CN112691659A - Method for preparing mesoporous carbon supported metal nanoparticle catalyst - Google Patents
Method for preparing mesoporous carbon supported metal nanoparticle catalyst Download PDFInfo
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- CN112691659A CN112691659A CN201911004046.XA CN201911004046A CN112691659A CN 112691659 A CN112691659 A CN 112691659A CN 201911004046 A CN201911004046 A CN 201911004046A CN 112691659 A CN112691659 A CN 112691659A
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- 239000002082 metal nanoparticle Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 30
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- 239000002184 metal Substances 0.000 claims abstract description 59
- 239000002243 precursor Substances 0.000 claims abstract description 37
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- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052737 gold Inorganic materials 0.000 claims abstract description 5
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
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- 238000005406 washing Methods 0.000 claims description 8
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 7
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 7
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- 239000005642 Oleic acid Substances 0.000 claims description 7
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 7
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- 238000004519 manufacturing process Methods 0.000 claims description 7
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 7
- MLPVBIWIRCKMJV-UHFFFAOYSA-N 2-ethylaniline Chemical compound CCC1=CC=CC=C1N MLPVBIWIRCKMJV-UHFFFAOYSA-N 0.000 claims description 6
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 6
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 5
- 229920001451 polypropylene glycol Polymers 0.000 claims description 5
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 3
- QMWOUSYSNFCKAZ-UHFFFAOYSA-N 3,7-dihydroxynaphthalene-2-carboxylic acid Chemical compound OC1=CC=C2C=C(O)C(C(=O)O)=CC2=C1 QMWOUSYSNFCKAZ-UHFFFAOYSA-N 0.000 claims description 3
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 3
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- CJQWLNNCQIHKHP-UHFFFAOYSA-N Ethyl 3-mercaptopropanoic acid Chemical compound CCOC(=O)CCS CJQWLNNCQIHKHP-UHFFFAOYSA-N 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 229920000469 amphiphilic block copolymer Polymers 0.000 claims description 3
- 150000003934 aromatic aldehydes Chemical class 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 claims description 3
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 claims description 3
- 230000002209 hydrophobic effect Effects 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229920002866 paraformaldehyde Polymers 0.000 claims description 3
- 229920001992 poloxamer 407 Polymers 0.000 claims description 3
- WPZSAUFQHYFIPG-UHFFFAOYSA-N propanethioamide Chemical compound CCC(N)=S WPZSAUFQHYFIPG-UHFFFAOYSA-N 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 3
- 229920001577 copolymer Polymers 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
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims 1
- 150000004820 halides Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 239000002923 metal particle Substances 0.000 abstract description 8
- 239000006185 dispersion Substances 0.000 abstract description 6
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 4
- 230000005518 electrochemistry Effects 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 3
- 230000003321 amplification Effects 0.000 abstract description 2
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- 239000002105 nanoparticle Substances 0.000 description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 7
- 239000012300 argon atmosphere Substances 0.000 description 7
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- 229910052700 potassium Inorganic materials 0.000 description 7
- 239000011591 potassium Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 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 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
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- 239000010931 gold Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
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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
- B01J23/44—Palladium
-
- 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
- B01J23/42—Platinum
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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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
- B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
- B01J2235/15—X-ray diffraction
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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
- B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
- B01J2235/30—Scanning electron microscopy; Transmission electron microscopy
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention provides a preparation method of a mesoporous carbon supported metal nanoparticle catalyst, which can synthesize the mesoporous carbon supported metal nanoparticle catalyst through two steps of hydrothermal and carbonization. In the hydrothermal process, a surfactant, an additive, a metal salt precursor (one, two or three of Pd, Au, Pt, Ag, Ru, Rh, Ir, Ni, Co, Zn and Cu) and a polymer precursor are dispersed in a water phase to prepare a uniform solution, and the solution is further heated to form the mesoporous polymer metal precursor-loaded composite material; in the carbonization process, the composite material of the polymer-loaded metal precursor is converted into the mesoporous carbon-loaded metal nanoparticle catalyst by adjusting the carbonization temperature, the protective atmosphere and the like. The method can obtain the high-dispersion supported catalyst with uniform metal particle size, has simple and convenient preparation process, easy amplification and universality, and has wide application prospect in the fields of catalytic hydrogenation, oxidation, electrochemistry and the like.
Description
Technical Field
The invention relates to a mesoporous carbon supported metal nanoparticle catalyst, which is a high-dispersion supported catalyst with uniform metal particle size constructed by hydrothermal and carbonization steps, and has wide application prospect in the fields of catalytic hydrogenation, oxidation, electrochemistry and the like.
Background
Most reactions in modern industry relate to heterogeneous catalysis process, and supported metal catalysts are important heterogeneous catalysts and widely applied to the fields of petrochemical industry, biomedicine, aerospace and the like. In recent years, the application of metal catalysts in the fields of biomass conversion, electrocatalysis and the like has also been rapidly developed.
Generally, metal nanoparticles with the metal particle size of 3-5 nm and uniform composition can show better catalytic performance, but the smaller the size of the metal nanoparticles, the larger the surface free energy of the metal nanoparticles is, so the stability is poor, and the metal nanoparticles are easy to aggregate and grow or run off in a catalytic reaction to cause catalyst deactivation, which is a difficult problem for limiting the application of a supported metal catalyst with the smaller metal nanoparticles size (chem.rev.2018,118, 4981-5079; adv.mater.,2019,31, 1803966; chem.soc.rev.,2017,46, 4774-. Controlling the size, distribution and limiting the loss of metal nanoparticles in catalytic reactions is the key to determining the performance of metal catalysts. The metal catalyst prepared by the traditional impregnation or coprecipitation method can improve the stability of the metal catalyst through strong interaction between metal and a carrier, but the size, distribution and the like of metal particles are often difficult to accurately control; the solvothermal method can synthesize metal nanoparticles with smaller and uniform size, but when the metal nanoparticles are deposited on the surface of a carrier by colloid deposition, the metal nanoparticles are easy to fall off or run off due to weak interaction force between the metal nanoparticles and the carrier, and particularly, the metal nanoparticles are easy to run off under some harsh multiphase reaction conditions (high temperature and high pressure, liquid phase conditions and the like).
Therefore, a novel universal controllable preparation technology of the high-dispersion supported metal catalyst is needed to be found to obtain the catalyst with uniform metal particle size, the preparation process is simplified, and the large-scale production is easy to realize, so that the industrial application is facilitated.
Disclosure of Invention
In order to solve the problems of size control of the metal nanoparticles, catalyst inactivation caused by loss in the catalytic reaction process and the like, the invention provides a preparation method of a high-dispersion supported metal catalyst.
The invention provides a preparation method of a mesoporous carbon supported metal nanoparticle catalyst, which comprises the following steps: providing an aqueous solution, wherein the aqueous solution comprises an aromatic compound, an aldehyde compound, a metal salt precursor, a surfactant and an additive; heating the aqueous solution to obtain a composite material of the mesoporous polymer loaded with the metal precursor; the obtained composite material can be used for obtaining the mesoporous carbon supported metal nanoparticle catalyst through a carbonization process.
The aromatic compound in the preparation method is required to contain at least one hydroxyl group, and the aromatic compound can be a phenyl compound, a naphthyl compound or an anthryl compound, such as one or more of phenol, resorcinol, aminophenol, p-hydroxybenzoic acid, 2, 4-dihydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 3, 7-dihydroxy-2-naphthoic acid and the like.
The aldehyde compound is one or more compounds selected from aliphatic C1 to C12 aliphatic aldehydes, such as formaldehyde, acetaldehyde, crotonaldehyde, aromatic aldehydes such as furfural, or one or more compounds decomposable into formaldehyde, such as hexamethylenetetramine or paraformaldehyde.
The molar ratio of the aldehyde compound to the aromatic compound is between 0.1:1 and 10:1, preferably between 0.5:1 and 5: 1.
The metal precursor salt can be one, two or three of Pd, Au, Pt, Ag, Ru, Rh, Ir, Ni, Co, Zn and Cu, and respectively corresponds to a single metal catalyst, a double metal catalyst or a trimetal catalyst.
The metal precursor salt can be one, two or three of nitrate, acetylacetone salt, halide salt, cyanide salt, acetate and carbonyl salt.
The molar ratio of metal precursor salt to aromatic compound is between 1:1 and 1:10000, preferably between 1:10 to 1:1000, more preferably between 1: 5 to 1: 500.
In the preparation of the bimetallic catalyst, precursor salts of two different metals are used, which may be mixed in any ratio.
In the preparation of the trimetallic catalysts, precursor salts of three different metals are used, which may be mixed in any ratio.
The surfactant is selected from one or more amphiphilic block copolymers, wherein the copolymer is required to have a hydrophobic segment part containing at least three carbon atoms, such as poly (ethylene oxide) -poly (propylene oxide) -poly (ethylene oxide), preferably Pluronic F127 or P123.
The additive is one or more selected from C3 to C30 compound molecules containing amino, sulfydryl, carboxyl and hydroxyl, such as oleic acid, oleylamine, 2-methylimidazole, melamine, pyrrole, pyridine, quinoline, mesitylene, toluene, ethylbenzene, 2-ethylaniline, thiourea, ethyl 3-mercaptopropionate, thiopropionamide and thioacetamide.
The molar ratio of surfactant to additive is between 1000:1 and 10:1, preferably between 500:1 and 10:1, more preferably between 100:1 and 10: 1.
The heating temperature of the aqueous solution is 40-200 ℃, preferably 60-150 ℃.
The aqueous solution is heated for a period of time ranging from 1 hour to 48 hours, preferably from 4 to 24 hours.
The carbonization temperature is selected from the interval of 150-1000 ℃, preferably 200-800 ℃, and more preferably 400-800 ℃.
The carbonization atmosphere is Ar and N2He or H2Mixed gas with other inert atmosphere.
Single metal, bimetallic, trimetallic catalysts can all be prepared by the methods described above.
As described above, the present invention provides a method for preparing a mesoporous carbon supported metal nanoparticle catalyst, which can synthesize a mesoporous carbon supported metal nanoparticle catalyst through two steps of hydrothermal and carbonization. In the hydrothermal synthesis process, firstly dispersing a surfactant, an additive, a metal salt precursor (one, two or three of Pd, Au, Pt, Ag, Ru, Rh, Ir, Ni, Co, Zn and Cu) and a polymer precursor in a water phase to prepare a uniform solution, and further heating the solution to form the mesoporous polymer metal precursor-loaded composite material; in the carbonization process, the composite material of the polymer-loaded metal precursor is converted into the mesoporous carbon-loaded metal nanoparticle catalyst by adjusting the carbonization temperature, the protective atmosphere and the like.
The method can obtain the high-dispersion supported catalyst with uniform metal particle size, has simple and convenient preparation process, easy amplification and universality, and has wide application prospect in the fields of catalytic hydrogenation, oxidation, electrochemistry and the like.
Additional aspects and advantages will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice.
Drawings
Fig. 1 is a schematic diagram of the preparation of a mesoporous carbon supported metal nanoparticle catalyst.
Fig. 2 is a TEM picture of the mesoporous carbon supported palladium nanoparticle catalyst prepared in example 1.
Fig. 3 is an SEM picture of the mesoporous carbon supported palladium nanoparticle catalyst prepared in example 1.
Fig. 4 is an XRD picture of the mesoporous carbon supported palladium nanoparticle catalyst prepared in example 1.
Fig. 5 is a physical diagram of the mesoporous carbon supported palladium nanoparticle catalyst prepared in example 1.
Detailed Description
The present invention relates to a method for preparing a mesoporous carbon supported metal nanoparticle catalyst, as described in detail below.
Firstly, dispersing an aromatic compound, an aldehyde compound, a metal salt precursor, a surfactant and an additive in a water phase to prepare a uniform solution.
The aromatic compound of the present invention is preferably an aromatic compound capable of undergoing a polymerization reaction with an aldehyde compound, such as an aromatic compound having at least one active group such as an amino group or a hydroxyl group. Among the various reactive groups, preferred aromatic compounds of the present invention contain at least one hydroxyl group. Because the hydroxyl groups can avoid the residue of impurity elements after the carbonization treatment in the later period.
Therefore, preferably, the aromatic compound includes at least one hydroxyl group, and the aromatic compound may be a phenyl compound, a naphthyl compound or an anthryl compound, such as one or more of phenol, resorcinol, aminophenol, p-hydroxybenzoic acid, 2, 4-dihydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 3, 7-dihydroxy-2-naphthoic acid, and the like.
The aldehyde compound is preferably one or more compounds selected from aliphatic C1 to C12 aliphatic aldehydes, such as formaldehyde, acetaldehyde, crotonaldehyde, aromatic aldehydes such as furfural, or one or more compounds that decompose to formaldehyde, such as hexamethylenetetramine or paraformaldehyde.
The molar ratio of the aldehyde compound to the aromatic compound is between 0.1:1 and 10:1, preferably between 0.5:1 and 5: 1.
The metal precursor salt is one, two or three of Pd, Au, Pt, Ag, Ru, Rh, Ir, Ni, Co, Zn and Cu, and respectively corresponds to a single metal catalyst, a double metal catalyst or a trimetal catalyst.
The metal precursor salt can be one, two or three of nitrate, acetylacetone salt, halide salt, cyanide salt, acetate and carbonyl salt.
The molar ratio of the metal precursor salt to the aromatic compound is between 1:1 and 1: 10000. When the molar ratio of the metal precursor salt to the aromatic compound is less than 1:1, the metal loading is extremely high and the size of the metal nanoparticles is not easy to control; when the molar ratio of the metal precursor salt to the aromatic compound is less than 1:10000, the metal loading is extremely low, and the method is not suitable for practical production application. Further preferably, the molar ratio of metal precursor salt to aromatic compound is further preferably in the range of 1:10 to 1:1000, more preferably between 1: 5 to 1: 500.
In the preparation of the bimetallic catalyst, the precursor salts of the two different metals may be mixed in any ratio.
In the preparation of the trimetallic catalyst, the precursor salts of the three different metals can be mixed in any proportion.
In the invention, the surfactant is used as a pore-forming agent of the carrier to form a mesoporous structure. The surfactant is selected from one or more amphiphilic block copolymers, wherein the hydrophobic segment part contains at least three carbon atoms, such as poly (ethylene oxide) -poly (propylene oxide) -poly (ethylene oxide), preferably Pluronic F127 or P123.
The amount of the surfactant added is 0.001 to 100 times, preferably 0.01 to 10 times by mass of the aromatic compound containing at least one hydroxyl group. When the amount of the surfactant is less than 0.001 times, the support cannot form mesopores; when the amount of the surfactant is more than 100 times, the polymerization rate of the carrier is slow and the economic cost is high.
In the present invention, an additive is used in order to promote uniform dispersion of the metal. The additive of the invention uses organic small molecule compounds. We have found that the additive has the functions of pore-expanding, micelle stabilizing and the like, and can uniformly disperse the metal particles. If no additives are added, large agglomerated particles may form or be unsupported. The additive is preferably a compound molecule of C3 to C30 containing amino, sulfydryl, carboxyl and hydroxyl, such as one or more of oleic acid, oleylamine, 2-methylimidazole, melamine, pyrrole, pyridine, quinoline, mesitylene, toluene, ethylbenzene, 2-ethylaniline, thiourea, ethyl 3-mercaptopropionate, thiopropionamide and thioacetamide.
The molar ratio of surfactant to additive is between 1000:1 and 10:1, preferably between 500:1 and 10:1, and more preferably between 100:1 and 10: 1.
And then heating the solution containing the aromatic compound, the aldehyde compound, the metal salt precursor, the surfactant and the additive, and obtaining the mesoporous polymer supported metal precursor composite material through a hydrothermal process.
The solution is heated to form the mesoporous polymer supported metal precursor composite material in one step. The solution heating temperature is preferably 40 ℃ to 200 ℃. When the heating temperature is lower than 40 ℃, the polymerization speed is slow, and the carrier is not easy to form; when the heating temperature is higher than 200 ℃, the carrier is rapidly molded, and simultaneously the metal salt is rapidly reduced, so that the catalyst with the non-uniform size distribution of the metal nanoclusters is obtained. Further, the solution heating temperature is further preferably 60 ℃ to 150 ℃.
The solution is heated for preferably at least 1 hour, more preferably at least 4 hours, to achieve sufficient heating polymerization. In view of the colloidal state, it is generally not more than 48 hours, preferably not more than 24 hours. The specific heating time may be adjusted according to the heating temperature and the composition of the solution.
And finally, the composite material of the mesoporous polymer loaded metal precursor is converted into the mesoporous carbon loaded metal nanoparticle catalyst through a carbonization process.
The carbonization temperature is selected from the interval of 150-1000nC, preferably 200-800nC, and more preferably 400-800 nC.
The time for carbonization at the carbonization temperature is preferably 1 to 15 hours, and more preferably 2 to 6 hours. In order to achieve sufficient carbonization, the carbonization time is generally at least 1 hour, and more preferably at least 2 hours. In view of energy consumption cost, it is generally not more than 15 hours, preferably not more than 10 hours, and more preferably not more than 8 hours.
The carbonization process atmosphere can be selected from Ar and N2He or H2Mixed gas with other inert atmosphere.
The synthesized catalyst can be characterized by Transmission Electron Microscopy (TEM), Scanning Electron Microscopy (SEM), X-ray diffraction (XRD), and the like.
The mesoporous carbon supported metal nanoparticle catalyst obtained by the method has the characteristics of uniform size distribution of metal particles, difficulty in loss and the like, can be prepared by only two steps of hydrothermal and carbonization, has simple and convenient preparation process, is easy to amplify, has universality, and can have wide application prospects in the fields of catalytic hydrogenation, oxidation, electrochemistry and the like.
For a more clear understanding of the technical features, objects and advantages of the present invention, reference is now made to the following detailed description of the embodiments of the present invention taken in conjunction with the accompanying drawings, which are included to illustrate and not to limit the scope of the present invention.
The invention can synthesize various single metal, double metal and tri-metal catalysts by changing and combining different types of metal precursors, and the preparation process is shown in figure 1. Taking the synthesis of a platinum catalyst or a palladium catalyst as an example, the metal salt is one of potassium chloropalladite, potassium chloroplatinite and platinum acetylacetonate, and the amount of the metal salt is 0.01mmol to 0.5 mmol. P123 or F127 is used as a surfactant, and the mass is 0.1 to 10 g. 2, 4-dihydroxybenzoic acid or resorcinol is used as a carrier precursor, and the mass is 0.1-5 g. The additive is one of oleic acid, oleylamine, polypropylene glycol 1000, toluene and chlorobenzene, and the mass of the additive is 0.1-15 g. The whole system is dissolved in 20-1000ml of water to form a uniform solution. The mesoporous carbon supported metal nanoparticle catalyst is synthesized by the following various reaction conditions.
Example 1
Dissolving 3.0g of 2, 4-dihydroxybenzoic acid, 0.9g of hexamethylenetetramine, 0.15g of oleic acid, 3.5g P123 and 0.25mmol of potassium chloropalladite in 80mL of water to form a uniform solution, reacting at 130nC for 4 hours, after the reaction is finished, performing suction filtration, washing, drying, and carbonizing at 500nC for 4 hours under an argon atmosphere to obtain the mesoporous carbon supported palladium nanoparticle catalyst (shown in figure 2-TEM, figure 3-SEM and figure 4-XRD).
In addition, the catalyst obtained by the method of the invention is naturally shaped in the preparation process. If it is naturally shaped during the heating process of the aqueous solution, the cylindrical catalyst is naturally obtained after the aqueous solution is placed in a glass tube and heated for polymerization, and the cake-shaped catalyst is naturally obtained after the aqueous solution is placed in a watch glass and heated for polymerization. As shown in fig. 5-physical diagram, the catalyst is a cylindrical mesoporous carbon supported palladium nanoparticle catalyst obtained by natural molding.
Therefore, the catalyst prepared by the invention can be easily and randomly molded, and the catalyst with various shapes such as powder, column, sheet and the like can be conveniently prepared.
Example 2
Dissolving 3.0g of 2, 4-dihydroxybenzoic acid, 0.9g of hexamethylenetetramine, 0.3g of polypropylene glycol 1000, 3.5g P123 and 0.25mmol of platinum acetylacetonate in 80mL of water to form a uniform solution, reacting at 130nC for 4 hours, after the reaction is finished, carrying out suction filtration, washing, drying, and carbonizing at 500nC for 4 hours under the argon atmosphere to obtain the mesoporous carbon supported platinum nanoparticle catalyst.
Example 3
Dissolving 3.0g of 2, 4-dihydroxybenzoic acid, 0.9g of hexamethylenetetramine, 0.22g of oleylamine, 3.5g P123 and 0.25mmol of platinum acetylacetonate in 80mL of water to form a uniform solution, reacting for 4 hours at 130 ℃, filtering after the reaction is finished, washing, drying, and carbonizing for 4 hours at 500 ℃ in an argon atmosphere to obtain the mesoporous carbon supported platinum metal nanoparticle catalyst.
Example 4
Dissolving 3.0g of 2, 4-dihydroxybenzoic acid, 0.9g of hexamethylenetetramine, 0.2g of toluene, 3.5g P123 and 0.25mmol of potassium chloropalladite in 80mL of water to form a uniform solution, reacting for 4 hours at 130 ℃, after the reaction is finished, performing suction filtration, washing, drying, and carbonizing for 4 hours at 500 ℃ in an argon atmosphere to obtain the mesoporous carbon-supported palladium nanoparticle catalyst.
Example 5
Dissolving 3.0g of 2, 4-dihydroxybenzoic acid, 0.9g of hexamethylenetetramine, 0.5g of chlorobenzene, 3.5g P123 and 0.25mmol of potassium chloroplatinite in 80mL of water to form a uniform solution, reacting for 4 hours at 130 ℃, after the reaction is finished, carrying out suction filtration, washing, drying, and carbonizing for 4 hours at 500 ℃ in an argon atmosphere to obtain the mesoporous carbon supported platinum metal nanoparticle catalyst.
Example 6
Dissolving 3.0g of resorcinol, 0.9g of hexamethylenetetramine, 0.15g of oleic acid, 3.5g P123 and 0.25mmol of potassium chloropalladite in 80mL of water to form a uniform solution, reacting for 4 hours at 130 ℃, after the reaction is finished, performing suction filtration, washing, drying, and carbonizing for 4 hours at 500 ℃ in an argon atmosphere to obtain the mesoporous carbon supported palladium metal nanoparticle catalyst.
Example 7
Dissolving 3.0g of resorcinol, 0.9g of hexamethylenetetramine, 0.15g of oleic acid, 3.5g F127 and 0.25mmol of potassium chloropalladite in 80mL of water to form a uniform solution, reacting for 4 hours at 130 ℃, after the reaction is finished, performing suction filtration, washing, drying, and carbonizing for 4 hours at 500 ℃ in an argon atmosphere to obtain the mesoporous carbon supported palladium metal nanoparticle catalyst.
The present invention has been made in view of the above description, and the preparation conditions of the catalyst of the present invention are clearly disclosed. It will be apparent, however, to one skilled in the art that certain modifications and improvements can be made to the invention. Therefore, any modification and improvement made to the present invention should be within the scope of the present invention as long as it does not depart from the spirit of the present invention.
Claims (16)
1. A method for preparing a mesoporous carbon supported metal nanoparticle catalyst comprises the following specific steps:
a) providing an aqueous solution comprising an aromatic compound, an aldehyde compound, a metal salt precursor, a surfactant, and an additive,
b) heating the solution in the step a) to obtain the mesoporous polymer loaded metal precursor composite material,
c) washing and drying the composite material obtained in the step b), and carrying out a carbonization process to obtain the mesoporous carbon supported metal nanoparticle catalyst.
2. The process for preparing a catalyst according to claim 1, characterized in that in step a) said aromatic compound comprises at least one hydroxyl group, preferably a phenyl compound, naphthyl compound or anthryl compound, such as one or more of phenol, resorcinol, aminophenol, p-hydroxybenzoic acid, 2, 4-dihydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 3, 7-dihydroxy-2-naphthoic acid.
3. The process for preparing a catalyst according to claim 1 or 2, characterized in that the one aldehyde compound in step a) is one or more selected from aliphatic C1 to C12 aliphatic aldehydes, such as formaldehyde, acetaldehyde, crotonaldehyde, aromatic aldehydes, such as furfural, or one or more compounds decomposable into formaldehyde, such as hexamethylenetetramine, paraformaldehyde.
4. The process for preparing a catalyst according to any one of claims 1 to 3, characterized in that in step a) the molar ratio of said one aldehyde compound to aromatic compound is between 0.1:1 and 10:1, preferably between 0.5:1 and 5: 1.
5. The method for preparing a catalyst according to any one of claims 1 to 4, wherein the metal precursor salt in step a) is a mixture comprising one, two or three of Pd, Au, Pt, Ag, Ru, Rh, Ir, Ni, Co, Zn and Cu, corresponding to a single metal catalyst, a bimetallic catalyst or a trimetallic catalyst, respectively.
6. The method for preparing catalyst according to any of claims 1 to 5, wherein in step a) the metal precursor salt is selected from one, two or three of nitrate, acetylacetonate, halide, cyanide, acetate and carbonyl salts.
7. The process for preparing a catalyst according to any one of claims 1 to 6, characterized in that in step a) the molar ratio of metal precursor salt to aromatic compound is between 1:1 and 1:10000, preferably between 1: 5 to 1: 500.
8. The method for preparing a catalyst according to any one of claims 5 to 7, characterized in that precursor salts of two different metals are used in step a) in any ratio to finally prepare the bimetallic catalyst.
9. The method for preparing a catalyst according to any one of claims 5 to 7, characterized in that precursor salts of three different metals are used in step a) in any ratio to finally prepare a trimetallic catalyst.
10. The process for the preparation of a catalyst according to any of claims 1 to 9, characterized in that in step a) the surfactant is selected from one or more amphiphilic block copolymers, which copolymers are such that the hydrophobic segment part comprises at least three carbon atoms, such as poly (ethylene oxide) -poly (propylene oxide) -poly (ethylene oxide), preferably Pluronic F127 or P123.
11. The method for preparing catalyst according to any of claims 1 to 10, characterized in that in step a) the additive is selected from one or more of the group consisting of molecules of compounds C3 to C30 containing amino, mercapto, carboxyl or hydroxyl groups, such as oleic acid, oleylamine, 2-methylimidazole, melamine, pyrrole, pyridine, quinoline, mesitylene, toluene, ethylbenzene, 2-ethylaniline, thiourea, ethyl 3-mercaptopropionate, thiopropionamide, thioacetamide.
12. The process for the preparation of a catalyst according to any of claims 1 to 11, characterized in that in step a) the molar ratio of the surfactant to the additive is between 1000:1 and 10:1, preferably between 100:1 and 10: 1.
13. A process for preparing a catalyst according to any one of claims 1 to 12, characterized in that the aqueous solution in step b) is heated to a temperature of 40 ℃ to 200 ℃, preferably 60 ℃ to 150 ℃.
14. Process for the preparation of a catalyst according to any one of claims 1 to 13, characterized in that the aqueous solution in step b) is heated for a period of at least 1 hour, preferably at least 4 hours. .
15. Process for the preparation of a catalyst according to any one of claims 1 to 14, characterized in that the carbonization temperature in step c) is selected from the interval of 150-1000 ℃, preferably 200-800 ℃.
16. The process for preparing a catalyst according to any one of claims 1 to 15, characterized in that the carbonization atmosphere in step c) is Ar, N2He or H2Mixed gas with other inert atmosphere.
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