CN110064423B - Ultra-small multi-element alloy composite material, preparation method and application thereof - Google Patents
Ultra-small multi-element alloy composite material, preparation method and application thereof Download PDFInfo
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- CN110064423B CN110064423B CN201910129162.8A CN201910129162A CN110064423B CN 110064423 B CN110064423 B CN 110064423B CN 201910129162 A CN201910129162 A CN 201910129162A CN 110064423 B CN110064423 B CN 110064423B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 49
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- 239000002243 precursor Substances 0.000 claims abstract description 28
- 238000007210 heterogeneous catalysis Methods 0.000 claims abstract description 6
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 43
- 238000010438 heat treatment Methods 0.000 claims description 34
- 239000007789 gas Substances 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 25
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- 238000005530 etching Methods 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
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- 239000001257 hydrogen Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
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- 229910052682 stishovite Inorganic materials 0.000 claims description 14
- 229910052905 tridymite Inorganic materials 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
- 239000011593 sulfur Substances 0.000 claims description 12
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical group C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 229910052723 transition metal Inorganic materials 0.000 claims description 11
- -1 transition metal salt Chemical class 0.000 claims description 11
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- 238000002156 mixing Methods 0.000 claims description 8
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- 150000003384 small molecules Chemical class 0.000 claims description 8
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- 238000001354 calcination Methods 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
- 239000008188 pellet Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910052787 antimony Inorganic materials 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052733 gallium Inorganic materials 0.000 claims description 5
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- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052745 lead Inorganic materials 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052702 rhenium Inorganic materials 0.000 claims description 5
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- 229910052706 scandium Inorganic materials 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 229910052727 yttrium Inorganic materials 0.000 claims description 5
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
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- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical group O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 3
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- 229910002621 H2PtCl6 Inorganic materials 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
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- 229910000952 Be alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 238000001016 Ostwald ripening Methods 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 229910002837 PtCo Inorganic materials 0.000 description 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- 229910019891 RuCl3 Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
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- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
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- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
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- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
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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
- 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
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
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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
- 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
- B01J35/396—Distribution of the active metal ingredient
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
- C07C209/365—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst by reduction with preservation of halogen-atoms in compounds containing nitro groups and halogen atoms bound to the same carbon skeleton
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
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Abstract
The invention provides an ultra-small multi-element alloy composite material, which comprises sulfur-doped mesoporous carbon and ultra-small alloy particles loaded on the surface of the sulfur-doped mesoporous carbon; the average size of the ultra-small alloy particles is 2 nm. The application also provides a preparation method of the ultra-small multi-element alloy composite material. The application also provides the application of the ultra-small multi-element alloy composite material in heterogeneous catalysis. The method synthesizes the ultra-small multi-element alloy composite material by regulating the type and temperature of the metal salt precursor, and the average size of alloy particles in the composite material is 2nm, the size is small, and the utilization rate is high; the method has universality, is simple to operate, has low cost and is easy for industrial production.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to an ultra-small multi-element alloy composite material, a preparation method and application thereof.
Background
In recent years, alloys are an important industrial heterogeneous catalyst, and compared with a single metal component, the catalytic stability, the activity and the selectivity of the catalyst are greatly improved. The parameters of the metal nano particles such as particle size, composition, surface structure, interface interaction with a carrier and the like have high influence on the catalytic performance of the supported metal catalyst. As the particle size decreases, the alloy exhibits some unique properties.
To date, various methods have been proposed to form the ultra-small bimetal cluster, such as a dendrimer templating method, a polymer protection and liquid phase reduction method, a direct heat treatment molecular metallo-organic precursor method, a Co-SEA method, and a surface inorganic metal chemical method. The above methods have many disadvantages, the catalysts of the first method and the second method are both liquid phase reduction and are wrapped by polymer, mass transfer with reactants is limited in the catalysis process, and the polymer synthesis is relatively complicated; the third synthesis method results in non-uniform particle size and is not amenable to large-scale production; the fourth synthesis method is limited by pH and has lower loading capacity; the fifth synthesis method is limited to binary alloys, with non-uniform particle size.
In order to obtain a high quality supported alloy catalyst of uniform size and uniform composition, the metal precursor must first be uniformly deposited on the support surface without agglomeration prior to conversion to alloy nanoparticles. Therefore, the alloy nano composite material which is uniform, stable and ultra-small in size is significant.
Disclosure of Invention
The invention aims to provide a uniform, stable and ultra-small alloy nano material and a preparation method thereof.
In view of the above, the present application provides an ultra-small multi-element alloy composite material, including sulfur-doped mesoporous carbon and ultra-small alloy particles loaded on the surface of the sulfur-doped mesoporous carbon; the average size of the ultra-small alloy particles is 2 nm.
Preferably, the loading amount of the ultra-small alloy particles is 1wt% to 20 wt%.
Preferably, the metal element of the ultra-small alloy particles is selected from two or more of Pt, Rh, Pd, Ir, Ru, Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Mo, Cd, In, Sn, Sb, Bi, Pb, Re, W, Ta and Hf.
The application also provides a preparation method of the ultra-small multi-element alloy composite material, which comprises the following steps:
mixing sulfur-doped mesoporous carbon, a metal salt precursor and a solvent, and drying to obtain an initial mixture; the metal salt precursor is a metal salt precursor of two or more different metal elements;
carrying out heat treatment on the initial mixture in a reducing atmosphere to obtain an ultra-small multi-element alloy composite material; the temperature of the heat treatment is 400-800 ℃.
Preferably, the preparation method of the sulfur-doped mesoporous carbon comprises the following steps:
sulfur-containing organic micromolecules, SiO2Mixing the pellets and transition metal salt in a solvent, drying and calcining at high temperature to obtain a carbon material;
and sequentially etching the carbon material by using sodium hydroxide and sulfuric acid to obtain the sulfur-doped mesoporous carbon.
Preferably, the sulfur-containing organic small molecule is 2, 2' -bithiophene, and the transition metal salt is selected from cobalt nitrate hexahydrate; the sulfur-containing small molecule, SiO2The molar ratio of the pellets to the transition metal salt is 2:2: 1; the calcining temperature is 600-1200 ℃.
Preferably, the metal salt precursor is selected from two or more of a noble metal salt and a non-noble metal salt; the noble metal elements In the noble metal salt are selected from one or more of Pt, Rh, Pd, Ir and Ru, and the non-noble metal elements In the non-noble metal salt are selected from one or more of Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Mo, Cd, In, Sn, Sb, Bi, Pb, Re, W, Ta and Hf.
Preferably, the reducing atmosphere is a hydrogen atmosphere or a hydrogen mixed gas atmosphere; the hydrogen mixed gas atmosphere is selected from the mixed gas of hydrogen and nitrogen, the mixed gas of hydrogen and argon or the mixed gas of hydrogen and carbon monoxide.
Preferably, the heating rate of the heat treatment is 2-20 ℃/min, and the time is 0.5-12 h.
The application also provides the application of the ultra-small multi-element alloy composite material or the preparation method of the ultra-small multi-element alloy composite material in heterogeneous catalysis.
The application provides an ultra-small multi-element alloy composite material, which comprises sulfur-doped mesoporous carbon and ultra-small alloy particles loaded on the surface of the sulfur-doped mesoporous carbon.
The application also provides a preparation method of the ultra-small multi-element alloy composite material, which comprises the steps of mixing the sulfur-doped mesoporous carbon, the metal salt precursor and the solvent, drying to obtain an initial mixture, and performing heat treatment on the initial mixture to obtain the ultra-small multi-element alloy composite material; the sulfur-doped mesoporous carbon has a good metal fixing effect and can provide enough anchoring points for alloy particles, so that the stability of the ultra-small multi-element alloy composite material is improved, and the sintering and agglomeration of the ultra-small multi-element alloy are inhibited; meanwhile, by adjusting the heat treatment temperature, the multielement alloy forms ultra-small alloy particles with the average size of 2nm, and the ultra-small alloy particles are stably loaded on the surface of the sulfur-doped mesoporous carbon.
On the other hand, the preparation method of the ultra-small multi-element alloy composite material has universality for most metals, can be used as a catalyst for heterogeneous catalysis, and has unique activity and stability.
Drawings
FIG. 1 is a graph of data for the S element in X-ray photoelectron spectroscopy (XPS) for 5 wt% Pt-Co in example 1 and 5 wt% Pt-Ir ultra small alloy in example 6 according to the present invention;
FIG. 2 is an X-ray powder diffraction characterization map of 5 wt% Pt-Co and other partially binary ultra-small alloys provided in example 1 of the present invention;
FIG. 3 is a HAADF-mapping characterization map of 5 wt% Pt-Co provided in example 1 of the present invention;
FIG. 4 is a line scan characterization plot of 5 wt% Pt-Co as provided in example 1 of the present invention;
FIG. 5 is a TPR characterization plot of 5 wt% Pt-Co as provided in example 1 of the present invention;
FIG. 6 is an X-ray powder diffraction characterization of a 5 wt% Pt-Pb-Ru-Rh quaternary ultra-small alloy provided in example 8 of the present invention;
FIG. 7 is a graph of the kinetic data of selective hydrogenation of p-chloronitrobenzene with 5 wt% Pt-Co provided in example 1 of the present invention;
FIG. 8 is a bar graph of the stability of 5 wt% Pt-Co in p-chloronitrobenzene selective hydrogenation provided in example 1 of the present invention;
FIG. 9 is a graph of the kinetics of selective oxidation of 5 wt% Pt-Bi in benzyl alcohol as provided in example 9 of the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
In view of the current situation of the load type ultra-small alloy particle composite material, the application provides an ultra-small multi-element alloy composite material and a preparation method thereof, multi-element alloy particles in the ultra-small multi-element alloy composite material are stably loaded on the surface of sulfur-doped mesoporous carbon, and due to the strong acting force of S and metal, the alloy particles are ultra-small in size and stable and uniform. Specifically, the embodiment of the invention discloses an ultra-small multi-element alloy composite material, which comprises sulfur-doped mesoporous carbon and ultra-small alloy particles loaded on the surface of the sulfur-doped mesoporous carbon; the average size of the ultra-small alloy particles is 2 nm.
For the ultra-small multi-element alloy composite material provided by the application, the ultra-small multi-element alloy composite material comprises sulfur-doped mesoporous carbon and ultra-small alloy particles, wherein the sulfur-doped mesoporous carbon is used as a carrier of the ultra-small alloy particles, and the ultra-small alloy particles are alloy particles formed by at least two metal elements and are small in size.
The sulfur-doped mesoporous carbon described herein may be prepared according to methods well known to those skilled in the art, and is not particularly limited in this application. According to the present invention, the alloy In the above-mentioned ultra-small alloy particles may be alloy particles formed of any two or more alloy elements well known to those skilled In the art, and exemplified by the ultra-small alloy particles selected from two or more of Pt, Rh, Pd, Ir, Ru, Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Mo, Cd, In, Sn, Sb, Bi, Pb, Re, W, Ta and Hf; more specifically, the ultra-small alloy particles may be Pt-Co alloy particles, Pt-Ir-Sn alloy particles, or Pt-Rh-Ru-Pb alloy particles. The average size of the ultra-small alloy particles is 2 nm. The load capacity of the ultra-small alloy particles is 1-20 wt%; in a specific embodiment, the loading of the ultra-small alloy particles is 5 wt% to 10 wt%. In the application, the ultra-small alloy particles in the ultra-small multi-element alloy composite material are loaded on the surface of the sulfur-doped mesoporous carbon.
The application also provides a preparation method of the ultra-small multi-element alloy composite material, which comprises the following steps:
mixing sulfur-doped mesoporous carbon, a metal salt precursor and a solvent, and drying to obtain an initial mixture; the metal salt precursor is a metal salt precursor of two or more different metal elements;
carrying out heat treatment on the initial mixture in a reducing atmosphere to obtain an ultra-small multi-element alloy composite material; the temperature of the heat treatment is 400-800 ℃.
The ultra-small multi-element alloy composite material provided by the application can be prepared by adopting a dipping and heat treatment mode, the method has universality on various metals, and the process operation is simple and easy to implement.
Specifically, in the process of preparing the ultra-small multi-element alloy composite material, firstly, sulfur-doped mesoporous carbon, a metal salt precursor and a solvent are mixed, and an initial mixture is obtained after drying; the process is a mixing process of sulfur-doped mesoporous carbon and a metal salt precursor; the preparation method of the sulfur-doped mesoporous carbon is as follows, and more specifically, the preparation method of the sulfur-doped mesoporous carbon comprises the following steps:
sulfur-containing organic micromolecules, SiO2Mixing the pellets and transition metal salt in a solvent, drying and calcining at high temperature to obtain a carbon material;
and sequentially etching the carbon material by using sodium hydroxide and sulfuric acid to obtain the sulfur-doped mesoporous carbon.
In the above process of preparing sulfur-doped mesoporous carbon, the sulfur-containing organic small molecule is selected from sulfur-containing small molecules well known to those skilled in the art, and in the present application, the sulfur-containing small molecule is selected from 2, 2' -bithiophene; the transition metal salt is also selected from transition metal salts well known to those skilled in the art, illustratively, in this application the transition metal salt is selected from cobalt nitrate hexahydrate and the solvent may be selected from tetrahydrofuran. The sulfur-containing small molecule, SiO2The molar ratio of the pellets to the transition metal salt is 2:2: 1; the calcining temperature is 600-1200 ℃. The preparation method of the sulfur-doped mesoporous carbon can be carried out according to the fieldThe preparation is carried out by methods known to the skilled worker, and the present application is not restricted in particular. And in the subsequent etching process, sodium hydroxide is used for etching away silicon dioxide in the carbon material, sulfuric acid is used for etching away metal particles in the carbon material, the two processes are sequentially carried out so as to respectively realize the etching of the silicon dioxide and the metal particles, and finally the sulfur-doped mesoporous carbon is obtained.
For another raw material metal salt precursor, the metal element is a metal element well known to those skilled in the art, and the metal salt precursor described herein may include a salt of a noble metal, a salt of a non-noble metal, a salt of a noble metal and a salt of a non-noble metal; wherein the noble metal element of the noble metal salt is selected from one or more of Pt, Rh, Pd, Ir and Ru, and the non-noble metal element of the non-noble metal salt is selected from one or more of Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Mo, Cd, In, Sn, Sb, Bi, Pb, Re, W, Ta and Hf. The metal salt precursor is a metal salt precursor of two or more different metal elements, which can be a salt of two or more noble metals, a salt of two or more non-noble metals, or a mixture of a salt of a noble metal and a salt of a non-noble metal; namely, the metal elements are randomly combined; for example: binary alloy Pt-Al/Pd/Ir/Rh/Fe/Co/Ni/Ga/Ge/Sn/In … …; ternary ultra-small alloy PtIrSn/PtIrRu/PtIrZn PtCoCu/PtCoGa/RhCoGa/RhIrRu … …; the quaternary super small alloy PtRuIrSn/PdRuIrSn/RhRuIrSn/PtRuIrCo/PtRuIrCu/PtFeCoNi … …. The salt form of the metal salt precursor is also not particularly limited, and may be a salt form well known to those skilled in the art; in the case of Pt, the salt of Pt may be H2PtCl6、Pt(acac)2、Pt(NH3)4Cl2… … are provided. The different metal salt precursors are not in proportion, and are reasonably added according to the loading amount of the precursors in the sulfur-doped mesoporous carbon.
In the process of obtaining the initial mixture, the solvent can be added by selecting a suitable solvent according to the kind of the metal salt precursor, for example, the metal precursor is an inorganic metal salt (CoCl)6·6H2O) Normal waterAs a solvent, organic metal salts generally use ethanol as a solvent, and inorganic metal salts are easily hydrolyzed (TiCl4) Organic solvents are required to be selected for dissolution; in this process, the solvent is mainly intended to be sufficiently miscible and not to undergo chemical reactions.
According to the invention, after the initial mixture is obtained, it is subjected to a heat treatment in a reducing atmosphere to obtain an ultra-small multi-element alloy composite material; the process is a reduction process of a metal salt precursor, the metal salt precursor is reduced after ligand removal, and the metal salt is converted into a metal phase. The specific process is as follows:
transferring the initial mixture into a quartz crucible or a corundum crucible, putting the quartz crucible or the corundum crucible into a tube furnace, taking hydrogen or hydrogen mixed gas as reducing atmosphere, heating to 400-800 ℃ at the speed of 2-20 ℃/min, preserving heat for 0.5-12 h, and naturally cooling to room temperature; during this process, the pressure inside the tube furnace was kept constant. The hydrogen gas mixture is selected from a mixture of hydrogen and nitrogen, a mixture of hydrogen and argon, or a mixture of hydrogen and carbon monoxide. In the above process, the rate is 5 to 10 ℃/min in the specific embodiment, and the temperature is more specifically 500 to 700 ℃. If the temperature rise rate is too high, alloy particles are too large; the temperature of the heat treatment will determine the homogenization degree of the alloy, with too low a temperature resulting in a lower alloying degree and too high a temperature resulting in too large alloy particles. In the above heat treatment process, under high temperature and reducing atmosphere, the metal particles are easily subjected to Ostwald ripening, and small particles migrate to the upper surface of large particles, resulting in an increase in particle size; meanwhile, the temperature is increased, so that mutual diffusion of two different metals (especially for incompatible metal phases) in the alloy is facilitated, and a more uniform composition is formed. Therefore, different metals need to be regulated and controlled at proper temperature and time to ensure that ultra-small alloy particles are obtained and the phenomenon of agglomeration is avoided.
The method prepares the ultra-small multi-element alloy composite material by using a dipping and heat treatment mode, and the composite material has strong interaction between metal and sulfur, so that the sintering resistance of metal particles can be improved; and the metal nano particles do not agglomerate under the high temperature condition, so that the multi-element alloy composite material with the ultra-small size is formed.
The ultra-small multi-element alloy composite material can be used as a catalyst for heterogeneous catalysis, and particularly can be used as a catalyst for p-chloronitrobenzene hydrogenation reaction, levulinic acid hydrogenation reaction or benzyl alcohol selective oxidation; the catalyst shows unique activity and high stability. When the ultra-small multi-element alloy composite material is used as a catalyst for heterogeneous catalysis, the proportion of alloy elements in alloy particles in the ultra-small multi-element alloy composite material has a large influence on the catalytic effect; on the basis, in the process of preparing the ultra-small multi-element alloy composite material, the proportional relation of metal elements in the metal salt precursor needs to be further regulated and controlled.
For further understanding of the present invention, the following examples are provided to illustrate the ultra small multicomponent alloy composite material, its preparation method and its application, and the scope of the present invention is not limited by the following examples.
Example 1
a. 0.5g of bithiophene, 0.5g of SiO2Aerogel with 0.25g Co (NO)3)2·6H2Dispersing O in tetrahydrofuran, stirring uniformly, and removing the solvent by rotary evaporation to obtain a uniform mixture; transferring the obtained uniform mixture into a quartz crucible or a corundum crucible, putting the quartz crucible or the corundum crucible into a tube furnace, introducing nitrogen as protective gas, heating the tube furnace to 800 ℃ at the speed of 5 ℃/min, and keeping the temperature for 2 hours; naturally cooling to room temperature, and keeping normal pressure in the tubular furnace; then transferring the obtained solution into a flask, adding about 40mL of 2mol/L NaOH solution, and stirring for 36 hours to carry out first alkali etching; then centrifuging the solution in a centrifuge for 5min under the condition of 8000 r; then pouring out the centrifuged supernatant, transferring the lower solid into the flask again, adding about 2mol/L NaOH solution 40mL, stirring for 36h, and carrying out second alkali etching; finally, centrifugally washing to be neutral, placing the obtained product in a 25ml round-bottom flask, carrying out oil bath in 0.5mol/L sulfuric acid solution at the temperature of 90 ℃, refluxing for 6 hours, then centrifugally washing, washing to be neutral, and drying to obtain the sulfur-doped mesoporous carbon nano material;
b. 47.5mg of the sulfur-doped mesoporous carbon nanomaterial S-C and H containing 1.5585mg of Pt2PtCl6And 0.9415mgCoCoCl of2(ensuring that the Pt/Co atomic ratio is 0.5) is placed in a 100mL round-bottom flask and diluted by adding water (the total volume is kept at 50mL) to obtain a mixture; carrying out ultrasonic treatment on the mixture for 2 hours, stirring for 12 hours, and carrying out rotary evaporation to obtain a catalyst-1;
c. the obtained catalyst-1 is put into a quartz boat, and 5 percent volH is introduced2Ar gas, heating the tube furnace to 700 ℃ at the speed of 5 ℃/min, and keeping for 2.0 h; naturally cooling to room temperature to obtain 5 wt% Pt-Co/SC.
FIG. 1 is data of S element in X-ray photoelectron spectroscopy (XPS) of 5 wt% Pt-Co/SC in example 1 of the present invention; as can be seen from fig. 1, the position of all the S peaks of the ultra-small alloy are shifted with respect to the sulfur-carbon, indicating a strong interaction between the sulfur-carbon support and the metal.
FIG. 2 is an X-ray powder diffraction characterization of 5 wt% Pt-Co/SC and other parts of binary ultra small alloys in example 1 of the present invention; no peaks of any metal were seen, indicating that the alloy size was particularly small, below the detection limit of X-rays.
FIG. 3 is a HAADF-mapping characterization of 5 wt% Pt-Co/SC provided in example 1 of the present invention, and it can be seen that the mapping of Pt and the mapping of Co completely overlap, indicating that the degree of alloying is particularly good.
FIG. 4 is a line scan characterization plot of 5 wt% Pt-Co/SC provided in example 1 of the present invention; as can be seen from fig. 4, the single particles contain signals of Pt and Co, indicating that the degree of alloying is good.
FIG. 5 is a TPR characterization of 5 wt% Pt-Co/SC provided in example 1 of the present invention; the reduction temperature of PtCo shifts to a lower temperature than Co, indicating that the H flooding effect occurs, demonstrating the formation of an alloy.
The 5 wt% Pt-Co/SC prepared in the embodiment is used for the hydrogenation reaction of p-chloronitrobenzene, and specifically comprises the following steps: in the selective hydrogenation of p-chloronitrobenzene, 315mg of p-chloronitrobenzene (2mmol) was used as solvent with 5ml of methanol, 7.804mg of 5 wt% Pt-Co/SC was added as catalyst (0.1% molar Pt), and 2.0bar H was added at 40 deg.C2Reacting under the condition; the other comparative catalysts were also run under the same conditions.
FIG. 7 is the kinetic data of selective hydrogenation reaction of 5 wt% Pt-Co/SC in p-chloronitrobenzene provided in example 1 of the present invention; the ultra-small alloy has good activity and selectivity.
FIG. 8 is a bar graph of the stability of 5 wt% Pt-Co/SC in selective hydrogenation of p-chloronitrobenzene in example 1 of the present invention; therefore, the Pt-Co/SC has better stability when being used as the chloronitrobenzene hydrogenation catalyst.
Example 2
a. 0.5g of bithiophene, 0.5g of SiO2Aerogel with 0.25g Co (NO)3)2·6H2Dispersing O in tetrahydrofuran, stirring uniformly, and removing the solvent by rotary evaporation to obtain a uniform mixture; transferring the obtained uniform mixture into a quartz crucible or a corundum crucible, putting the quartz crucible or the corundum crucible into a tubular furnace, introducing nitrogen as protective gas, heating the tubular furnace to 800 ℃ at the speed of 5 ℃/min, keeping the temperature for 2 hours, naturally cooling to room temperature, and keeping the pressure in the tubular furnace at normal pressure; then transferring the obtained solution into a flask, adding about 40mL of 2mol/L NaOH solution, stirring for 36h, and carrying out primary alkali etching; centrifuging the solution in a centrifuge for 5min at 8000r, pouring out the supernatant, transferring the lower solid into the flask again, adding about 40mL of 2mol/L NaOH solution, stirring for 36h, and performing secondary alkali etching; finally, centrifugally washing to be neutral, placing the obtained product in a 25ml round-bottom flask, carrying out oil bath in 0.5mol/L sulfuric acid solution at the temperature of 90 ℃, refluxing for 6 hours, then centrifugally washing, washing to be neutral, and drying to obtain the sulfur-doped mesoporous carbon nano material;
b. 47.5mg of the sulfur-doped mesoporous carbon nanomaterial S-C obtained above and H containing 1.5585mg of Pt2PtCl6And 0.9415mgCo of Co (acac)2Placing the mixture into a 100mL round-bottom flask, adding acetone for dilution (the total volume is kept to be 50mL) to obtain a mixture, carrying out ultrasonic treatment on the mixture for 2 hours, stirring for 12 hours, and carrying out rotary evaporation to obtain a catalyst-1;
c. the obtained catalyst-1 is put into a quartz boat, and 5 percent volH is introduced2Ar gas, heating the tube furnace to 700 ℃ at the speed of 5 ℃/min, and keeping for 2.0 h; naturally cooling to room temperature to obtain 5 wt% Pt-Co/SC.
Example 3
a. 0.5g of bithiophene, 0.5g of SiO2Aerogel with 0.25g Co (NO)3)2·6H2Dispersing O in tetrahydrofuran, stirring uniformly, and removing the solvent by rotary evaporation to obtain a uniform mixture; transferring the obtained uniform mixture into a quartz crucible or a corundum crucible, putting the quartz crucible or the corundum crucible into a tubular furnace, introducing nitrogen as protective gas, heating the tubular furnace to 800 ℃ at the speed of 5 ℃/min, keeping the temperature for 2 hours, naturally cooling to room temperature, and keeping the pressure in the tubular furnace at normal pressure; then transferring the obtained solution into a flask, adding about 40mL of 2mol/L NaOH solution, stirring for 36h, and carrying out primary alkali etching; centrifuging the solution in a centrifuge for 5min at 8000r, pouring out the supernatant, transferring the lower solid into the flask again, adding about 40mL of 2mol/L NaOH solution, stirring for 36h, and performing secondary alkali etching; then centrifugally washing to be neutral, placing the obtained product in a 25ml round-bottom flask, carrying out oil bath in 0.5mol/L sulfuric acid solution at the temperature of 90 ℃, refluxing for 6 hours, then centrifugally washing, washing to be neutral, and drying to obtain the sulfur-doped mesoporous carbon nano material;
b. 47.5mg of S-C obtained from the sulfur-doped mesoporous carbon nanomaterial and 2.357mg of Pt-H2PtCl6And 0.1424mgCo in CoCl2Placing the mixture into a 100mL round-bottom flask, adding water to dilute the mixture (keeping the total volume between 50mL) to obtain a mixture, carrying out ultrasonic treatment on the mixture for 2 hours, stirring the mixture for 12 hours, and carrying out rotary evaporation to obtain a catalyst-1;
c. putting the obtained catalyst-1 into a quartz boat, and introducing 5% vol H2Ar gas, heating the tube furnace to 700 ℃ at the speed of 5 ℃/min, and keeping for 2.0 h; naturally cooling to room temperature to obtain 5 wt% Pt-Co/SC.
Example 4
a. 0.5g of bithiophene, 0.5g of SiO2Aerogel with 0.25g Co (NO)3)2·6H2Dispersing O in tetrahydrofuran, stirring uniformly, and removing the solvent by rotary evaporation to obtain a uniform mixture; transferring the obtained uniform mixture into a quartz crucible or a corundum crucible, putting the quartz crucible or the corundum crucible into a tube furnace, introducing nitrogen as protective gas, and enabling the tube furnace to be at a speed of 5 ℃/minThe temperature is raised to 800 ℃ at the speed, the temperature is kept for 2 hours, then the temperature is naturally reduced to room temperature, and the normal pressure is kept in the tube furnace; then transferring the obtained solution into a flask, adding about 40mL of 2mol/L NaOH solution, stirring for 36h, and carrying out primary alkali etching; centrifuging the solution in a centrifuge for 5min at 8000r, pouring out the supernatant, transferring the lower solid into the flask again, adding about 40mL of 2mol/L NaOH solution, stirring for 36h, and performing secondary alkali etching; then centrifugally washing to be neutral, placing the obtained product in a 25ml round-bottom flask, carrying out oil bath in 0.5mol/L sulfuric acid solution at the temperature of 90 ℃, refluxing for 6 hours, then centrifugally washing, washing to be neutral, and drying to obtain the sulfur-doped mesoporous carbon nano material;
b. 40mg of the sulfur-doped mesoporous carbon nanomaterial S-C obtained above and H containing 9.4304mg of Pt2PtCl6And 0.5696mgCo in CoCl2Placing the mixture into a 100mL round-bottom flask, adding water to dilute the mixture (keeping the total volume between 50mL) to obtain a mixture, carrying out ultrasonic treatment on the mixture for 2 hours, stirring the mixture for 12 hours, and carrying out rotary evaporation to obtain a catalyst-1;
c. putting the obtained catalyst-1 into a quartz boat, and introducing 5% vol H2Ar gas, heating the tube furnace to 700 ℃ at the speed of 5 ℃/min, and keeping for 2.0 h; naturally cooling to room temperature to obtain the Pt-Co/SC with the concentration of 20 wt%.
Example 5
a. 0.5g of bithiophene, 0.5g of SiO2Aerogel with 0.25g Co (NO)3)2·6H2Dispersing O in tetrahydrofuran, stirring uniformly, and removing the solvent by rotary evaporation to obtain a uniform mixture; transferring the obtained uniform mixture into a quartz crucible or a corundum crucible, putting the quartz crucible or the corundum crucible into a tube furnace, introducing nitrogen as protective gas, heating the tube furnace to 800 ℃ at the speed of 5 ℃/min, and keeping the temperature for 2 hours; naturally cooling to room temperature, and keeping normal pressure in the tubular furnace; then transferring the obtained solution into a flask, adding about 40mL of 2mol/L NaOH solution, stirring for 36h, and carrying out primary alkali etching; centrifuging the solution at 8000r for 5min, pouring out supernatant, transferring the lower solid into flask, and addingStirring about 40mL of 2mol/L NaOH solution for 36h, and carrying out second alkali etching; then centrifugally washing to be neutral, placing the obtained product in a 25ml round-bottom flask, carrying out oil bath in 0.5mol/L sulfuric acid solution at the temperature of 90 ℃, refluxing for 6 hours, then centrifugally washing, washing to be neutral, and drying to obtain the sulfur-doped mesoporous carbon nano material;
b. 47.5mg of the sulfur-doped mesoporous carbon nanomaterial S-C obtained above and H containing 1.25mg of Pt2PtCl6And 1.25mgIr in IrCl3(ensuring that the atomic ratio of Pt/Ir is 1) is placed in a 100mL round-bottom flask, water is added for dilution (the total volume is kept at 50mL) to obtain a mixture, the mixture is subjected to ultrasonic treatment for 2 hours, stirred for 12 hours, and rotary evaporation is carried out to obtain the catalyst-1.
c. Putting the obtained catalyst-1 into a quartz boat, and introducing 5% vol H2Ar gas, heating the tube furnace to 700 ℃ at the speed of 5 ℃/min, and keeping for 2.0 h; naturally cooling to room temperature to obtain 5 wt% of Pt-Ir/SC.
Example 6
a. 0.5g of bithiophene, 0.5g of SiO2Aerogel with 0.25g Co (NO)3)2·6H2Dispersing O in tetrahydrofuran, stirring uniformly, and removing the solvent by rotary evaporation to obtain a uniform mixture; transferring the obtained uniform mixture into a quartz crucible or a corundum crucible, putting the quartz crucible or the corundum crucible into a tubular furnace, introducing nitrogen as protective gas, heating the tubular furnace to 800 ℃ at the speed of 5 ℃/min, keeping the temperature for 2 hours, naturally cooling to room temperature, and keeping the pressure in the tubular furnace at normal pressure; then transferring the obtained solution into a flask, adding about 40mL of 2mol/L NaOH solution, stirring for 36h, and carrying out primary alkali etching; centrifuging the solution in a centrifuge for 5min at 8000r, pouring out the supernatant, transferring the lower solid into the flask again, adding about 40mL of 2mol/L NaOH solution, stirring for 36h, and performing secondary alkali etching; then centrifugally washing to be neutral, placing the obtained product in a 25ml round-bottom flask, carrying out oil bath in 0.5mol/L sulfuric acid solution at the temperature of 90 ℃, refluxing for 6 hours, then centrifugally washing, washing to be neutral, and drying to obtain the sulfur-doped mesoporous carbon nano material;
b. the above mentioned station47.5mg of sulfur-doped mesoporous carbon nano material S-C and H containing 1.25mg of Pt are obtained2PtCl6And 1.25mgIr in IrCl3Placing the obtained product in a 100mL round-bottom flask, adding water to dilute the product (the total volume is kept to be 50mL) to obtain a mixture, carrying out ultrasonic treatment on the mixture for 2 hours, stirring the mixture for 12 hours, and carrying out rotary evaporation to obtain a catalyst-1;
c. putting the obtained catalyst-1 into a quartz boat, and introducing 5% vol H2Ar gas, heating the tube furnace to 400 ℃ at the speed of 5 ℃/min, and keeping the temperature for 8.0 h; naturally cooling to room temperature to obtain 5 wt% of Pt-Ir/SC.
The 5 wt% Pt-Ir/SC prepared in the embodiment is used as a catalyst for hydrogenation of levulinic acid, and specifically comprises the following steps: during the hydrogenation reaction of levulinic acid, 1ml of n-butanol is added as a solvent in 4.0MPaH250ul (0.5mmol) levulinic acid, 2.0mg 5 wt% Pt-Ir/SC (0.1% molar amount of Pt) at 200 ℃ for 60 min.
Table 1 lists data for different catalysts for levulinic acid hydrogenation reactions; as shown in table 1:
TABLE 1 data table of different catalysts for the hydrogenation of levulinic acid
| Catalyst and process for preparing same | Conversion rate% | Selectivity% |
| 5wt％Pt-Ir/ |
100 | >99 |
| 20wt％Pt-Ir/SC | 89 | 84.36 |
| Pt/SC | 87.5 | 76.27 |
| Ir/SC | 46.08 | 33 |
| C/Pt | 82.06 | 82.46 |
| C/Ir | 74.07 | 100 |
| V-72-PtIr | 84.96 | 42.0 |
| K-300J-PtIr | 89.56 | >99 |
As can be seen from Table 1, the 5 wt% Pt-Ir/SC catalyst with different loading amounts and the 20wt% Pt-Ir/SC catalyst have better 5 wt% Pt-Ir/SC activity under the condition of adding the same metal molar weight, which shows the advantage of the particle size of the ultra-small alloy (the 5 wt% Pt-Ir/SC is smaller than the 20wt% Pt-Ir/SC particle size); meanwhile, the 5 wt% Pt-Ir/SC has better catalytic activity and selectivity than single metal Ir/SC and Pt/SC; the performance of the catalyst is better than that of a commercial catalyst, and a bimetallic coordination effect is shown; compared with the catalyst V-72-PtIr and K-300J-PtIr which are loaded on a common carbon carrier, the carrier S-C has the carrier effect for improving the catalysis, and the conversion rate and the selectivity are improved due to the interaction between the carrier and the ultra-small alloy.
Example 7
a. 0.5g of bithiophene, 0.5g of SiO2Aerogel with 0.25g Co (NO)3)2·6H2Dispersing O in tetrahydrofuran, stirring uniformly, and removing the solvent by rotary evaporation to obtain a uniform mixture; transferring the obtained uniform mixture into a quartz crucible or a corundum crucible, putting the quartz crucible or the corundum crucible into a tubular furnace, introducing nitrogen as protective gas, heating the tubular furnace to 800 ℃ at the speed of 5 ℃/min, keeping the temperature for 2 hours, naturally cooling to room temperature, and keeping the pressure in the tubular furnace at normal pressure; transferring the obtained solution into a flask, adding about 40mL of 2mol/L NaOH solution, stirring for 36h, performing primary alkali etching, centrifuging the solution in a centrifuge for 5min at 8000r, pouring out the centrifuged supernatant, transferring the lower-layer solid into the flask again, adding about 40mL of 2mol/L NaOH solution, stirring for 36h, and performing secondary alkali etching; then centrifugally washing to be neutral, placing the obtained product in a 25ml round-bottom flask, carrying out oil bath in 0.5mol/L sulfuric acid solution at the temperature of 90 ℃, refluxing for 6 hours, then centrifugally washing, washing to be neutral, and drying to obtain the sulfur-doped mesoporous carbon nano material;
b. 47.5mg of S-C obtained above was mixed with H containing 0.9639mg of Pt2PtCl60.5865 SnCl of mgSn2And 0.9496mgIr in IrCl3Placing the obtained product in a 100mL round-bottom flask, adding water to dilute the product (the total volume is kept to be 50mL) to obtain a mixture, carrying out ultrasonic treatment on the mixture for 2 hours, stirring the mixture for 12 hours, and carrying out rotary evaporation to obtain a catalyst-1;
c. putting the obtained catalyst-1 into a quartz boat, and introducing 5% vol H2Ar gas, heating the tube furnace to 400 ℃ at the speed of 5 ℃/min, and keeping for 2.0 h; naturally cooling to room temperature to obtain 5 wt% of Pt-Ir-Sn/SC (ternary ultra-small alloy).
Example 8
a. 0.5g of bithiophene, 0.5g of SiO2Aerogel with 0.25g Co (NO)3)2·6H2Dispersing O in tetrahydrofuran, stirring uniformly, and removing the solvent by rotary evaporation to obtain a uniform mixture; transferring the obtained uniform mixture into a quartz crucible or a corundum crucible,putting the tube furnace into a tube furnace, introducing nitrogen as protective gas, heating the tube furnace to 800 ℃ at the speed of 5 ℃/min, keeping for 2 hours, naturally cooling to room temperature, and keeping the pressure in the tube furnace at normal pressure; then transferring the obtained solution into a flask, adding about 40mL of 2mol/L NaOH solution, stirring for 36h, and carrying out primary alkali etching; centrifuging the solution in a centrifuge for 5min at 8000r, pouring out the supernatant, transferring the lower solid into the flask again, adding about 40mL of 2mol/L NaOH solution, stirring for 36h, and performing secondary alkali etching; then centrifugally washing to be neutral, placing the obtained product in a 25ml round-bottom flask, carrying out oil bath in 0.5mol/L sulfuric acid solution at the temperature of 90 ℃, refluxing for 6 hours, then centrifugally washing, washing to be neutral, and drying to obtain the sulfur-doped mesoporous carbon nano material;
b. 47.5mg of the sulfur-doped mesoporous carbon nanomaterial S-C obtained above and H containing 0.0625mg of Pt2PtCl60.0625mgRu RuCl30.0625mgPb of Pb (NO)3)2And 0.0625mgRh in RhCl3(ensuring that the mass ratio of Pt/Rh/Ru/Pb is 1/1/1) is placed in a 100mL round-bottom flask, water is added for dilution (the total volume is kept at 50mL) to obtain a mixture, the mixture is subjected to ultrasonic treatment for 2 hours, stirred for 12 hours, and rotary evaporation is carried out to obtain a catalyst-1;
c. putting the obtained catalyst-1 into a quartz boat, and introducing 5% vol H2Ar gas, heating the tube furnace to 400 ℃ at the speed of 5 ℃/min, and keeping for 2.0 h; naturally cooling to room temperature to obtain 5 wt% Pt-Rh-Ru-Pb/SC (quaternary ultra-small alloy).
FIG. 6 is an X-ray powder diffraction characterization of a 5 wt% Pt-Pb-Ru-Rh/SC quaternary ultra-small alloy provided in example 8 of the present invention; illustrating the relatively small size of the quaternary alloy.
Example 9
The Pt-Bi/SC composite material is prepared according to the method and is used as a catalyst for benzyl alcohol oxidation, and the method specifically comprises the following steps: in the course of the oxidation of benzyl alcohol, without solvent, 1ml of benzyl alcohol (9.6mmol) was added, 37.45mg of catalyst (0.1% molar amount of Pt)5 wt% Pt-Bi/SC, 1500r, O at 100 ℃ under 0.2MPa2And (4) reacting.
FIG. 9 is a graph showing the kinetics of selective oxidation of benzyl alcohol to benzaldehyde.
Table 2 shows a table of the activity of the benzyl alcohol oxidation reaction over different catalysts, as shown in Table 2:
TABLE 2 data table of the activity of the oxidation of benzyl alcohol in the presence of different catalysts
As can be seen from Table 2, the activity of the PtBi ultra-small alloy in the PtBi/SC catalyst is obviously superior to that of single metals Pt and Bi, physically mixed Pt + Bi and commercial catalyst Pt/C; while selectivity is superior to that of single metal and commercial catalysts.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (5)
1. An ultra-small multi-element alloy composite material comprises sulfur-doped mesoporous carbon and ultra-small alloy particles loaded on the surface of the sulfur-doped mesoporous carbon; the average size of the ultra-small alloy particles is 2 nm;
the preparation method of the ultra-small multi-element alloy composite material comprises the following steps:
mixing sulfur-doped mesoporous carbon, a metal salt precursor and a solvent, and drying to obtain an initial mixture; the metal salt precursor is a metal salt precursor of two or more different metal elements;
carrying out heat treatment on the initial mixture in a reducing atmosphere to obtain an ultra-small multi-element alloy composite material; the temperature of the heat treatment is 400 or 700 ℃;
the heating rate of the heat treatment is 5-10 ℃/min, and the time is 0.5-12 h;
the metal elements of the ultra-small alloy particles are two or more selected from Pt, Rh, Pd, Ir, Ru, Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Mo, Cd, In, Sn, Sb, Bi, Pb, Re, W, Ta and Hf;
the preparation method of the sulfur-doped mesoporous carbon comprises the following specific steps:
sulfur-containing organic micromolecules, SiO2Mixing the pellets and transition metal salt in a solvent, drying and calcining at high temperature to obtain a carbon material;
and sequentially etching the carbon material by using sodium hydroxide and sulfuric acid to obtain the sulfur-doped mesoporous carbon.
2. The ultra small multi-element alloy composite material as claimed in claim 1, wherein the loading of the ultra small alloy particles is 1wt% to 20 wt%.
3. The ultra-small multi-element alloy composite material as claimed in claim 1, wherein the sulfur-containing organic small molecule is 2, 2' -bithiophene, and the transition metal salt is selected from cobalt nitrate hexahydrate; the sulfur-containing small molecule, SiO2The molar ratio of the pellets to the transition metal salt is 2:2: 1; the calcining temperature is 600-1200 ℃.
4. The ultra small multi-element alloy composite material as claimed in claim 1, wherein the reducing atmosphere is a hydrogen atmosphere or a hydrogen mixture atmosphere; the hydrogen mixed gas atmosphere is selected from the mixed gas of hydrogen and nitrogen, the mixed gas of hydrogen and argon or the mixed gas of hydrogen and carbon monoxide.
5. The use of the ultra small multicomponent alloy composite of any of claims 1 to 4 in heterogeneous catalysis.
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