 preferably,/He, the flow rate is 50
mL/min is preferred.
Compared with the existing platinum-iron alloy material preparation and crystalline phase modulation method, the method has the following characteristics: (1) in the solution phase, oleylamine is used as a surfactant, carbon monoxide is used as a reducing agent, and Pt with uniform size is prepared 3 Fe nanoparticles; (2) pt is prepared by reverse microemulsion solution consisting of cyclohexane, Igepal CO-520 and ammonia water 3 Fe@SiO 2 Core-shell structured nanoparticles; (3) using SiO 2 The space confinement effect of the shell layer effectively avoids Pt 3 The size and the shape structure of the Fe particles are changed in the high-temperature phase change process, and the obtained A1 phase and L1 phase 2 Phase Pt 3 Pt in Fe alloy material 3 The average grain diameter of the Fe alloy nano particles is kept unchanged before and after the crystal phase modulation; (4) synthesized A1 phase and L1 2 Phase Pt 3 The Fe alloy nano particles show excellent catalytic activity and ethylene selectivity in acetylene catalytic hydrogenation reaction.
Drawings
FIG. 1 shows Pt prepared according to example 1 3 And (3) a transmission electron microscope photo of the Fe nano particles.
FIG. 2 shows Pt prepared according to example 4 3 Fe@SiO 2 And (3) a transmission electron microscope photo of the core-shell structure nano particles.
FIG. 3 shows phase A1 Pt prepared according to example 9 3 And (4) a transmission electron microscope photo of the Fe alloy nano particles.
FIG. 4 shows phase A1 Pt prepared according to example 9 3 Powder X-ray diffraction spectrum of the Fe alloy nano particles.
FIG. 5 is L1 prepared according to example 10 2 Phase Pt 3 And (4) a transmission electron microscope photo of the Fe alloy nano particles.
FIG. 6 is L1 prepared according to example 10 2 Phase Pt 3 Powder X-ray diffraction spectrum of the Fe alloy nano particles.
FIG. 7 shows phase A1 Pt as tested in example 13 3 The Fe alloy nano particle acetylene has the performance of catalytic hydrogenation reaction.
FIG. 8 shows L1 tested in example 14 2 Phase Pt 3 The Fe alloy nano particle acetylene has the performance of catalytic hydrogenation reaction.
Detailed Description
The invention is further illustrated by the following examples in order to provide a better understanding of the invention, but should not be construed to limit the scope of the invention.
Example 1
59.1mg of platinum acetylacetonate and 18.6mg of iron acetylacetonate were added to 20mL of oleylamine, and dissolved by stirring at 80 ℃. After complete dissolution, introducing 200mL/min of carbon monoxide, heating to 240 ℃, stirring for reaction for 40min, and cooling to 25 ℃. Centrifugally separating the product, washing with ethanol to obtain black Pt 3 Fe nanoparticles. Prepared Pt 3 The Fe nano-particles have regular nearly spherical shapes, the particle diameter of the particles is 7.2 +/-0.4 nm, and an electron microscope photo thereof is shown in figure 1.
Example 2
89.0mg of platinum acetylacetonate and 27.5mg of iron acetylacetonate were added to 20mL of oleylamine, and dissolved by stirring at 60 ℃. After complete dissolution, 50mL/min of carbon monoxide is introduced, the temperature is raised to 280 ℃, the reaction is stirred for 50min, and the temperature is reduced to 25 ℃. Centrifugally separating the product, washing with ethanol to obtain black Pt 3 Fe nanoparticles. Prepared Pt 3 The Fe nano-particles have regular nearly spherical shapes, and the particle size is 6.8 +/-0.3 nm.
Example 3
103.4mg of platinum acetylacetonate and 32.2mg of iron acetylacetonate were added to 20mL of oleylamine, and dissolved by stirring at 90 ℃. After complete dissolution, introducing 120mL/min of carbon monoxide, heating to 300 ℃, stirring for reaction for 60min, and cooling to 25 ℃. Centrifugally separating the product, washing with ethanol to obtain black Pt 3 Fe nanoparticles. Prepared Pt 3 The Fe nano-particles have regular nearly spherical shapes, and the particle size is 7.6 +/-0.3 nm.
Example 4
Pt obtained in example 1 was added 3 The Fe nanoparticles are ultrasonically dispersed in cyclohexane with the concentration of 0.48g/L, and 200mL is taken. With stirring, 57g of Igepal CO-520(Sigma-Aldrich, M) were added w 441) and 800mL of cyclohexane, sonicated for 30 min. After uniform ultrasonic dispersion, 7.8mL of concentrated ammonia water (mass concentration 25-28%) is added under magnetic stirring. After stirring again, 100mL of a cyclohexane solution of 17.8g/L n-dodecyltriethoxysilane and 100mL of a cyclohexane solution of 50.0g/L tetraethyl orthosilicate were added quickly. Stirring and reacting for 12h at 28 ℃, and adding 450mL of ethanol for demulsification. Centrifugally separating the product, washing with ethanol for 2 times, and roasting at 500 deg.C for 8 hr to obtain black Pt 3 Fe@SiO 2 Core-shell structured nanoparticles. Prepared Pt 3 Fe@SiO 2 The nano particles have a typical core-shell structure, and an inner core Pt 3 The grain diameter of the Fe particles is 7.2 +/-0.4 nm and SiO 2 The thickness of the shell layer is 9.1 +/-0.7 nm, and the electron microscope characterization result is shown in figure 2.
Example 5
Pt obtained in example 2 was added 3 The Fe nanoparticles are ultrasonically dispersed in cyclohexane with the concentration of 0.35g/L, and 100mL is taken. 19g of Igepal CO-520(Sigma-Aldrich, M) were added with stirring w 441) and 300mL of cyclohexane, sonicated for 20 min. After uniform ultrasonic dispersion, 2.6mL of concentrated ammonia water (mass concentration 25-28%) is added under magnetic stirring. After stirring again, 30mL of a cyclohexane solution of 17.8g/L n-dodecyltriethoxysilane and 30mL of a cyclohexane solution of 50.0g/L tetraethyl orthosilicate were added quickly. Stirring and reacting for 12h at 28 ℃, and adding 250mL of ethanol for demulsification. Centrifugally separating the product, washing with ethanol for 2 times, and roasting at 600 deg.C for 5 hr to obtain black Pt 3 Fe@SiO 2 Core-shell structured nanoparticles. Prepared Pt 3 Fe@SiO 2 The nano particles have a typical core-shell structure, and an inner core Pt 3 The grain diameter of Fe particle is 6.7 +/-0.4 nm and SiO 2 The thickness of the shell layer is 7.0 +/-0.5 nm.
Example 6
Pt obtained in example 1 was added 3 The Fe nanoparticles are ultrasonically dispersed in cyclohexane with the concentration of 0.64g/L, and 50mL is taken. With stirring, 19g of Igepal CO-520 (Si) were addedgma-Aldrich，M w 441) and 300mL of cyclohexane, sonicated for 30 min. After uniform ultrasonic dispersion, 2.6mL of concentrated ammonia water (mass concentration 25-28%) is added under magnetic stirring. After stirring again, 30mL of a cyclohexane solution of 17.8g/L n-dodecyltriethoxysilane and 30mL of a cyclohexane solution of 50.0g/L tetraethyl orthosilicate were added quickly. Stirring and reacting for 12h at 28 ℃, and adding 150mL of ethanol for demulsification. Centrifugally separating the product, washing with ethanol for 2 times, and roasting at 500 deg.C for 4 hr to obtain black Pt 3 Fe@SiO 2 Core-shell structured nanoparticles. Prepared Pt 3 Fe@SiO 2 The nano particles have a typical core-shell structure, and an inner core Pt 3 The grain diameter of the Fe particles is 7.0 +/-0.4 nm and SiO 2 The thickness of the shell layer is 7.3 +/-0.9 nm.
Example 7
Pt obtained in example 3 was added 3 The Fe nanoparticles are ultrasonically dispersed in cyclohexane with the concentration of 0.48g/L, and 100mL is taken. 38g of Igepal CO-520(Sigma-Aldrich, M) were added with stirring w 441) and 600mL of cyclohexane, sonicated for 40 min. After uniform ultrasonic dispersion, 5.2mL of concentrated ammonia water (mass concentration 25-28%) is added under magnetic stirring. After stirring again, 40mL of a cyclohexane solution of 17.8g/L n-dodecyltriethoxysilane and 60mL of a cyclohexane solution of 50.0g/L tetraethyl orthosilicate were added quickly. Stirring and reacting for 16h at 31 ℃, and adding 450mL of ethanol for demulsification. Centrifugally separating the product, washing with ethanol for 2 times, and roasting at 400 deg.C for 4 hr to obtain black Pt 3 Fe@SiO 2 Core-shell structured nanoparticles. Prepared Pt 3 Fe@SiO 2 The nano particles have a typical core-shell structure, and an inner core Pt 3 The grain diameter of the Fe particles is 7.5 +/-0.3 nm and SiO 2 The thickness of the shell layer is 10.4 +/-0.9 nm.
Example 8
50mg of Pt obtained in example 6 were used 3 Fe@SiO 2 Heating core-shell structured nano particles in a tube furnace to 400 ℃, and introducing H with the volume concentration of 15 percent 2 Performing reduction treatment on the Pt/He for 3h, and cooling to 25 ℃ to obtain A1 phase Pt 3 Fe alloy nanoparticles. Obtained A1 phase Pt 3 In Fe alloy nanoparticles, Pt 3 The grain diameter of the Fe particles is 7.1 +/-0.2 nm. Relative diffraction peak of X-ray diffraction spectrumThe shift of the diffraction peak position to high angle (main diffraction peak is shifted from 39.7 deg. to 39.9 deg.) in metal Pt standard card JCPDS #65-2868 shows that A1 phase Pt forming disordered occupying of Pt and Fe atoms in the crystal lattice 3 An Fe alloy.
Example 9
50mg of Pt obtained in example 4 were used 3 Fe@SiO 2 Core-shell structured nanoparticles, heating to 500 ℃ in a tube furnace, and introducing H with the volume concentration of 10% 2 Performing reduction treatment for 2h with/He, cooling to 25 ℃ to obtain A1 phase Pt 3 The test result of the Fe alloy nano particles by an electron microscope is shown in figure 3. A1 phase Pt 3 In Fe alloy nanoparticles, Pt 3 The grain diameter of the Fe particles is 7.2 +/-0.4 nm. The X-ray diffraction pattern is shown in FIG. 4, and the diffraction peak is shifted to a high angle (the main diffraction peak is shifted from 39.7 degrees to 40.0 degrees) relative to the position of the diffraction peak in the metal Pt standard card JCPDS #65-2868, which indicates that A1 phase Pt forming disordered occupation of Pt and Fe atoms in the crystal lattice 3 An Fe alloy.
Example 10
50mg of Pt obtained in example 4 were used 3 Fe@SiO 2 Heating core-shell structured nano particles in a tube furnace to 700 ℃, and introducing H with the volume concentration of 10 percent 2 Performing reduction treatment for 2h with/He, cooling to 25 deg.C to obtain L1 2 Phase Pt 3 The Fe alloy nano-particles and the electron microscope test result are shown in figure 5. L1 2 Phase Pt 3 In Fe alloy nanoparticles, Pt 3 The grain diameter of the Fe particles is still 7.2 +/-0.4 nm. The X-ray diffraction test result is shown in figure 6, the position of the diffraction peak of the spectrogram is consistent with that of the diffraction peak in the standard card JCPDS #89-2050, and the result shows that the ordered L1 of the Pt occupying face center site and the Fe occupying top site in the same face center cubic unit cell is formed 2 Phase Pt 3 An Fe alloy.
Example 11
50mg of Pt obtained in example 5 were used 3 Fe@SiO 2 Heating core-shell structured nano particles in a tube furnace to 700 ℃, and introducing H with the volume concentration of 10 percent 2 Performing He reduction treatment for 1h, cooling to 25 deg.C to obtain L1 2 Phase Pt 3 Fe alloy nanoparticles. L1 2 Phase Pt 3 In Fe alloy nanoparticles, Pt 3 The grain diameter of the Fe particles is 6.7 +/-0.3 nm. X-ray diffraction test junctionThe results show that the diffraction peak positions of the spectrogram are consistent with those of the standard card JCPDS #89-2050, which indicates that the ordered L1 of Pt occupying the face center site and Fe occupying the top site in the same face center cubic unit cell is formed 2 Phase Pt 3 An Fe alloy.
Example 12
50mg of Pt obtained in example 7 were used 3 Fe@SiO 2 Heating core-shell structured nano particles in a tube furnace to 700 ℃, and introducing H with the volume concentration of 5 percent 2 Performing reduction treatment for 2h with/He, cooling to 25 deg.C to obtain L1 2 Phase Pt 3 Fe alloy nanoparticles. L1 obtained 2 Phase Pt 3 In Fe alloy nanoparticles, Pt 3 The grain diameter of the Fe particles is 7.4 +/-0.4 nm. The X-ray diffraction test result shows that the position of a spectrogram diffraction peak is consistent with that of a diffraction peak in a standard card JCPDS #89-2050, and the ordered L1 of Pt occupying a face center site and Fe occupying a top site in the same face center cubic unit cell is formed 2 Phase Pt 3 An Fe alloy.
Example 13
50mg of Pt as A1 phase obtained in example 9 was added 3 Placing Fe alloy nano particles into a quartz reaction tube, heating to 180 ℃, and introducing C with the volume concentration of 1 percent 2 H 2 /2％H 2 And (3) carrying out acetylene catalytic hydrogenation reaction performance test on reaction raw material gas/He with the flow rate set to be 50 mL/min. As shown in FIG. 7, phase A1 Pt 3 The acetylene conversion rate on the Fe alloy nano particles is 51%, and the ethylene selectivity is 76%.
Example 14
50mg of L1 obtained in example 10 were added 2 Phase Pt 3 Placing Fe alloy nano particles into a quartz reaction tube, heating to 180 ℃, and introducing C with the volume concentration of 1 percent 2 H 2 /2％H 2 And (3) carrying out acetylene catalytic hydrogenation reaction performance test on reaction raw material gas/He with the flow rate set to be 50 mL/min. As shown in fig. 8, L1 2 Phase Pt 3 The acetylene conversion rate on the Fe alloy nano particles is 99%, and the ethylene selectivity is 83%.
Claims (10)
1. Pt 3 The preparation method of the Fe nano particles is characterized by comprising the following steps: with platinum acetylacetonate and acetylacetoneUsing ketoferric as precursor, and obtaining Pt with particle size of 6.2-8.0nm by liquid phase reduction method 3 And Fe particles.
2. Pt according to claim 1 3 The preparation method of the Fe nano particles is characterized by comprising the following process steps:
(1) dissolving platinum acetylacetonate and ferric acetylacetonate in oleylamine at 50-100 ℃ to form a solution with the platinum concentration of 3-16mmol/L and the iron concentration of 1-5 mmol/L;
(2) taking 20-25mL of the solution prepared according to the step (1), and introducing carbon monoxide gas with the flow rate of 50-200 mL/min;
(3) heating to 200-300 ℃, reacting for 40-60min, centrifugally separating the product, and washing with ethanol to obtain Pt 3 Fe nanoparticles.
3. Pt prepared by the preparation method of claim 1 or 2 3 Fe nanoparticles.
4. Pt 3 Fe@SiO 2 The preparation method of the core-shell structure nano particle is characterized by comprising the following steps: the reverse microemulsion solution of claim 3 wherein said Pt is formed from cyclohexane, Igepal CO-520 and ammonia 3 The surface of the Fe nano-particle is uniformly coated with a layer of SiO with the thickness of 7-12nm 2 Shell layer of formed Pt 3 Fe@SiO 2 Core-shell structured nanoparticles.
5. Pt according to claim 4 3 Fe@SiO 2 The preparation method of the core-shell structure nano particle is characterized by comprising the following process steps:
(1) utilizing the Pt of claim 3 3 Fe nano particles are used as raw materials and are dispersed in cyclohexane and Pt by ultrasonic 3 The concentration of the Fe nano particles in the dispersion liquid is 0.30-0.70 g/L;
(2) to 30-210mL of the above Pt 3 Adding 15-60g of Igepal CO-520 and 250-850mL of cyclohexane into the Fe nano particle dispersion, carrying out ultrasonic treatment for 20-40min, and stirring;
(3) adding 2.0-8.0mL of concentrated ammonia water (with mass concentration of 25-28%) into the solution obtained in the step (2), and stirring;
(4) adding 20-150mL of cyclohexane solution of n-dodecyl triethoxysilane with the concentration of 17-19g/L and 10-120mL of cyclohexane solution of tetraethyl orthosilicate with the concentration of 48-52g/L into the solution obtained in the step (3), and reacting for 12-16h at the temperature of 25-35 ℃ under the stirring condition;
(5) adding 100-500mL ethanol into the solution after the reaction in step (4), centrifugally separating the product, washing with ethanol, drying, and roasting at 400-600 ℃ for 4-8h to obtain Pt 3 Fe@SiO 2 Core-shell structured nanoparticles.
6. Pt prepared by the preparation method of claim 4 or 5 3 Fe@SiO 2 Core-shell structured nanoparticles.
7. Modulated Pt 3 The method for preparing the Fe alloy nanoparticle crystal phase is characterized by comprising the following steps: pt according to claim 6 3 Fe@SiO 2 The core-shell structure nano particle is a precursor with the volume concentration of 2-15% H 2 Heating reduction in the atmosphere of/He to obtain A1 phase Pt 3 Fe alloy nanoparticles and/or L1 2 Phase Pt 3 Fe alloy nanoparticles, Pt in crystalline phase modulation 3 The average grain diameter of Fe particles is maintained at 6.2-8.0nm, SiO 2 The thickness of the shell layer is 7-12 nm.
8. The modulated Pt of claim 7 3 The method for preparing the Fe alloy nano particle crystalline phase is characterized by comprising the following process steps: utilizing the Pt of claim 6 3 Fe@SiO 2 The core-shell structure nano-particle is a precursor, and the volume concentration of H is 2-15% at 400- 2 Reducing for 1-3h in the atmosphere of/He, cooling to 20-30 ℃ to obtain A1 phase Pt 3 Fe alloy nanoparticles; or using the Pt of claim 6 3 Fe@SiO 2 The core-shell structure nano-particle is a precursor, and the volume concentration of H is 2-15% at the temperature of 600-700 DEG C 2 Reducing in He atmosphere for 1-3h, cooling to 20-30 deg.C to obtain L1 2 Phase Pt 3 Fe alloy nanoparticles.
9. The modulated Pt of claim 7 or 8 3 A1 phase Pt obtained by Fe alloy nanoparticle crystal phase method 3 Fe alloy nanoparticles and/or L1 2 Phase Pt 3 Fe alloy nanoparticles.
10. The A1 phase Pt of claim 9 3 Fe alloy nanoparticles and/or L1 2 Phase Pt 3 The Fe alloy nano particles are applied to acetylene catalytic hydrogenation reaction.
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