CN114570359A - Precious metal/carbon nanosheet composite material and preparation method thereof - Google Patents
Precious metal/carbon nanosheet composite material and preparation method thereof Download PDFInfo
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- CN114570359A CN114570359A CN202111617554.2A CN202111617554A CN114570359A CN 114570359 A CN114570359 A CN 114570359A CN 202111617554 A CN202111617554 A CN 202111617554A CN 114570359 A CN114570359 A CN 114570359A
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- 239000002135 nanosheet Substances 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000010970 precious metal Substances 0.000 title claims description 10
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 81
- 150000003839 salts Chemical class 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 21
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 21
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 21
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004202 carbamide Substances 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims description 36
- 238000001816 cooling Methods 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000000197 pyrolysis Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 4
- 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 3
- 239000000178 monomer Substances 0.000 claims description 3
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 3
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 150000002503 iridium Chemical class 0.000 claims description 2
- 150000002940 palladium Chemical class 0.000 claims description 2
- 150000003057 platinum Chemical class 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 150000003283 rhodium Chemical class 0.000 claims description 2
- 150000003303 ruthenium Chemical class 0.000 claims description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000002905 metal composite material Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000003321 amplification Effects 0.000 abstract 1
- 238000003199 nucleic acid amplification method Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 16
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 13
- 229910052741 iridium Inorganic materials 0.000 description 10
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- 239000002082 metal nanoparticle Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 4
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- -1 primary amine modified activated carbon Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- MBVAQOHBPXKYMF-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MBVAQOHBPXKYMF-LNTINUHCSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Natural products CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- HLYTZTFNIRBLNA-LNTINUHCSA-K iridium(3+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ir+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O HLYTZTFNIRBLNA-LNTINUHCSA-K 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 1
Images
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/468—Iridium
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a noble metal/carbon nanosheet composite material and a preparation method thereof, wherein noble metal salt, polyvinylpyrrolidone and urea are uniformly mixed according to a certain proportion, heated and polymerized to form a solid state at the temperature of 240 ℃ under the condition of 160-. The method solves the technical problems of incomplete conversion of the noble metal raw material and easy shedding of the noble metal in the preparation process of the noble metal catalyst, can prepare the double-element or multi-element noble metal composite material, does not need acid washing, is environment-friendly, has simple preparation process, and is beneficial to industrial amplification production.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a precious metal/carbon nanosheet composite material and a preparation method thereof.
Background
The noble metal catalyst has the advantages of excellent catalytic activity, catalytic selectivity and the like, and is widely applied to the fields of medicine synthesis, chemical production, energy catalysis and the like. Because the reserves of the noble metal in the earth crust are small and the price is high, the improvement of the utilization rate of the noble metal and the development of the noble metal catalyst with high activity and high stability are very important.
In the prior art, a traditional impregnation method is used for preparing the carbon-supported noble metal nano material, and a noble metal salt solution and an activated carbon base are fully mixed, dried and reduced at a high temperature to prepare the carbon-supported noble metal catalyst. The noble metal nano particles in the noble metal catalyst material prepared by the method have wider particle size distribution, and meanwhile, the noble metal nano particles are easy to fall off in the using process, so that the activity of the catalyst is reduced. Patent CN111129511A proposes a method for preparing a nitrogen-doped carbon-supported platinum-based catalyst, which is to prepare a nitrogen-doped carbon carrier from polymer fibers obtained by high-temperature pyrolysis electrostatic spinning, and then grow platinum nanoparticles on the nitrogen-doped carbon carrier by a liquid-phase reduction method. The obtained catalyst material has large platinum loading capacity, but the preparation process is complex, and high-toxicity reducing agents and solvents such as sodium borohydride, N-dimethylformamide and the like are used, so that the environment hazard is large. Patent CN106916110A proposes a preparation method of a supported noble metal nanoparticle composite material, which takes metal organic framework combination (ZIF-67) as a carrier to obtain the ZIF-67 supported noble metal nanocomposite material by an in-situ reduction method. The noble metal composite material obtained by the method has the advantages of small noble metal particle size and narrow particle size distribution, but the preparation cost of the metal organic framework compound is high, toxic reducing agents such as sodium borohydride or hydrazine hydrate are used for obtaining noble metal nano particles, and simultaneously, the noble metal salt is not fully reduced, so that the waste of noble metal raw materials is caused. Patent CN109569686A uses an ultraviolet light reduction method to grow noble metal nanoparticles on primary amine modified activated carbon carrier, the invention adopts halo to avoid the use of reducing agents such as sodium borohydride and the like, and is environment-friendly, but the light reduction method has the problems of insufficient reduction of noble metal salt raw material and low utilization rate of raw material.
Therefore, the method for improving the conversion rate of the noble metal salt and the stability of the noble metal composite material and developing an environment-friendly preparation method for preparing the high-quality noble metal catalyst are an important research and development direction in the technical field.
Disclosure of Invention
In view of the above problems and technical deficiencies, the present invention aims to provide a method for preparing a noble metal/carbon nanosheet composite, which is obtained by uniformly mixing a noble metal salt, polyvinylpyrrolidone and urea, heating the mixture at a temperature of 160-.
The technical scheme for solving the problem is as follows:
a preparation method of a precious metal/carbon nanosheet composite material comprises the following steps:
(1) uniformly mixing noble metal salt, polyvinylpyrrolidone and urea according to a certain proportion, heating and polymerizing at the temperature of 160-240 ℃ until the mixture is completely solidified, and naturally cooling to room temperature to obtain a precursor;
(2) heating the precursor obtained in the step (1) to 800-1000 ℃ for pyrolysis under the conditions of program temperature control and protection of non-oxidizing gas, and then naturally cooling to room temperature to obtain the noble metal/carbon nanosheet composite material;
further, the noble metal salt in the step (1) is platinum salt, palladium salt, iridium salt, ruthenium salt or rhodium salt.
Further, the noble metal salt used in the step (1) is one or more of a noble metal acid salt, a noble metal chloride, a noble metal nitrate and a noble metal acetylacetone compound.
Further, the noble metal salt used in the step (1) is one or more of chloroplatinic acid, platinum tetrachloride, platinum dichloride, platinum acetylacetonate and platinum nitrate.
Furthermore, in the step (1), the mass ratio of the polyvinylpyrrolidone to the urea is 1:4-1:30, and the molar weight of the monomer in the polyvinylpyrrolidone is more than 4 times that of the noble metal salt.
Further, the heating time in the step (1) is 2-6h, and the temperature rise rate in the step (2) is 1-10 ℃/min; the pyrolysis time is 1-4 h.
Further, the non-oxidizing gas used in the step (2) is one or a mixture of hydrogen, nitrogen, argon and helium.
Further, the noble metal salt used in the step (1) is one or more of chloroplatinic acid, platinum tetrachloride, platinum dichloride, platinum acetylacetonate, platinum nitrate, palladium chloride, palladium nitrate, palladium acetylacetonate, iridium trichloride, chloroiridic acid, iridium acetylacetonate, ruthenium trichloride, rhodium trichloride and rhodium acetylacetonate.
Preferably, the heating temperature in the step (1) is 200-220 ℃.
Preferably, the temperature rise rate of the program in the step (2) is 3-5 ℃/min.
Preferably, the pyrolysis time in the step (2) is 2 h.
Preferably, the non-oxidizing gas in step (2) is nitrogen.
Preferably, the molar weight of the monomer in the polyvinylpyrrolidone in the step (1) is 8-20 times of that of the noble metal salt.
Preferably, the mass ratio of the polyvinylpyrrolidone to the urea in the step (1) is 1:5-1: 20.
The noble metal/carbon nanosheet composite material is prepared according to the method.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages:
(1) the preparation method of the noble metal/carbon nanosheet composite material is suitable for preparing various noble metal composite materials, including single-element or multi-element noble metals of platinum, palladium, rhodium, iridium and ruthenium.
(2) The preparation method of the noble metal/carbon nanosheet composite material can realize the complete conversion of the noble metal salt into the metal nanoparticles, the noble metal ions are reduced by carbon at high temperature to generate the nanoparticles, the conversion rate of the noble metal salt reaches 100%, the waste of the noble metal salt raw material is avoided, and the economy is good.
(3) According to the preparation method of the noble metal/carbon nanosheet composite material, noble metal ions are pyrolyzed to directly obtain the noble metal/carbon nanosheet composite material, the urea forms a graphite-phase carbon nitride sheet-shaped structural material at the temperature of 500-600 ℃, the polyvinylpyrrolidone is pyrolyzed by taking the graphite-phase carbon nitride nanosheet as a template to generate the sheet-shaped structure nitrogen-doped carbon material, the product does not need post-treatment, and the preparation method is environment-friendly.
(4) The preparation method of the noble metal/carbon nanosheet composite material directly obtains the noble metal/carbon nanosheet composite material by pyrolyzing the polyvinylpyrrolidone, the urea and the noble metal salt, wherein the content of the noble metal component is continuously adjustable, the metal content can reach more than 40 wt%, and the noble metal loading is high.
(5) In the noble metal/carbon nanosheet composite material prepared by the preparation method of the noble metal/carbon nanosheet composite material, the noble metal nanoparticles are firmly combined on the carbon nanosheets, are not easy to fall off in the using process, and have long service life when used as a catalyst.
(6) The raw materials used in the invention have low price and simple preparation process, and are beneficial to industrial scale-up production.
Drawings
FIG. 1 is a TEM image of the ruthenium/carbon nanosheet composite obtained in example 1;
FIG. 2 is an X-ray diffraction pattern of the ruthenium/carbon nanosheet composite obtained in example 2;
FIG. 3 is a TEM image of the ruthenium/carbon nanosheet composite obtained in example 3;
FIG. 4 is a TEM image of the iridium/carbon nanosheet composite obtained in example 4;
FIG. 5 is a TEM image of the iridium/carbon nanosheet composite obtained in example 5;
fig. 6 is a TEM image of the iridium/carbon nanosheet composite obtained in example 6.
Detailed Description
The foregoing and other technical and scientific aspects, features and utilities of the present invention will be apparent from the following detailed description of the embodiments, which is to be read in connection with the accompanying drawings of fig. 1-6. The structural contents mentioned in the following embodiments are all referred to the attached drawings of the specification.
Example 1
A preparation method of a precious metal/carbon nanosheet composite material comprises the following steps:
(1) uniformly mixing 120g of urea, 10g of polyvinylpyrrolidone and 2.0g of ruthenium trichloride, heating to 200 ℃, stirring for 4 hours until the mixture is completely solid, and naturally cooling to room temperature to obtain a precursor; (2) and putting the obtained precursor into a tube furnace, controlling the heating rate to be 4 ℃/min under the protection of argon, heating to 900 ℃, preserving the heat for 2h, and naturally cooling to room temperature to obtain the ruthenium/carbon nanosheet composite material, wherein the mass fraction of ruthenium in the ruthenium/carbon nanosheet composite material is 20%.
Example 2
A preparation method of a precious metal/carbon nanosheet composite material comprises the following steps:
(1) uniformly mixing 100g of urea, 8.0g of polyvinylpyrrolidone and 1.0g of ruthenium trichloride, heating to 190 ℃, stirring for 2 hours until the mixture is completely solid, and naturally cooling to room temperature to obtain a precursor; (2) and putting the obtained precursor into a tube furnace, controlling the heating rate to be 10 ℃/min under the protection of nitrogen, heating to 1000 ℃, preserving heat for 3h, and naturally cooling to room temperature to obtain the ruthenium/carbon nanosheet composite material, wherein the mass fraction of ruthenium in the ruthenium/carbon nanosheet composite material is 10%.
Example 3
A preparation method of a precious metal/carbon nanosheet composite material comprises the following steps:
(1) uniformly mixing 90g of urea, 6g of polyvinylpyrrolidone and 0.4g of ruthenium trichloride, heating to 230 ℃, stirring for 6 hours until the mixture is completely solid, and naturally cooling to room temperature to obtain a precursor; (2) and putting the obtained precursor into a tube furnace, controlling the heating rate to be 3 ℃/min under the protection of nitrogen, heating to 900 ℃, preserving the heat for 4h, and naturally cooling to room temperature to obtain the ruthenium/carbon nanosheet composite material, wherein the mass fraction of ruthenium in the ruthenium/carbon nanosheet composite material is 5%.
Example 4
A preparation method of a precious metal/carbon nanosheet composite material comprises the following steps:
(1) uniformly mixing 28g of urea, 2.8g of polyvinylpyrrolidone and 0.4g of iridium trichloride, heating to 220 ℃, stirring for 4 hours until the mixture is completely solid, and naturally cooling to room temperature to obtain a precursor; (2) and (3) putting the obtained precursor into a tube furnace, controlling the heating rate to be 5 ℃/min under the protection of argon, heating to 1000 ℃, preserving the heat for 4h, and naturally cooling to room temperature to obtain the iridium/carbon nanosheet composite material, wherein the mass fraction of iron in the iridium/carbon nanosheet composite material is 40%.
Example 5
(1) Uniformly mixing 60g of urea, 4.0g of polyvinylpyrrolidone and 0.4g of iridium trichloride, heating to 180 ℃, stirring for 4 hours until the mixture is completely solid, and naturally cooling to room temperature to obtain a precursor; (2) and (3) putting the obtained precursor into a tube furnace, controlling the heating rate to be 10 ℃/min under the protection of nitrogen, heating to 1000 ℃, preserving the heat for 1h, and naturally cooling to room temperature to obtain the iridium/carbon nanosheet composite material, wherein the mass fraction of iron in the iridium/carbon nanosheet composite material is 10%. .
Example 6
(1) Uniformly mixing 100g of urea, 8g of polyvinylpyrrolidone and 0.4g of tungsten hexachloride, heating to 160 ℃, stirring for 6 hours until the mixture is completely solid, and naturally cooling to room temperature to obtain a precursor; (2) and (3) putting the obtained precursor into a tube furnace, under the protection of argon, controlling the heating rate to be 8 ℃/min, heating to 900 ℃, preserving the temperature for 2h, and naturally cooling to room temperature to obtain the iridium/carbon nanosheet composite material, wherein the mass fraction of iron in the iridium/carbon nanosheet composite material is 5%.
Example 7
(1) Uniformly mixing 45g of urea, 3.0g of polyvinylpyrrolidone and 1.0g of palladium acetylacetonate, heating to 220 ℃, stirring for 6 hours until the mixture is completely solid, and naturally cooling to room temperature to obtain a precursor; (2) and putting the obtained precursor into a tube furnace, controlling the heating rate to be 1 ℃/min under the protection of argon, heating to 800 ℃, preserving the temperature for 2h, and naturally cooling to room temperature to obtain the palladium/carbon nanosheet composite material, wherein the mass fraction of palladium in the obtained palladium/carbon nanosheet composite material is 5%.
Example 8
(1) Uniformly mixing 40g of urea, 4g of polyvinylpyrrolidone and 0.4g of platinum dichloride, heating to 240 ℃, stirring for 6 hours until the mixture is completely solid, and naturally cooling to room temperature to obtain a precursor; (2) and (3) putting the obtained precursor into a tube furnace, controlling the heating rate to be 5 ℃/min under the protection of nitrogen, heating to 800 ℃, preserving the heat for 4h, and naturally cooling to room temperature to obtain the platinum/carbon nanosheet composite material, wherein the mass fraction of platinum in the obtained platinum/carbon nanosheet composite material is 10%.
Example 9
(1) Uniformly mixing 40g of urea, 3.0g of polyvinylpyrrolidone and 1.0g of chloroplatinic acid hexahydrate, heating to 210 ℃, stirring for 4 hours until the mixture is completely solid, and naturally cooling to room temperature to obtain a precursor; (2) and (3) putting the precursor into a tube furnace, controlling the heating rate to be 3 ℃/min under the protection of argon, heating to 1000 ℃, preserving the temperature for 2h, and naturally cooling to room temperature to obtain the platinum/carbon nanosheet composite material, wherein the mass fraction of platinum in the platinum/carbon nanosheet composite material is 20%.
While the present invention has been described in further detail with reference to specific embodiments thereof, it should not be construed that the present invention is limited thereto; for those skilled in the art to which the present invention pertains and related technologies, the noble metal/carbon nanosheet composite material is prepared by adjusting the ratio to change the noble metal loading amount, changing the noble metal salt type, and the like, but the technical principle is the same as that of the present invention, and the extension, operation method and data replacement should fall within the protection scope of the present invention.
Claims (8)
1. A preparation method of a noble metal/carbon nanosheet composite material is characterized by comprising the following steps:
(1) uniformly mixing noble metal salt, polyvinylpyrrolidone and urea according to a certain proportion, heating and polymerizing at 160-240 ℃ until solid is completely formed, and naturally cooling to room temperature to obtain a precursor;
(2) heating the precursor obtained in the step (1) to 800-1000 ℃ for pyrolysis under the conditions of program temperature control and protection of non-oxidizing gas, and then naturally cooling to room temperature to obtain the noble metal/carbon nanosheet composite material;
the noble metal salt in the step (1) is platinum salt, palladium salt, iridium salt, ruthenium salt and rhodium salt.
2. A method for preparing a noble metal/carbon nanosheet composite according to claim 1, wherein the noble metal salt used in step (1) is one or more of a noble metal acid salt, a noble metal chloride, a noble metal nitrate, and a noble metal acetylacetonate.
3. The method for preparing a precious metal/carbon nanosheet composite according to claim 1, wherein the precious metal salt used in step (1) is one or more of chloroplatinic acid, platinum tetrachloride, platinum dichloride, platinum acetylacetonate and platinum nitrate.
4. The method for preparing a noble metal/carbon nanosheet composite according to claim 1, wherein the mass ratio of polyvinylpyrrolidone to urea in step (1) is from 1:4 to 1:30, and the molar amount of monomer in polyvinylpyrrolidone is 4 times or more the noble metal salt.
5. The method for preparing a noble metal/carbon nanosheet composite according to claim 1, wherein the heating time in step (1) is from 2 to 6 hours, and the programmed temperature rise rate in step (2) is from 1 to 10 ℃/min; the pyrolysis time is 1-4 h.
6. The method for preparing a noble metal/carbon nanosheet composite according to claim 1, wherein the non-oxidizing gas used in step (2) is one or a mixture of hydrogen, nitrogen, argon, helium.
7. The method for preparing the noble metal/carbon nanosheet composite material and the method for preparing the same as defined in claim 1, wherein the heating temperature in step (1) is 200-.
8. The noble metal/carbon nanosheet composite prepared by the method of any one of claims 1 to 7.
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