CN114951646B - One-step ultrafast preparation method of graphene material loaded by metal nanoparticles - Google Patents
One-step ultrafast preparation method of graphene material loaded by metal nanoparticles Download PDFInfo
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- CN114951646B CN114951646B CN202210573349.9A CN202210573349A CN114951646B CN 114951646 B CN114951646 B CN 114951646B CN 202210573349 A CN202210573349 A CN 202210573349A CN 114951646 B CN114951646 B CN 114951646B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 261
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 239
- 239000000463 material Substances 0.000 title claims abstract description 63
- 239000002082 metal nanoparticle Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 48
- 229910052751 metal Inorganic materials 0.000 claims abstract description 38
- 239000002184 metal Substances 0.000 claims abstract description 38
- 238000010791 quenching Methods 0.000 claims abstract description 35
- 230000000171 quenching effect Effects 0.000 claims abstract description 35
- 239000000758 substrate Substances 0.000 claims abstract description 29
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 150000003839 salts Chemical class 0.000 claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 23
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 5
- 239000000956 alloy Substances 0.000 claims abstract description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 220
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 111
- 239000011159 matrix material Substances 0.000 claims description 55
- 239000010931 gold Substances 0.000 claims description 53
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 51
- 229910052737 gold Inorganic materials 0.000 claims description 51
- 229910052697 platinum Inorganic materials 0.000 claims description 38
- 239000002253 acid Substances 0.000 claims description 28
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 229910052763 palladium Inorganic materials 0.000 claims description 13
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 12
- 239000004917 carbon fiber Substances 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- -1 tungsten nitride Chemical class 0.000 claims description 5
- 230000005587 bubbling Effects 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 238000005530 etching Methods 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 150000004767 nitrides Chemical class 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 claims description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- 229910000570 Cupronickel Inorganic materials 0.000 claims description 2
- 229910039444 MoC Inorganic materials 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 2
- 229920000297 Rayon Polymers 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- GPBUGPUPKAGMDK-UHFFFAOYSA-N azanylidynemolybdenum Chemical compound [Mo]#N GPBUGPUPKAGMDK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002134 carbon nanofiber Substances 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims description 2
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 2
- 239000006260 foam Substances 0.000 claims description 2
- 239000011888 foil Substances 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- 239000001119 stannous chloride Substances 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims description 2
- 238000001069 Raman spectroscopy Methods 0.000 abstract description 18
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- 239000000243 solution Substances 0.000 description 54
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 42
- 235000019441 ethanol Nutrition 0.000 description 33
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 28
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 28
- 239000011521 glass Substances 0.000 description 28
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 27
- 229910004298 SiO 2 Inorganic materials 0.000 description 24
- 239000010410 layer Substances 0.000 description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 22
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
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- 238000001228 spectrum Methods 0.000 description 3
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- 125000004429 atom Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- 238000011066 ex-situ storage Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
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- 229920000642 polymer Polymers 0.000 description 2
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- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
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- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BKFAZDGHFACXKY-UHFFFAOYSA-N cobalt(II) bis(acetylacetonate) Chemical compound [Co+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O BKFAZDGHFACXKY-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/145—Chemical treatment, e.g. passivation or decarburisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention relates to the field of preparation of metal nano particles and graphene materials, in particular to a one-step ultrafast preparation method of a graphene material loaded by metal nano particles, which is suitable for rapid and efficient preparation of the graphene material loaded by metal nano particles. According to the method, a high-temperature substrate is rapidly cooled (quenched) in a liquid carbon source of metal salt, the metal salt is heated and decomposed into metal nano particles in the quenching process, and graphene grows on the surface of the substrate through the heated and decomposed liquid carbon source, so that the graphene material loaded by the metal nano particles is rapidly prepared. The preparation method disclosed by the invention has the advantages of simple preparation process, high efficiency, low cost and good controllability, can be used for rapidly preparing the graphene materials loaded by various metal nano particles, and lays a foundation for the application of the materials in the fields of photoelectrocatalysis, industrial catalysis, raman enhancement, high-entropy alloy, gas sensing, electromagnetic shielding and the like.
Description
Technical field:
the invention relates to the field of preparation of metal nano particles and graphene materials, in particular to a one-step ultrafast preparation method of a graphene material loaded by metal nano particles, which is suitable for rapid and efficient preparation of the graphene material loaded by metal nano particles.
The background technology is as follows:
with the advent of research on nanomaterials, metal nanomaterials represented by metal nanoparticles have been widely studied and paid attention to because they have unique properties different from bulk metals. The graphene is also used as a typical representative of a two-dimensional material, and has important application prospects in the aspects of electronic devices, optoelectronic devices, sensing devices, electrochemical energy storage, composite materials, thermal management and the like due to the unique two-dimensional structure, the ultrahigh specific surface area, excellent physical and chemical properties such as electricity, heat, mechanics, optics and chemical stability. At present, aiming at a composite of the metal nanoparticle and the graphene, the graphene material loaded by the metal nanoparticle has the excellent characteristics of the metal nanoparticle and the graphene, and has shown great advantages in the application fields of industrial catalysis, surface enhanced Raman, gas sensing and the like.
Efficient preparation of metal nanoparticle-loaded graphene materials is critical in determining their application. The main preparation methods of the graphene materials loaded by the metal nano particles at present can be divided into an in-situ preparation method and an ex-situ preparation method. The "in situ preparation" method refers to the direct deposition of noble metal particles onto the graphene surface, and can be specifically subdivided into: chemical reduction by using a reducing agent, high-temperature assisted thermal reduction, photo-assisted photochemical reduction and physical vapor deposition. The method is simple and convenient, but the morphology, the size and the distribution of the particles are difficult to control. The "ex-situ preparation" method refers to the preparation of graphene and noble metal separately, and then anchoring the metal particles on the surface of graphene by covalent bonding or non-covalent bonding. Although this method is more complex than the "in situ preparation method", it is more advantageous in controlling the morphology, density, and size of the metal nanoparticles. Although the preparation of the graphene material loaded by the metal nanoparticles can be realized by the two methods, the graphene material needs to be prepared firstly as a substrate for particle growth, and the one-step preparation of graphene and the metal nanoparticles cannot be realized. In addition, considering the two-step synthesis time of graphene and metal particles, the cycle of the two methods for preparing the metal nanoparticle-loaded graphene material is more than several hours, which is definitely unfavorable for the efficient preparation of the metal nanoparticle-loaded graphene material.
The invention comprises the following steps:
the invention aims to provide a one-step ultrafast preparation method of a graphene material loaded by metal nano particles, which solves the problems that the existing preparation method is complex in process, long in production period, high in cost, incapable of realizing one-step preparation and the like, and lays a foundation for researching the physicochemical properties of the graphene material loaded by the metal nano particles and realizing the large-scale application of the graphene material.
The technical scheme of the invention is as follows:
a one-step ultrafast preparation method of a graphene material loaded by metal nano particles adopts a high-temperature matrix, a liquid carbon source solution of metal salt is used as quenching liquid in inert protective atmosphere, the high-temperature matrix is quenched in the liquid carbon source of the metal salt and is rapidly cooled, the metal salt is heated and decomposed to form the metal nano particles in the quenching process, and the liquid carbon source is heated and decomposed to grow graphene on the surface of the matrix, so that the graphene material loaded by the metal nano particles is rapidly prepared in one step.
According to the one-step ultrafast preparation method of the graphene material loaded by the metal nano particles, the matrix is one or more than two of metal, carbon fiber, carbide, nitride and oxide, and the shape is any shape of foil, porous foam or powder.
The metal nano particle loaded graphene material is prepared by one or more than two of copper, platinum, nickel, cobalt, gold, ruthenium, palladium, molybdenum, tungsten, aluminum, copper-nickel alloy and molybdenum-nickel alloy; the carbon fiber is one or two of polyacrylonitrile-based carbon fiber, pipe pitch-based carbon fiber, viscose-based carbon fiber, phenolic-based carbon fiber and vapor grown carbon fiber; the carbide is one or more of silicon carbide, tungsten carbide and molybdenum carbide; the nitride is one or more than two of silicon nitride, tungsten nitride and molybdenum nitride; the oxide is one or more of silicon oxide, aluminum oxide, magnesium oxide, copper oxide and nickel oxide.
According to the one-step ultrafast preparation method of the graphene material loaded by the metal nano particles, a liquid carbon source is a carbon-containing compound which is dissolved in a solvent or is in a molten state at room temperature and is solid, the carbon-containing compound comprises but is not limited to paraffin or a high molecular polymer, and the high molecular polymer is one or more than two of polymethyl methacrylate, polycarbonate, polystyrene, polyethylene and polypropylene; the metal salt used comprises one or more than two of ferric chloride, nickel chloride, cobalt chloride, copper chloride, stannous chloride, chloroplatinic acid, chloroauric acid, palladium chloride, ferric nitrate, nickel nitrate, cobalt nitrate, copper nitrate, silver nitrate, palladium nitrate, ferrocene, nickel dicyclopentadienyl, cobaltous acetylacetonate, cobalt acetylacetonate and nickel acetylacetonate; solvents include, but are not limited to, one or more of methanol, ethanol, isopropanol, acetone, benzene, toluene, cyclohexane, acetaldehyde, diethyl ether, acetic acid, ethyl acetate, carbon disulfide.
According to the one-step ultrafast preparation method of the graphene material loaded by the metal nano particles, the initial temperature of the high-temperature matrix is between the temperature above the decomposition temperature of the metal salt and below the melting point of the matrix, and the temperature of the quenching liquid is between the temperature above the solidification temperature and below the vaporization temperature of the quenching liquid.
According to the one-step ultrafast preparation method of the graphene material loaded by the metal nano particles, in the preparation process, the inert protective atmosphere is nitrogen or inert gas or mixed gas of the nitrogen and the inert gas.
According to the one-step ultrafast preparation method of the graphene material loaded by the metal nano particles, the thickness and the crystallinity of graphene are controlled by changing the components, thickness and initial temperature of a matrix and the types and the temperatures of liquid carbon sources.
According to the one-step ultrafast preparation method of the graphene material loaded by the metal nanoparticles, the components, the sizes and the number of the metal nanoparticles are controlled by changing the components, the thickness, the initial temperature and the types and the concentrations of metal salts of a matrix.
The one-step ultrafast preparation method of the graphene material loaded by the metal nano particles adopts a quenching method to grow the graphene material loaded by the metal nano particles on the surface of the matrix, and adopts an etching method or an electrochemical gas bubbling method to separate the graphene material from the surface of the matrix or use the graphene material together with the matrix.
The design principle of the invention is as follows:
after the growth substrate is heated to a certain temperature, the growth substrate is placed in the liquid carbon source solution of the metal salt, the liquid carbon source can be rapidly decomposed to generate a large number of carbon atoms after contacting the high-temperature substrate, the metal salt can be decomposed into metal atoms after being heated, and then the graphene loaded by the metal nano particles is formed on the surface of the substrate, and meanwhile, the temperature of the graphene is rapidly reduced, namely quenching, along with the heat transferred to the liquid carbon source solution of the metal salt by the substrate. When the substrate temperature is reduced to a certain extent, it will not be sufficient to continue to provide energy to decompose the liquid carbon source and metal salt, the graphene and metal nanoparticles will stop growing. The growth of graphene and metal nano particles occurs in the substrate cooling process, and the substrate cooling rate in the liquid carbon source is extremely high, so that the growth rate is extremely high.
The invention has the advantages and beneficial effects that:
1. the invention provides a method for preparing graphene loaded by metal nano particles in one step in an ultrafast way, and the growth of the graphene and the metal nano particles can be completed within a few seconds, so that the method has the advantages of simple process, high efficiency, low requirements on equipment, convenience in operation, low cost, easiness in performance regulation and batch preparation.
2. The number of layers of the graphene obtained by the method is 1-10, the grain size is 1 nm-100 mu m, and the shape and the size depend on the shape and the size of a used matrix.
3. The size of the metal nano particles obtained by the method is 1 nm-200 nm, and the components, the morphology and the size depend on the type and the concentration of the metal salt solution, the shape and the size of a matrix, the temperature used for quenching and the like.
4. The invention provides a precondition for the large-scale application of the graphene material loaded by the metal nano particles in the fields of photoelectrocatalysis, industrial catalysis, raman enhancement, high-entropy alloy, gas sensing and the like.
Description of the drawings:
fig. 1: schematic of one-step ultrafast preparation of metal nanoparticle-loaded graphene materials.
Fig. 2: the gold nanoparticle-loaded graphene film is prepared by quenching a platinum foil with the thickness of 1mm and the initial temperature of 900 ℃ in a chloroauric acid ethanol solution with the concentration of 0.1 mol/L. a is the Cooling curve (in the figure, cooling time on the abscissa represents Cooling time s and Temperature on the ordinate represents Temperature ℃) of the platinum matrix (Hot Pt Foil) during the preparation, b is the transfer to SiO 2 Scanning Electron Microscope (SEM) photograph of gold nanoparticle-loaded graphene on Si substrate, c-chart being transferred to SiO 2 Gold nanoparticles on Si substratesHigh-power scanning electron microscope photograph of Particle-supported graphene, d graph is size statistics of gold nanoparticles (in the graph, the abscissa Particle size represents Particle size nm, and the ordinate Percentage represents Percentage of different Particle sizes), e is transfer to SiO 2 Atomic force microscope photograph of graphene loaded with gold nanoparticles (Au NPs) on Si substrate, f is transfer to SiO 2 X-ray diffraction pattern of graphene loaded with gold nanoparticles on Si substrate (in the figure, the abscissa 2θ represents diffraction angle, and the ordinate Intensity represents relative Intensity a.u.), and the h-pattern is a spherical aberration correction transmission electron microscope photograph.
Fig. 3: the gold nanoparticle-loaded graphene film is prepared by quenching a platinum foil with the thickness of 1mm and the initial temperature of 900 ℃ in a chloroauric acid ethanol solution with the concentration of 0.15 mol/L. a is the transfer to SiO 2 Low-power scanning electron microscope photograph of gold nanoparticle-loaded graphene on Si substrate, and b-graph is transferred to SiO 2 High-power scanning electron microscope photograph of gold nanoparticle-loaded graphene on Si substrate, c-plot is transferred to SiO 2 High-power scanning electron microscope pictures of graphene loaded by gold nanoparticles on Si matrix, and d graph is size statistics of gold nanoparticles (in the graph, the abscissa Particle size represents Particle size nm, and the ordinate Percentage represents Percentage of different Particle sizes).
Fig. 4: the gold nanoparticle-loaded graphene film is prepared by quenching a platinum foil with a thickness of 1mm and an initial temperature of 900 ℃ in 0.1mol/L ethanol chloroplatinic acid solution. a is the transfer to SiO 2 Low-magnification scanning electron microscope photograph of graphene loaded by platinum nano particles on Si matrix, and b diagram is transferred to SiO 2 High-power Scanning Electron Microscope (SEM) photograph of graphene loaded by platinum nano-particles on Si substrate, c is X-ray photoelectron spectrum of platinum element (in the figure, binding energy represents Binding energy eV, and ordinate represents relative Intensity a.u.), d is high-power transmission electron microscope photograph, e is high-power transmission electron microscope photograph, and f is X-ray energy spectrum (EDS) composition distribution diagram of platinum nano-particles.
Fig. 5: and (3) quenching the platinum foil with the thickness of 150 mu m and the initial temperature of 1200 ℃ in 0.1mol/L palladium chloride ethanol solution to prepare the palladium nanoparticle-loaded graphene film. Panel a shows a low power transmission electron micrograph, panel b shows a high power transmission electron micrograph, panel c shows a statistics of the size of the palladium nanoparticles (in the figures, the abscissa Particle size represents the Particle size nm, the ordinate Percentage represents the Percentage of the different Particle sizes, panel d shows a high angle annular dark field (HADDF) photograph, panel e shows an EDS component profile of the palladium nanoparticles, panel f shows a characteristic X-ray Energy spectrum of the sample (in the figures, the abscissa Energy represents the Energy eV, and the ordinate Intensity represents the Intensity Counts).
Fig. 6: and (3) quenching the platinum foil with the thickness of 150 mu m and the initial temperature of 1200 ℃ in 0.1mol/L ferric chloride ethanol solution to prepare the graphene film loaded by the iron nano particles. a is the transfer to SiO 2 Optical microscopy pictures of graphene films (Gr film) loaded with iron nanoparticles (Fe NPs) on Si matrix, b graph is a low power transmission electron microscopy picture, c graph is a size statistic of iron nanoparticles (in the figure, the abscissa Particle size represents the Particle size nm, the ordinate Percentage represents the Percentage of different Particle sizes, d graph is a high power transmission electron microscopy picture, e graph is an iron element EDS composition profile of nanoparticles, and f graph is an oxygen element EDS composition profile of nanoparticles).
Fig. 7: the nickel nanoparticle-loaded graphene film is prepared by quenching a platinum foil with a thickness of 150 mu m and an initial temperature of 1200 ℃ in a nickel chloride ethanol solution with a concentration of 0.1 mol/L. Graph a is a low power transmission electron micrograph, graph b is a high power transmission electron micrograph, graph c is a size statistic of the nickel nanoparticles (in the graph, the abscissa Particle size represents the Particle size nm, the ordinate Percentage represents the different Particle sizes, graph d is a HADDF photograph, graph e is an EDS composition profile of the nickel nanoparticles, graph f is a characteristic X-ray Energy spectrum of the sample (in the graph, the abscissa Energy represents the Energy eV, and the ordinate concentration represents the Intensity Counts).
Fig. 8: a copper nanoparticle-loaded graphene film prepared by quenching a platinum foil with a thickness of 150 μm and an initial temperature of 1200 ℃ in a copper chloride ethanol solution with a concentration of 0.1 mol/L. Graph a is a low-power transmission electron microscope photograph, graph b is a high-power transmission electron microscope photograph, graph c is a dimension statistic of copper nano-particles (in the graph, the abscissa of Particle size represents the Particle size nm, the ordinate of Percentage represents the different Particle sizes, graph d is a HADDF photograph, graph e is a copper element EDS component distribution diagram of the nano-particles, and graph f is an oxygen element EDS component distribution diagram of the nano-particles).
The specific embodiment is as follows:
in the specific implementation process, the substrate is heated to a preset temperature under inert protective atmosphere, the adopted heating method comprises high-frequency electromagnetic induction heating, resistance wire heating, electric heating furnace heating and the like, then the high-temperature substrate is placed into a liquid carbon source of metal salt to be rapidly cooled (quenched), the graphene material loaded by metal nano particles is grown on the surface of the substrate by utilizing carbon atoms generated by decomposition of the liquid carbon source and the metal salt in the quenching process and the metal atoms, and the graphene material is separated from the surface of the substrate by an etching method or a gas bubbling method or is directly used together with the substrate.
The invention is further described below by way of examples and figures.
Example 1
Firstly, the embodiment adopts a common vertical furnace (the bottom of a quartz tube of the vertical furnace is connected with a glass container filled with an ethanol solution of chloroauric acid by a flange) to realize the one-step ultrafast growth of graphene loaded by gold nanoparticles. An argon gas inlet is arranged at the upper end of the vertical furnace, a platinum foil (20 mm multiplied by 10mm multiplied by 150 mu m, the purity is 99.95 wt%) is placed down to the center of a hearth by a push-pull rod (the temperature of the center of the hearth is always kept at 900 ℃), after the platinum foil is raised to 900 ℃ in the argon atmosphere, the platinum foil falls into a glass container filled with 0.1mol/L chloroauric acid ethanol solution (absolute ethanol, analytically pure) at 0 ℃ to be rapidly cooled (quenched), and the growth of gold nanoparticle-loaded graphene is completed in the quenching process. And taking out the platinum foil after the temperature of the platinum foil is reduced to room temperature, and drying the platinum foil in a nitrogen atmosphere.
Then, the surface of the platinum foil with graphene was covered with a solution of polymethyl methacrylate (PMMA) in ethyl lactate (polymethyl methacrylate 4 wt%), spin-coated uniformly at 2000 rpm for 60s using a spin coater, and then baked at 180 ℃ for 20 minutes and then cooled naturally. The platinum foil covered with PMMA/graphene film is used as the cathode of the electrolytic cell (NaOH aqueous solution with molar concentration of 1M is used as electrolyte, and the anode is a platinum electrode) The separation of the PMMA/graphene film and the platinum foil is realized by utilizing hydrogen bubbles generated on the surface of the platinum foil under the current of 0.2A, and the PMMA/graphene film is transferred to SiO 2 And (3) dissolving and removing PMMA on the Si matrix by using acetone at the temperature of 70 ℃ to finish the transfer of the graphene loaded by the gold nanoparticles. Wherein SiO is 2 The Si matrix is SiO deposited on the surface of the monocrystalline Si sheet with nano-scale thickness 2 Film, siO 2 The thickness of the film was 290nm.
The quality, uniformity, layer number and appearance and size of the gold nanoparticles of the graphene film are characterized by using an optical microscope, a Raman spectrometer and a transmission electron microscope, and the obtained graphene film is uniform single-layer graphene, the thickness is 0.9nm, the grain size is 3.6nm, the appearance of the gold nanoparticles loaded on the surface is spherical, and the average size is 20nm.
Example 2
Firstly, the embodiment adopts a common vertical furnace (the bottom of a quartz tube of the vertical furnace is connected with a glass container filled with an ethanol solution of chloroauric acid by a flange) to realize the one-step ultrafast growth of graphene loaded by gold nanoparticles. An argon gas inlet is arranged at the upper end of the vertical furnace, a platinum foil (20 mm multiplied by 10mm multiplied by 150 mu m, purity is 99.95 wt%) is placed down to the center of a hearth by a push-pull rod (the temperature of the center of the hearth is always kept at 1200 ℃), after the platinum foil is raised to 1200 ℃ in an argon atmosphere, the platinum foil falls into a glass container filled with 0.1mol/L chloroauric acid ethanol solution (absolute ethanol, analytically pure) at 0 ℃ to be rapidly cooled (quenched), and the growth of gold nanoparticle-loaded graphene is completed in the quenching process. And taking out the platinum foil after the temperature of the platinum foil is reduced to room temperature, and drying the platinum foil in a nitrogen atmosphere.
Then, the surface of the platinum foil with graphene was covered with a solution of polymethyl methacrylate (PMMA) in ethyl lactate (polymethyl methacrylate 4 wt%), spin-coated uniformly at 2000 rpm for 60s using a spin coater, and then baked at 180 ℃ for 20 minutes and then cooled naturally. A platinum foil covered with a PMMA/graphene film is used as a cathode of an electrolytic cell (NaOH aqueous solution with molar concentration of 1M is used as an electrolyte, and an anode is a platinum electrode), and hydrogen bubbles generated on the surface of the platinum foil are used for realizing the PMMA/graphene film and platinum under the current of 0.2AFoil separation, transfer of PMMA/graphene film to SiO 2 And (3) dissolving and removing PMMA on the Si matrix by using acetone at the temperature of 70 ℃ to finish the transfer of the graphene loaded by the gold nanoparticles. Wherein SiO is 2 The Si matrix is SiO deposited on the surface of the monocrystalline Si sheet with nano-scale thickness 2 Film, siO 2 The thickness of the film was 290nm.
The quality, uniformity, layer number and appearance and size of the gold nanoparticles of the graphene film are characterized by using an optical microscope, a Raman spectrometer and a transmission electron microscope, and the obtained graphene film is a few layers of graphene, the thickness is 2nm, the grain size is 30nm, the appearance of the gold nanoparticles loaded on the surface is spherical, and the average size is 30nm.
Example 3
Firstly, the embodiment adopts a common vertical furnace (the bottom of a quartz tube of the vertical furnace is connected with a glass container filled with an ethanol solution of chloroauric acid by a flange) to realize the one-step ultrafast growth of graphene loaded by gold nanoparticles. An argon gas inlet is arranged at the upper end of the vertical furnace, a platinum foil (20 mm multiplied by 10mm multiplied by 1mm, purity is 99.95 wt%) is placed down to the center of a hearth by a push-pull rod (the temperature of the center of the hearth is always kept at 900 ℃), after the platinum foil is raised to 900 ℃ in an argon atmosphere, the platinum foil falls into a glass container filled with 0.1mol/L chloroauric acid ethanol solution (absolute ethanol, analytically pure) at 0 ℃ to be rapidly cooled (quenched), and the growth of gold nanoparticle-loaded graphene is completed in the quenching process. And taking out the platinum foil after the temperature of the platinum foil is reduced to room temperature, and drying the platinum foil in a nitrogen atmosphere.
Then, the surface of the platinum foil with graphene was covered with a solution of polymethyl methacrylate (PMMA) in ethyl lactate (polymethyl methacrylate 4 wt%), spin-coated uniformly at 2000 rpm for 60s using a spin coater, and then baked at 180 ℃ for 20 minutes and then cooled naturally. Taking a platinum foil covered with a PMMA/graphene film as an electrolytic cell cathode (NaOH aqueous solution with molar concentration of 1M is taken as an electrolyte, and an anode is taken as a platinum electrode), separating the PMMA/graphene film from the platinum foil by utilizing hydrogen bubbles generated on the surface of the platinum foil under the current of 0.2A, and transferring the PMMA/graphene film to SiO 2 On a Si substrate, then with acetone at a temperature of 70 DEG CAnd (3) dissolving and removing PMMA to finish the transfer of the graphene loaded by the gold nanoparticles. Wherein SiO is 2 The Si matrix is SiO deposited on the surface of the monocrystalline Si sheet with nano-scale thickness 2 Film, siO 2 The thickness of the film was 290nm.
The quality, uniformity, layer number and appearance and size of the gold nanoparticles of the graphene film are characterized by using an optical microscope, a Raman spectrometer and a transmission electron microscope, and the obtained graphene film is uniform single-layer graphene, the thickness is 0.9nm, the grain size is 3.6nm, the appearance of the gold nanoparticles loaded on the surface is spherical, triangular and hexagonal, and the average size is 143nm.
Example 4
Firstly, the embodiment adopts a common vertical furnace (the bottom of a quartz tube of the vertical furnace is connected with a glass container filled with an ethanol solution of chloroauric acid by a flange) to realize the one-step ultrafast growth of graphene loaded by gold nanoparticles. An argon gas inlet is arranged at the upper end of the vertical furnace, a platinum foil (20 mm multiplied by 10mm multiplied by 1mm, purity is 99.95 wt%) is placed down to the center of a hearth by a push-pull rod (the temperature of the center of the hearth is always kept at 900 ℃), after the platinum foil is raised to 900 ℃ in the argon atmosphere, the platinum foil falls into a glass container filled with 0.15mol/L chloroauric acid ethanol solution (absolute ethanol, analytically pure) at 0 ℃ to be rapidly cooled (quenched), and the growth of gold nanoparticle-loaded graphene is completed in the quenching process. And taking out the platinum foil after the temperature of the platinum foil is reduced to room temperature, and drying the platinum foil in a nitrogen atmosphere.
Then, the surface of the platinum foil with graphene was covered with a solution of polymethyl methacrylate (PMMA) in ethyl lactate (polymethyl methacrylate 4 wt%), spin-coated uniformly at 2000 rpm for 60s using a spin coater, and then baked at 180 ℃ for 20 minutes and then cooled naturally. Taking a platinum foil covered with a PMMA/graphene film as an electrolytic cell cathode (NaOH aqueous solution with molar concentration of 1M is taken as an electrolyte, and an anode is taken as a platinum electrode), separating the PMMA/graphene film from the platinum foil by utilizing hydrogen bubbles generated on the surface of the platinum foil under the current of 0.2A, and transferring the PMMA/graphene film to SiO 2 On a Si matrix, then, acetone is used for dissolving and removing PMMA at the temperature of 70 ℃ to finish the transfer of graphene loaded by gold nanoparticles. Wherein SiO is 2 The Si matrix is SiO deposited on the surface of the monocrystalline Si sheet with nano-scale thickness 2 Film, siO 2 The thickness of the film was 290nm.
The quality, uniformity, layer number and appearance and size of the gold nanoparticles of the graphene film are characterized by using an optical microscope, a Raman spectrometer and a transmission electron microscope, and the obtained graphene film is uniform single-layer graphene, the thickness is 0.9nm, the grain size is 3.6nm, the appearance of the gold nanoparticles loaded on the surface is spherical, triangular and hexagonal, and the average size is 101nm.
Example 5
Firstly, the embodiment adopts a common vertical furnace (the bottom of a quartz tube of the vertical furnace is connected with a glass container filled with an ethanol solution of chloroauric acid by a flange) to realize the one-step ultrafast growth of graphene loaded by gold nanoparticles. An argon gas inlet is arranged at the upper end of the vertical furnace, a platinum foil (20 mm multiplied by 10mm multiplied by 1mm, purity is 99.95 wt%) is placed down to the center of a hearth by a push-pull rod (the temperature of the center of the hearth is always kept at 1200 ℃), after the platinum foil is raised to 1200 ℃ in an argon atmosphere, the platinum foil falls into a glass container filled with 0.1mol/L chloroauric acid ethanol solution (absolute ethanol, analytically pure) at 0 ℃ to be rapidly cooled (quenched), and the growth of gold nanoparticle-loaded graphene is completed in the quenching process. And taking out the platinum foil after the temperature of the platinum foil is reduced to room temperature, and drying the platinum foil in a nitrogen atmosphere.
Then, the surface of the platinum foil with graphene was covered with a solution of polymethyl methacrylate (PMMA) in ethyl lactate (polymethyl methacrylate 4 wt%), spin-coated uniformly at 2000 rpm for 60s using a spin coater, and then baked at 180 ℃ for 20 minutes and then cooled naturally. Taking a platinum foil covered with a PMMA/graphene film as an electrolytic cell cathode (NaOH aqueous solution with molar concentration of 1M is taken as an electrolyte, and an anode is taken as a platinum electrode), separating the PMMA/graphene film from the platinum foil by utilizing hydrogen bubbles generated on the surface of the platinum foil under the current of 0.2A, and transferring the PMMA/graphene film to SiO 2 And (3) dissolving and removing PMMA on the Si matrix by using acetone at the temperature of 70 ℃ to finish the transfer of the graphene loaded by the gold nanoparticles. Wherein SiO is 2 The Si matrix is formed by depositing nano-particles on the surface of a single crystal Si waferSiO of meter-scale thickness 2 Film, siO 2 The thickness of the film was 290nm.
The quality, uniformity, layer number and appearance and size of the gold nanoparticles of the graphene film are characterized by using an optical microscope, a Raman spectrometer and a transmission electron microscope, and the obtained graphene film is a few layers of graphene, the thickness is 2.3nm, the grain size is 30nm, and the appearance of the gold nanoparticles loaded on the surface is spherical, triangular and hexagonal.
Example 6
Firstly, the embodiment adopts a common vertical furnace (the bottom of a quartz tube of the vertical furnace is connected with a glass container filled with an ethanol solution of chloroauric acid by a flange) to realize the one-step ultrafast growth of graphene loaded by gold nanoparticles. An argon gas inlet is arranged at the upper end of the vertical furnace, a platinum foil (20 mm multiplied by 10mm multiplied by 1mm, purity is 99.95 wt%) is placed down to the center of a hearth by a push-pull rod (the temperature of the center of the hearth is always kept at 1200 ℃), after the platinum foil is raised to 1200 ℃ in an argon atmosphere, the platinum foil falls into a glass container filled with 0.15mol/L chloroauric acid ethanol solution (absolute ethanol, analytically pure) at 0 ℃ to be rapidly cooled (quenched), and the growth of gold nanoparticle-loaded graphene is completed in the quenching process. And taking out the platinum foil after the temperature of the platinum foil is reduced to room temperature, and drying the platinum foil in a nitrogen atmosphere.
Then, the surface of the platinum foil with graphene was covered with a solution of polymethyl methacrylate (PMMA) in ethyl lactate (polymethyl methacrylate 4 wt%), spin-coated uniformly at 2000 rpm for 60s using a spin coater, and then baked at 180 ℃ for 20 minutes and then cooled naturally. Taking a platinum foil covered with a PMMA/graphene film as an electrolytic cell cathode (NaOH aqueous solution with molar concentration of 1M is taken as an electrolyte, and an anode is taken as a platinum electrode), separating the PMMA/graphene film from the platinum foil by utilizing hydrogen bubbles generated on the surface of the platinum foil under the current of 0.2A, and transferring the PMMA/graphene film to SiO 2 And (3) dissolving and removing PMMA on the Si matrix by using acetone at the temperature of 70 ℃ to finish the transfer of the graphene loaded by the gold nanoparticles. Wherein SiO is 2 The Si matrix is SiO deposited on the surface of the monocrystalline Si sheet with nano-scale thickness 2 Film, siO 2 The thickness of the film was 290nm.
The quality, uniformity, layer number and appearance and size of the gold nanoparticles of the graphene film are characterized by using an optical microscope, a Raman spectrometer and a transmission electron microscope, and the obtained graphene film is a few layers of graphene, the thickness is 3nm, the grain size is 35nm, and the appearance of the gold nanoparticles loaded on the surface is spherical, triangular and hexagonal.
Example 7
Firstly, the embodiment adopts a common vertical furnace (the bottom of a quartz tube of the vertical furnace is connected with a glass container filled with ethanol solution of chloroplatinic acid by a flange) to realize the one-step ultrafast growth of the graphene loaded by platinum nano particles. Firstly, an ordinary vertical furnace (the bottom of a quartz tube of the vertical furnace and an ethanol solution end filled with chloroplatinic acid are provided with argon gas inlets), platinum foil (20 mm multiplied by 10mm multiplied by 150 mu m and purity of 99.95 wt%) is placed down to the center of a hearth by a push-pull rod (the center temperature of the hearth is always kept at 900 ℃), after the platinum foil is raised to 900 ℃ in an argon atmosphere, the platinum foil falls into a glass container filled with 0.1mol/L ethanol solution (absolute ethanol, analytical purity) of chloroplatinic acid at 0 ℃ to be rapidly cooled (quenched), and the growth of graphene loaded with gold nanoparticles is completed in the quenching process.
Then, the surface of the platinum foil with graphene was covered with a solution of polymethyl methacrylate (PMMA) in ethyl lactate (polymethyl methacrylate 4 wt%), spin-coated uniformly at 2000 rpm for 60s using a spin coater, and then baked at 180 ℃ for 20 minutes and then cooled naturally. Taking a platinum foil covered with a PMMA/graphene film as an electrolytic cell cathode (NaOH aqueous solution with molar concentration of 1M is taken as an electrolyte, and an anode is taken as a platinum electrode), separating the PMMA/graphene film from the platinum foil by utilizing hydrogen bubbles generated on the surface of the platinum foil under the current of 0.2A, and transferring the PMMA/graphene film to SiO 2 And (3) dissolving and removing PMMA on the Si matrix by using acetone at the temperature of 70 ℃ to finish the transfer of the graphene loaded by the gold nanoparticles. Wherein SiO is 2 The Si matrix is SiO deposited on the surface of the monocrystalline Si sheet with nano-scale thickness 2 Film, siO 2 The thickness of the film was 290nm.
The quality, uniformity, layer number and appearance and size of the gold nanoparticles of the graphene film are characterized by utilizing an optical microscope, a Raman spectrometer and a transmission electron microscope, and the obtained graphene film is uniform single-layer graphene, the thickness is 0.9nm, the grain size is 3.6nm, and the appearance of the platinum nanoparticles loaded on the surface is spherical or agglomerate.
Example 8
Firstly, the embodiment adopts a common vertical furnace (the bottom of a quartz tube of the vertical furnace is connected with a glass container filled with ethanol solution of chloroplatinic acid by a flange) to realize the one-step ultrafast growth of the graphene loaded by platinum nano particles. An argon gas inlet is arranged at the upper end of the vertical furnace, a platinum foil (20 mm multiplied by 10mm multiplied by 150 mu m, purity is 99.95 wt%) is placed down to the center of a hearth by a push-pull rod (the temperature of the center of the hearth is always kept at 1200 ℃), after the platinum foil is raised to 1200 ℃ in an argon atmosphere, the platinum foil falls into a glass container filled with 0.1mol/L chloroplatinic acid ethanol solution (absolute ethyl alcohol, analytically pure) at 0 ℃ to be rapidly cooled (quenched), and the growth of the graphene loaded by platinum nano particles is completed in the quenching process. And taking out the platinum foil after the temperature of the platinum foil is reduced to room temperature, and drying the platinum foil in a nitrogen atmosphere.
Then, the surface of the platinum foil with graphene was covered with a solution of polymethyl methacrylate (PMMA) in ethyl lactate (polymethyl methacrylate 4 wt%), spin-coated uniformly at 2000 rpm for 60s using a spin coater, and then baked at 180 ℃ for 20 minutes and then cooled naturally. Taking a platinum foil covered with a PMMA/graphene film as an electrolytic cell cathode (NaOH aqueous solution with molar concentration of 1M is taken as an electrolyte, and an anode is taken as a platinum electrode), separating the PMMA/graphene film from the platinum foil by utilizing hydrogen bubbles generated on the surface of the platinum foil under the current of 0.2A, and transferring the PMMA/graphene film to SiO 2 And (3) dissolving and removing PMMA on the Si matrix by using acetone at the temperature of 70 ℃ to finish the transfer of the graphene loaded by the gold nanoparticles. Wherein SiO is 2 The Si matrix is SiO deposited on the surface of the monocrystalline Si sheet with nano-scale thickness 2 Film, siO 2 The thickness of the film was 290nm.
The quality, uniformity, layer number and appearance and size of the graphene film are characterized by utilizing an optical microscope, a Raman spectrometer and a transmission electron microscope, and the obtained graphene film is a few-layer graphene, the thickness is 2nm, the grain size is 31nm, and the appearance of the platinum nano particles loaded on the surface is spherical or agglomerate.
Example 9
Firstly, the embodiment adopts a common vertical furnace (the bottom of a quartz tube of the vertical furnace is connected with a glass container filled with ethanol solution of chloroplatinic acid by a flange) to realize the one-step ultrafast growth of the graphene loaded by platinum nano particles. An argon gas inlet is arranged at the upper end of the vertical furnace, a platinum foil (20 mm multiplied by 10mm multiplied by 1mm, purity is 99.95 wt%) is placed down to the center of a hearth by a push-pull rod (the temperature of the center of the hearth is always kept at 900 ℃), after the platinum foil is raised to 900 ℃ in an argon atmosphere, the platinum foil falls into a glass container filled with 0.1mol/L chloroplatinic acid ethanol solution (absolute ethyl alcohol, analytically pure) at 0 ℃ to be rapidly cooled (quenched), and the growth of the graphene loaded by platinum nano particles is completed in the quenching process. And taking out the platinum foil after the temperature of the platinum foil is reduced to room temperature, and drying the platinum foil in a nitrogen atmosphere.
Then, the surface of the platinum foil with graphene was covered with a solution of polymethyl methacrylate (PMMA) in ethyl lactate (polymethyl methacrylate 4 wt%), spin-coated uniformly at 2000 rpm for 60s using a spin coater, and then baked at 180 ℃ for 20 minutes and then cooled naturally. Taking a platinum foil covered with a PMMA/graphene film as an electrolytic cell cathode (NaOH aqueous solution with molar concentration of 1M is taken as an electrolyte, and an anode is taken as a platinum electrode), separating the PMMA/graphene film from the platinum foil by utilizing hydrogen bubbles generated on the surface of the platinum foil under the current of 0.2A, and transferring the PMMA/graphene film to SiO 2 And (3) dissolving and removing PMMA on the Si matrix by using acetone at the temperature of 70 ℃ to finish the transfer of the graphene loaded by the platinum nano particles. Wherein SiO is 2 The Si matrix is SiO deposited on the surface of the monocrystalline Si sheet with nano-scale thickness 2 Film, siO 2 The thickness of the film was 290nm.
The quality, uniformity, layer number and appearance and size of the platinum nano particles of the graphene film are characterized by utilizing an optical microscope, a Raman spectrometer and a transmission electron microscope, and the obtained graphene film is uniform single-layer graphene, the thickness is 0.9nm, the grain size is 3.7nm, and the appearance of the platinum nano particles loaded on the surface is spherical or agglomerate.
Example 10
Firstly, the embodiment adopts a common vertical furnace (the bottom of a quartz tube of the vertical furnace is connected with a glass container filled with ethanol solution of chloroplatinic acid by a flange) to realize the one-step ultrafast growth of the graphene loaded by platinum nano particles. An argon gas inlet is arranged at the upper end of the vertical furnace, a platinum foil (20 mm multiplied by 10mm multiplied by 1mm, purity is 99.95 wt%) is placed down to the center of a hearth by a push-pull rod (the temperature of the center of the hearth is always kept at 1200 ℃), after the platinum foil is raised to 1200 ℃ in an argon atmosphere, the platinum foil falls into a glass container filled with 0.1mol/L chloroplatinic acid ethanol solution (absolute ethyl alcohol, analytically pure) at 0 ℃ to be rapidly cooled (quenched), and the growth of the graphene loaded by platinum nano particles is completed in the quenching process. And taking out the platinum foil after the temperature of the platinum foil is reduced to room temperature, and drying the platinum foil in a nitrogen atmosphere.
Then, the surface of the platinum foil with graphene was covered with a solution of polymethyl methacrylate (PMMA) in ethyl lactate (polymethyl methacrylate 4 wt%), spin-coated uniformly at 2000 rpm for 60s using a spin coater, and then baked at 180 ℃ for 20 minutes and then cooled naturally. Taking a platinum foil covered with a PMMA/graphene film as an electrolytic cell cathode (NaOH aqueous solution with molar concentration of 1M is taken as an electrolyte, and an anode is taken as a platinum electrode), separating the PMMA/graphene film from the platinum foil by utilizing hydrogen bubbles generated on the surface of the platinum foil under the current of 0.2A, and transferring the PMMA/graphene film to SiO 2 And (3) dissolving and removing PMMA on the Si matrix by using acetone at the temperature of 70 ℃ to finish the transfer of the graphene loaded by the platinum nano particles. Wherein SiO is 2 The Si matrix is SiO deposited on the surface of the monocrystalline Si sheet with nano-scale thickness 2 Film, siO 2 The thickness of the film was 290nm.
The quality, uniformity, layer number and appearance and size of the graphene film are characterized by utilizing an optical microscope, a Raman spectrometer and a transmission electron microscope, and the obtained graphene film is a few-layer graphene, the thickness is 2.5nm, the grain size is 32nm, and the appearance of the platinum nano particles loaded on the surface is spherical or agglomerate.
Example 11
Firstly, the embodiment adopts a common vertical furnace (the bottom of a quartz tube of the vertical furnace is connected with a glass container filled with ethanol solution of palladium chloride by a flange) to realize the one-step ultrafast growth of the graphene loaded by palladium nano particles. An argon gas inlet is arranged at the upper end of the vertical furnace, a platinum foil (20 mm multiplied by 10mm multiplied by 150 mu m, purity is 99.95 wt%) is placed down to the center of a hearth by a push-pull rod (the temperature of the center of the hearth is always kept at 1200 ℃), after the platinum foil is raised to 1200 ℃ in an argon atmosphere, the platinum foil falls into a glass container filled with 0.1mol/L palladium chloride ethanol solution (absolute ethanol, analytically pure) at 0 ℃ to be rapidly cooled (quenched), and the growth of the graphene loaded by palladium nano particles is completed in the quenching process. And taking out the platinum foil after the temperature of the platinum foil is reduced to room temperature, and drying the platinum foil in a nitrogen atmosphere.
Then, the surface of the platinum foil with graphene was covered with a solution of polymethyl methacrylate (PMMA) in ethyl lactate (polymethyl methacrylate 4 wt%), spin-coated uniformly at 2000 rpm for 60s using a spin coater, and then baked at 180 ℃ for 20 minutes and then cooled naturally. Taking a platinum foil covered with a PMMA/graphene film as an electrolytic cell cathode (NaOH aqueous solution with molar concentration of 1M is taken as an electrolyte, and an anode is taken as a platinum electrode), separating the PMMA/graphene film from the platinum foil by utilizing hydrogen bubbles generated on the surface of the platinum foil under the current of 0.2A, and transferring the PMMA/graphene film to SiO 2 And (3) dissolving and removing PMMA on the Si matrix by using acetone at the temperature of 70 ℃ to finish the transfer of the graphene loaded by the palladium nano particles. Wherein SiO is 2 The Si matrix is SiO deposited on the surface of the monocrystalline Si sheet with nano-scale thickness 2 Film, siO 2 The thickness of the film was 290nm.
The quality, uniformity, layer number and appearance and size of the palladium nano particles of the graphene film are characterized by utilizing an optical microscope, a Raman spectrometer and a transmission electron microscope, and the obtained graphene film is a few layers of graphene, the thickness is 2.6nm, the grain size is 31nm, the appearance of the palladium nano particles loaded on the surface is spherical, and the average size is 10.7nm.
Example 12
Firstly, the embodiment adopts a common vertical furnace (the bottom of a quartz tube of the vertical furnace is connected with a glass container filled with ethanol solution of ferric chloride by a flange) to realize the one-step ultrafast growth of graphene loaded by iron nano particles. An argon gas inlet is arranged at the upper end of the vertical furnace, a platinum foil (20 mm multiplied by 10mm multiplied by 150 mu m, the purity is 99.95 wt%) is placed down to the center of a hearth by a push-pull rod (the temperature of the center of the hearth is always kept at 1200 ℃), after the platinum foil is raised to 1200 ℃ in an argon atmosphere, the platinum foil falls into a glass container filled with 0.1mol/L ferric chloride ethanol solution (absolute ethanol, analytically pure) at 0 ℃ to be rapidly cooled (quenched), and the growth of graphene loaded by iron nano particles is completed in the quenching process. And taking out the platinum foil after the temperature of the platinum foil is reduced to room temperature, and drying the platinum foil in a nitrogen atmosphere.
Then, the surface of the platinum foil with graphene was covered with a solution of polymethyl methacrylate (PMMA) in ethyl lactate (polymethyl methacrylate 4 wt%), spin-coated uniformly at 2000 rpm for 60s using a spin coater, and then baked at 180 ℃ for 20 minutes and then cooled naturally. Taking a platinum foil covered with a PMMA/graphene film as an electrolytic cell cathode (NaOH aqueous solution with molar concentration of 1M is taken as an electrolyte, and an anode is taken as a platinum electrode), separating the PMMA/graphene film from the platinum foil by utilizing hydrogen bubbles generated on the surface of the platinum foil under the current of 0.2A, and transferring the PMMA/graphene film to SiO 2 And (3) dissolving and removing PMMA on the Si matrix by using acetone at the temperature of 70 ℃ to finish the transfer of the graphene loaded by the iron nano particles. Wherein SiO is 2 The Si matrix is SiO deposited on the surface of the monocrystalline Si sheet with nano-scale thickness 2 Film, siO 2 The thickness of the film was 290nm.
The quality, uniformity, layer number and appearance and size of the graphene film are characterized by using an optical microscope, a Raman spectrometer and a transmission electron microscope, and the obtained graphene film is a few layers of graphene, the thickness is 2.1nm, the grain size is 29nm, the appearance of the surface-loaded iron nanoparticle is spherical, and the average size is 13.1nm.
Example 13
Firstly, the embodiment adopts a common vertical furnace (the bottom of a quartz tube of the vertical furnace is connected with a glass container filled with ethanol solution of nickel chloride by a flange) to realize the one-step ultrafast growth of the graphene loaded by the nickel nano particles. An argon gas inlet is arranged at the upper end of the vertical furnace, a platinum foil (20 mm multiplied by 10mm multiplied by 150 mu m, purity is 99.95 wt%) is placed down to the center of a hearth by a push-pull rod (the temperature of the center of the hearth is always kept at 1200 ℃), after the platinum foil is raised to 1200 ℃ in an argon atmosphere, the platinum foil falls into a glass container filled with 0.1mol/L nickel chloride ethanol solution (absolute ethanol, analytically pure) at 0 ℃ to be rapidly cooled (quenched), and the growth of the cobalt nanoparticle loaded graphene is completed in the quenching process. And taking out the platinum foil after the temperature of the platinum foil is reduced to room temperature, and drying the platinum foil in a nitrogen atmosphere.
Then, the surface of the platinum foil with graphene was covered with a solution of polymethyl methacrylate (PMMA) in ethyl lactate (polymethyl methacrylate 4 wt%), spin-coated uniformly at 2000 rpm for 60s using a spin coater, and then baked at 180 ℃ for 20 minutes and then cooled naturally. Taking a platinum foil covered with a PMMA/graphene film as an electrolytic cell cathode (NaOH aqueous solution with molar concentration of 1M is taken as an electrolyte, and an anode is taken as a platinum electrode), separating the PMMA/graphene film from the platinum foil by utilizing hydrogen bubbles generated on the surface of the platinum foil under the current of 0.2A, and transferring the PMMA/graphene film to SiO 2 And (3) dissolving and removing PMMA on the Si matrix by using acetone at the temperature of 70 ℃ to finish the transfer of the graphene loaded by the nickel nano particles. Wherein SiO is 2 The Si matrix is SiO deposited on the surface of the monocrystalline Si sheet with nano-scale thickness 2 Film, siO 2 The thickness of the film was 290nm.
The quality, uniformity, layer number and appearance and size of the cobalt nano particles of the graphene film are characterized by utilizing an optical microscope, a Raman spectrometer and a transmission electron microscope, and the obtained graphene film is a few layers of graphene, the thickness is 1.9nm, the grain size is 29nm, the appearance of the nickel nano particles loaded on the surface is spherical, and the average size is 3.3nm.
Example 14
Firstly, the embodiment adopts a common vertical furnace (the bottom of a quartz tube of the vertical furnace is connected with a glass container filled with ethanol solution of copper chloride by a flange) to realize the one-step ultrafast growth of the graphene loaded by copper nano particles. An argon gas inlet is arranged at the upper end of the vertical furnace, a platinum foil (20 mm multiplied by 10mm multiplied by 150 mu m, purity is 99.95 wt%) is placed down to the center of a hearth by a push-pull rod (the temperature of the center of the hearth is always kept at 1200 ℃), after the platinum foil is raised to 1200 ℃ in an argon atmosphere, the platinum foil falls into a glass container filled with 0.1mol/L copper chloride ethanol solution (absolute ethanol, analytically pure) at 0 ℃ to be rapidly cooled (quenched), and the growth of the graphene loaded by copper nano particles is completed in the quenching process. And taking out the platinum foil after the temperature of the platinum foil is reduced to room temperature, and drying the platinum foil in a nitrogen atmosphere.
Then, the surface of the platinum foil with graphene was covered with a solution of polymethyl methacrylate (PMMA) in ethyl lactate (polymethyl methacrylate 4 wt%), spin-coated uniformly at 2000 rpm for 60s using a spin coater, and then baked at 180 ℃ for 20 minutes and then cooled naturally. Taking a platinum foil covered with a PMMA/graphene film as an electrolytic cell cathode (NaOH aqueous solution with molar concentration of 1M is taken as an electrolyte, and an anode is taken as a platinum electrode), separating the PMMA/graphene film from the platinum foil by utilizing hydrogen bubbles generated on the surface of the platinum foil under the current of 0.2A, and transferring the PMMA/graphene film to SiO 2 And (3) dissolving and removing PMMA on the Si matrix by using acetone at the temperature of 70 ℃ to finish the transfer of the graphene loaded by the copper nano particles. Wherein SiO is 2 The Si matrix is SiO deposited on the surface of the monocrystalline Si sheet with nano-scale thickness 2 Film, siO 2 The thickness of the film was 290nm.
The quality, uniformity, layer number and morphology and size of the copper nano particles of the graphene film are characterized by using an optical microscope, a Raman spectrometer and a transmission electron microscope, and the obtained graphene film is a few layers of graphene, the thickness is 1.8nm, the grain size is 28nm, the morphology of the copper nano particles loaded on the surface is spherical, and the average size is 29.9nm.
As shown in fig. 1, a schematic diagram of one-step ultrafast preparation of a metal nanoparticle-supported graphene material. And (3) heating the substrate to a preset temperature under the protection of inert gas, then placing the heated substrate in a liquid carbon source solution of metal salt, rapidly cooling (Quenching) to room temperature, and rapidly growing a graphene material (Au NPs@graphene) loaded by metal nano particles on the surface of a platinum Foil (Pt Foil) of the substrate.
As shown in fig. 2, example 1 illustrates that the graphene material loaded by gold nanoparticles can be prepared by the method, the morphology of the gold nanoparticles is spherical, triangular and hexagonal, the crystallization quality is good, and the average size of the particles is 143nm.
As shown in FIG. 3, the gold nanoparticles obtained in example 3 had an average size of 101nm.
As shown in fig. 4, example 9 illustrates that the present method can prepare graphene materials loaded with platinum nanoparticles, and the morphology of the platinum nanoparticles is spherical or agglomerate.
As shown in fig. 5, example 11 illustrates that the method can prepare graphene materials loaded with palladium nanoparticles, wherein the shape of the palladium nanoparticles is spherical, and the average size of the palladium nanoparticles is 10.7nm.
As shown in fig. 6, example 12 illustrates that the method can prepare graphene materials loaded with iron nanoparticles, wherein the morphology of the iron nanoparticles is spherical, and the average size of the iron nanoparticles is 13.1nm.
As shown in fig. 7, example 13 illustrates that the method can prepare a graphene material loaded with nickel nanoparticles, wherein the morphology of the nickel nanoparticles is spherical, and the average size of the nickel nanoparticles is 3.3nm.
As shown in fig. 8, example 14 illustrates that the method can prepare a graphene material loaded with copper nanoparticles, wherein the morphology of the copper nanoparticles is spherical, and the average size of the copper nanoparticles is 29.9nm.
The results show that the graphene material loaded by the metal nano particles can be rapidly grown in one step by rapidly cooling (quenching) the graphene material in a liquid carbon source of metal salt by adopting a high-temperature matrix, and then the graphene loaded by the metal nano particles is obtained by bubbling separation or matrix etching, or the graphene material is directly used together with the matrix. The film, powder and three-dimensional macroscopic body can be prepared by using matrixes with different shapes, and the components, the sizes and the number of the metal nano particles are controlled by changing the components, the thickness, the initial temperature and the types and the concentrations of the metal salts of the matrixes. The preparation method disclosed by the invention has the advantages of simple preparation process, high efficiency, low cost and good controllability, can be used for rapidly preparing the graphene materials loaded by various metal nano particles, and lays a foundation for the application of the materials in the fields of photoelectrocatalysis, industrial catalysis, raman enhancement, high-entropy alloy, gas sensing, electromagnetic shielding and the like.
Claims (9)
1. A one-step ultrafast preparation method of a graphene material loaded by metal nano particles is characterized in that a high-temperature matrix is adopted, a liquid carbon source solution of metal salt is used as quenching liquid in an inert protective atmosphere, the high-temperature matrix is quenched and rapidly cooled in the liquid carbon source of the metal salt, the metal salt is heated and decomposed to form the metal nano particles in the quenching process, and the liquid carbon source is heated and decomposed to grow graphene on the surface of the matrix, so that the graphene material loaded by the metal nano particles is rapidly prepared in one step.
2. The one-step ultrafast preparation method of a graphene material loaded with metal nanoparticles according to claim 1, wherein the matrix is one or more of metal, carbon fiber, carbide, nitride and oxide, and is in the shape of foil, porous foam or powder.
3. The one-step ultrafast preparation method of a graphene material supported by metal nanoparticles according to claim 2, wherein the metal is one or more of copper, platinum, nickel, cobalt, gold, ruthenium, palladium, molybdenum, tungsten, aluminum, copper-nickel alloy, molybdenum-nickel alloy; the carbon fiber is one or two of polyacrylonitrile-based carbon fiber, pipe pitch-based carbon fiber, viscose-based carbon fiber, phenolic-based carbon fiber and vapor grown carbon fiber; the carbide is one or more of silicon carbide, tungsten carbide and molybdenum carbide; the nitride is one or more than two of silicon nitride, tungsten nitride and molybdenum nitride; the oxide is one or more of silicon oxide, aluminum oxide, magnesium oxide, copper oxide and nickel oxide.
4. The one-step ultrafast preparation method of the graphene material loaded with the metal nanoparticles according to claim 1, wherein the liquid carbon source solution of the metal salt is an ethanol solution of the metal salt, and the metal salt is one or more of ferric chloride, nickel chloride, cobalt chloride, copper chloride, stannous chloride, chloroplatinic acid, chloroauric acid, palladium chloride, ferric nitrate, nickel nitrate, cobalt nitrate, copper nitrate, silver nitrate, palladium nitrate, ferrocene, nickel dicyclopentadienyl, cobalt acetylacetonate and nickel acetylacetonate.
5. The one-step ultrafast preparation method of a metal nanoparticle supported graphene material according to claim 4, wherein the initial temperature of the high-temperature matrix is between above the decomposition temperature of the metal salt and below the melting point of the matrix.
6. The one-step ultrafast preparation method of the graphene material loaded with the metal nanoparticles according to claim 1, wherein in the preparation process, the inert protective atmosphere is nitrogen or inert gas or mixed gas of the nitrogen and the inert gas.
7. The one-step ultrafast preparation method of a metal nanoparticle-supported graphene material according to claim 1, wherein the control of the thickness and crystallinity of graphene is achieved by changing the composition, thickness, starting temperature and temperature of the liquid carbon source of the matrix.
8. The one-step ultrafast preparation method of the metal nanoparticle-supported graphene material according to claim 1, wherein the composition, the size and the number of the metal nanoparticles are controlled by changing the composition, the thickness and the initial temperature of the matrix and the type and the concentration of the metal salt.
9. The one-step ultrafast preparation method of a metal nanoparticle-supported graphene material according to claim 1, wherein the metal nanoparticle-supported graphene material grown on the surface of the substrate by a quenching method is separated from the surface of the substrate by an etching method or an electrochemical gas bubbling method or is used together with the substrate.
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