CN112774666A - Monoatomic noble metal/graphene catalyst for hydrogenation of cinnamaldehyde and preparation method thereof - Google Patents
Monoatomic noble metal/graphene catalyst for hydrogenation of cinnamaldehyde and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 60
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 58
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 title claims abstract description 42
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 42
- 229940117916 cinnamic aldehyde Drugs 0.000 title claims abstract description 38
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 30
- 239000010439 graphite Substances 0.000 claims abstract description 30
- 230000005855 radiation Effects 0.000 claims abstract description 23
- 239000006185 dispersion Substances 0.000 claims abstract description 18
- 150000003839 salts Chemical class 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000009830 intercalation Methods 0.000 claims abstract description 7
- 230000002687 intercalation Effects 0.000 claims abstract description 6
- 238000005868 electrolysis reaction Methods 0.000 claims description 33
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 16
- 229960000583 acetic acid Drugs 0.000 claims description 15
- 239000012362 glacial acetic acid Substances 0.000 claims description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 13
- 230000002378 acidificating effect Effects 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 12
- 239000008151 electrolyte solution Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- SESFRYSPDFLNCH-UHFFFAOYSA-N benzyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC1=CC=CC=C1 SESFRYSPDFLNCH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 229960002903 benzyl benzoate Drugs 0.000 claims description 3
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 abstract description 16
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- OOCCDEMITAIZTP-UHFFFAOYSA-N allylic benzylic alcohol Natural products OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 12
- 239000002253 acid Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000002985 plastic film Substances 0.000 description 6
- 229920006255 plastic film Polymers 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
Abstract
The invention particularly relates to a preparation method of a monatomic noble metal/graphene catalyst for hydrogenation of cinnamaldehyde, which comprises the following steps: and carrying out electrochemical intercalation and ultrasonic stripping on graphite to load noble metal salt on graphene, and reducing by microwave radiation to prepare the monatomic noble metal/graphene catalyst for hydrogenation of cinnamaldehyde. According to the monatomic noble metal/graphene catalyst for hydrogenation of cinnamaldehyde prepared by the method, the active component noble metal is loaded on graphene in an atomic form with high dispersion and high stability, and the catalyst shows high activity, high selectivity and high stability when used in a reaction of selective hydrogenation of cinnamaldehyde to generate cinnamyl alcohol.
Description
Technical Field
The invention belongs to the technical field of catalyst synthesis, and particularly relates to a monatomic noble metal/graphene catalyst for hydrogenation of cinnamaldehyde and a preparation method thereof.
Background
The alpha, beta-unsaturated alcohol generated by the selective hydrogenation of the alpha, beta-unsaturated aldehyde is an important raw material and an intermediate for the production of spices, medicaments and other fine chemical products, and is widely applied to organic synthesis. Cinnamaldehyde, a representative example of α, β unsaturated aldehydes, has a benzene ring, a C ═ O double bond, and a C ═ C double bond, and forms a conjugated system, and since the bond energy (615KJ · mol ∼ 1) of the C ═ C bond is lower than that of the C ═ O bond (715KJ · mol —. 1), the hydrogenation of the former is more thermodynamically favorable, so that it is difficult to selectively hydrogenate the C ═ O bond without destroying C ═ C, and the hydrogenation selectivity is poor. One of the keys to solving the above problems is to design a suitable catalyst.
The monatomic noble metal catalyst is a novel catalyst, based on an atom-level metal active component, has great advantages in the aspects of maximizing the number of active sites, enhancing the selectivity of a target product, improving the inherent catalytic activity and reducing the consumption of noble metals, is expected to be used for generating cinnamyl alcohol by selective hydrogenation of cinnamyl aldehyde, and has the main challenges of synthesizing the monatomic catalyst at present: how to uniformly disperse the formed single atoms and avoid the agglomeration of metal atoms.
Graphene is a single-atomic-layer graphite, is composed of atomic monolayers with tightly connected carbon atoms hybridized in sp2, and is a true two-dimensional atomic crystal with a two-dimensional honeycomb lattice structure formed by close packing of monolayer carbon atoms physically. Graphene has high electrical conductivity, thermal conductivity, good mechanical strength, flexibility, chemical stability and high specific surface area, is a basic unit constituting other carbonaceous materials, and has been widely noticed by various scholars since being discovered in 2004. If the noble metal center can be dispersed into/on the graphene skeleton, the dispersion degree of the active center can be obviously improved, and the number of the active center in unit area can be increased.
At present, no document report exists that a monoatomic noble metal/graphene composite material is used as a catalyst for hydrogenation of cinnamaldehyde to generate cinnamyl alcohol.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a monatomic noble metal catalyst/graphene for hydrogenation of cinnamaldehyde, and the catalyst prepared by the method has the advantages that the noble metal serving as an active component is highly dispersed and stably loaded on the graphene in an atomic scale form, and the catalyst shows high activity, high selectivity and high stability when being used for a reaction of selective hydrogenation of cinnamaldehyde to generate cinnamyl alcohol.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of a monatomic noble metal/graphene catalyst for hydrogenation of cinnamaldehyde comprises the following steps: and carrying out electrochemical intercalation and ultrasonic stripping on graphite to load noble metal salt on graphene, and reducing by microwave radiation to prepare the monatomic noble metal/graphene catalyst for hydrogenation of cinnamaldehyde.
Preferably, the preparation method of the monatomic noble metal/graphene catalyst for hydrogenation of cinnamaldehyde specifically comprises the following steps:
(1) taking natural crystalline flake graphite as an anode and a platinum sheet as a cathode, and carrying out constant current electrolysis in an electrolyte solution, wherein the electrolyte consists of a noble metal salt and an acidic substance; after the electrolysis is finished, neutralizing, washing, filtering and drying the electrolysis product to obtain intercalated graphite;
(2) dispersing the intercalated graphite obtained in the step (1) in a solution for ultrasonic stripping to obtain a graphene dispersion liquid;
(3) carrying out microwave radiation on the graphene dispersion liquid in the step (2); and after the microwave radiation is finished, washing, filtering and drying the microwave radiation product to obtain the monatomic noble metal/graphene catalyst for hydrogenation of the cinnamaldehyde.
Preferably, the noble metal salt in the step (1) is an inorganic salt of Pt, and the concentration of the noble metal salt in the electrolyte solution is 0.0001-0.01 mol/L.
Preferably, in the step (1), the acidic substance is any one or a mixture of two or more of concentrated sulfuric acid, perchloric acid and glacial acetic acid, and the concentration of the acidic substance in the electrolyte solution is 3-15 mol/L.
More preferably, the acidic substance in step (1) is composed of perchloric acid and glacial acetic acid, the concentration of the perchloric acid is 2.5-10 mol/L, and the concentration of the glacial acetic acid is 2.5-10 mol/L.
Preferably, the concentration of the electrolyte solution in the step (1) is 30 to 70 wt%, and the noble metal salt is added in an amount such that the noble metal content in the finally prepared catalyst is 0.01 to 2% by atom based on the weight of the catalyst.
Preferably, the current density of the electrolysis in the step (1) is 20-70 mA/cm2, the temperature of the electrolysis is 10-60 ℃, and the time of the electrolysis is 20-120 min.
Preferably, the drying temperature in the step (1) is 40-70 ℃, and the drying time is 6-12 h.
Preferably, the solvent in step (2) is any one or a mixture of more than two of ethanol, ethylene glycol, isopropanol, N-dimethylformamide, tetrahydrofuran, N-methylpyrrolidone and benzyl benzoate.
Preferably, the power of the ultrasound in the step (2) is 20-30W, and the time of the ultrasound is 1-6 h.
Preferably, the power of the microwave radiation in the step (3) is 600-1000 w, and the time of the microwave radiation is 1-10 min.
Preferably, the drying temperature in the step (3) is 40-70 ℃, and the drying time is 6-12 h.
According to the monatomic noble metal/graphene catalyst for cinnamaldehyde hydrogenation prepared by the method, the active component noble metal is loaded on graphene in an atomic form with high dispersion and high stability, and can be used in the reaction of cinnamaldehyde hydrogenation to generate cinnamyl alcohol.
Compared with the prior art, the preparation process is simple, the noble metal is uniformly inserted between graphite layers in situ in an anion mode by electrochemically intercalating the graphite, and meanwhile, the noble metal anions are limited between the graphite layers by utilizing the layered structure of the graphite to obtain the intercalated graphite with uniform intercalation, and the whole intercalation process is simple and easy to regulate; then carrying out ultrasonic stripping on the intercalated graphite to obtain graphene; finally, reducing the metal salt loaded on the graphene into a monoatomic metal through microwave radiation to obtain a monoatomic noble metal/graphene catalyst for hydrogenation of cinnamaldehyde; the large specific surface area of the graphene provides a better place for the dispersion and stability of the noble metal, and simultaneously the graphene can be better contacted with a substrate cinnamyl aldehyde of a hydrogenation reaction for reaction; pi electrons in the graphene structure can form a delocalized pi bond, so that the adsorption capacity of the catalyst on cinnamyl aldehyde serving as a substrate of a hydrogenation reaction is enhanced; the graphene has certain hydrogen adsorption capacity, and the hydrogen adsorption capacity of the graphene can be further improved by loading the noble metal; the prepared catalyst has the active component noble metal which is loaded on the graphene in an atomic form with high dispersion and high stability, and shows high activity, high selectivity and high stability when being used in the reaction of generating cinnamyl alcohol by selective hydrogenation of cinnamyl aldehyde.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments.
The preparation method of the monatomic noble metal/graphene catalyst for hydrogenation of cinnamaldehyde comprises the following steps: and carrying out electrochemical intercalation and ultrasonic stripping on graphite to load noble metal salt on graphene, and reducing by microwave radiation to prepare the monatomic noble metal/graphene catalyst for hydrogenation of cinnamaldehyde.
Preferably, the preparation method of the monatomic noble metal/graphene catalyst for hydrogenation of cinnamaldehyde specifically comprises the following steps:
(1) taking natural crystalline flake graphite as an anode and a platinum sheet as a cathode, and carrying out constant current electrolysis in an electrolyte solution, wherein the electrolyte consists of a noble metal salt and an acidic substance; after the electrolysis is finished, neutralizing, washing, filtering and drying the electrolysis product to obtain intercalated graphite;
(2) dispersing the intercalated graphite obtained in the step (1) in a solution for ultrasonic stripping to obtain a graphene dispersion liquid;
(3) carrying out microwave radiation on the graphene dispersion liquid in the step (2); and after the microwave radiation is finished, washing, filtering and drying the microwave radiation product to obtain the monatomic noble metal/graphene catalyst for hydrogenation of the cinnamaldehyde.
Preferably, the noble metal salt in step (1) is an inorganic salt of Pt, and may be any one or a mixture of two or more of chloroplatinic acid, platinum chloride, platinum nitrate, sodium chloroplatinate, and potassium chloroplatinate, and the concentration of the noble metal salt in the electrolyte solution is 0.0001-0.01 mol/L.
Preferably, in the step (1), the acidic substance is any one or a mixture of two or more of concentrated sulfuric acid, perchloric acid and glacial acetic acid, and the concentration of the acidic substance in the electrolyte solution is 3-15 mol/L.
More preferably, the acidic substance in step (1) is composed of perchloric acid and glacial acetic acid, the concentration of the perchloric acid is 2.5-10 mol/L, and the concentration of the glacial acetic acid is 2.5-10 mol/L.
Preferably, the concentration of the electrolyte solution in the step (1) is 30 to 70 wt%, and the noble metal salt is added in an amount such that the noble metal content in the finally prepared catalyst is 0.01 to 2% by atom based on the weight of the catalyst.
Preferably, the current density of the electrolysis in the step (1) is 20-70 mA/cm2, the temperature of the electrolysis is 10-60 ℃, and the time of the electrolysis is 20-120 min.
Preferably, the drying temperature in the step (1) is 40-70 ℃, and the drying time is 6-12 h.
Preferably, the solvent in step (2) is any one or a mixture of more than two of ethanol, ethylene glycol, isopropanol, N-dimethylformamide, tetrahydrofuran, N-methylpyrrolidone and benzyl benzoate.
Preferably, the power of the ultrasound in the step (2) is 20-30W, and the time of the ultrasound is 1-6 h.
Preferably, the power of the microwave radiation in the step (3) is 600-1000 w, and the time of the microwave radiation is 1-10 min.
Preferably, the drying temperature in the step (3) is 40-70 ℃, and the drying time is 6-12 h.
According to the monatomic noble metal/graphene catalyst for hydrogenation of cinnamaldehyde prepared by the method, the active component noble metal is loaded on graphene in an atomic form with high dispersion and high stability.
The monatomic noble metal/graphene catalyst for cinnamaldehyde hydrogenation prepared by the method can be used in reactions for generating cinnamyl alcohol through cinnamaldehyde hydrogenation.
The performance evaluation of the catalyst is carried out in a 50mL high-pressure reaction kettle, the solvent is 30mL of isopropanol, 1g of cinnamaldehyde and 0.05g of catalyst, the reaction gas is hydrogen (1.5MPa), the reaction temperature is 80 ℃, and the reaction time is 2 h. After the reaction, the reaction mixture was cooled to room temperature, and the centrifuged filtrate was quantitatively measured by gas chromatography, model C of Shimadzu GC-2014.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
Example 1
Wrapping 10g of natural flake graphite with a plastic film with holes, fixing and adhering the plastic film to a stainless steel plate as an anode, taking a platinum sheet as a cathode, and carrying out constant current electrolysis in 100mL of electrolyte aqueous solution, wherein the electrolyte consists of chloroplatinic acid, perchloric acid and glacial acetic acid, the concentration of the chloroplatinic acid in the electrolyte aqueous solution is 0.0001mol/L, the concentration of the perchloric acid is 10mol/L, the concentration of the glacial acetic acid is 2.5mol/L, the current density is 20mA/cm2, the electrolysis temperature is 60 ℃, the electrolysis time is 20min, after the electrolysis is finished, an electrolysis product is neutralized, washed and filtered, and dried at 40 ℃ for 12h to obtain the intercalated graphite.
Dispersing the intercalated graphite in 100mL of glycol solution, carrying out ultrasonic treatment for 6h by 20W to obtain graphene dispersion liquid, radiating the graphene dispersion liquid in 600W of microwave for 10min, washing a microwave radiation product with water, filtering, and carrying out vacuum drying for 12h at 40 ℃ to obtain the monatomic noble metal/graphene catalyst for hydrogenation of cinnamaldehyde.
Example 2
Wrapping 10g of natural flake graphite with a plastic film with holes, fixing and adhering the plastic film to a stainless steel plate as an anode, taking a platinum sheet as a cathode, and carrying out constant current electrolysis in 100mL of electrolyte aqueous solution, wherein the electrolyte consists of chloroplatinic acid, perchloric acid and glacial acetic acid, the concentration of the chloroplatinic acid in the electrolyte aqueous solution is 0.01mol/L, the concentration of the perchloric acid is 2.5mol/L, the concentration of the glacial acetic acid is 10mol/L, the current density is 70mA/cm2, the electrolysis temperature is 10 ℃, the electrolysis time is 120min, after the electrolysis is finished, an electrolysis product is neutralized, washed and filtered, and dried at 70 ℃ for 12h to obtain the intercalated graphite.
Weighing 1g of the intercalated graphite, dispersing the intercalated graphite in 100mL of ethanol solution, carrying out 30W ultrasonic treatment for 1h to obtain graphene dispersion liquid, then radiating the graphene dispersion liquid in 1000W microwave for 1min, washing a microwave radiation product, filtering, and carrying out vacuum drying at 70 ℃ for 6h to obtain the monatomic noble metal/graphene catalyst for hydrogenation of cinnamaldehyde.
Example 3
Wrapping 10g of natural flake graphite with a plastic film with holes, fixing and adhering the plastic film to a stainless steel plate as an anode, taking a platinum sheet as a cathode, and carrying out constant current electrolysis in 100mL of electrolyte aqueous solution, wherein the electrolyte consists of chloroplatinic acid, perchloric acid and glacial acetic acid, the concentration of the chloroplatinic acid in the electrolyte aqueous solution is 0.0002mol/L, the concentration of the perchloric acid is 10mol/L, the concentration of the glacial acetic acid is 2.5mol/L, the current density is 60mA/cm2, the electrolysis temperature is 10 ℃, the electrolysis time is 100min, after the electrolysis is finished, an electrolysis product is neutralized, washed and filtered, and dried at 40 ℃ for 12h to obtain the intercalated graphite.
Dispersing the intercalated graphite in 100mL of DMF solution, carrying out 30W ultrasonic treatment for 3h to obtain graphene dispersion liquid, then radiating the graphene dispersion liquid in 800W microwave for 2min, washing the microwave radiation product with water, filtering, and carrying out vacuum drying at 60 ℃ for 12h to obtain the monatomic noble metal/graphene catalyst for hydrogenation of cinnamaldehyde.
The results of using the monatomic noble metal/graphene catalyst for cinnamaldehyde hydrogenation of examples 1 to 3 in the reaction for preparing cinnamaldehyde by selective hydrogenation of cinnamaldehyde are shown in table 1.
As can be seen from table 1, when the monatomic noble metal/graphene catalyst for hydrogenation of cinnamaldehyde is used in a reaction for preparing cinnamyl alcohol through selective hydrogenation of cinnamaldehyde, the catalyst shows the characteristics of high activity and high selectivity, and is repeatedly used for many times, the sintering agglomeration phenomenon does not occur, the activity and selectivity are not obviously reduced, and the catalyst shows the characteristics of high stability.
The above embodiments describe the technical solutions of the present invention in detail. It will be clear that the invention is not limited to the described embodiments. Based on the embodiments of the present invention, those skilled in the art can make various changes, but any changes equivalent or similar to the present invention are within the protection scope of the present invention.
Claims (10)
1. A preparation method of a monatomic noble metal/graphene catalyst for hydrogenation of cinnamaldehyde is characterized by comprising the following steps: and carrying out electrochemical intercalation and ultrasonic stripping on graphite to load noble metal salt on graphene, and reducing by microwave radiation to prepare the monatomic noble metal/graphene catalyst for hydrogenation of cinnamaldehyde.
2. The preparation method according to claim 1, comprising the following steps:
(1) taking natural crystalline flake graphite as an anode and a platinum sheet as a cathode, and carrying out constant current electrolysis in an electrolyte solution, wherein the electrolyte consists of a noble metal salt and an acidic substance; after the electrolysis is finished, neutralizing, washing, filtering and drying the electrolysis product to obtain intercalated graphite;
(2) dispersing the intercalated graphite obtained in the step (1) in a solution for ultrasonic stripping to obtain a graphene dispersion liquid;
(3) carrying out microwave radiation on the graphene dispersion liquid in the step (2); and after the microwave radiation is finished, washing, filtering and drying the microwave radiation product to obtain the monatomic noble metal/graphene catalyst for hydrogenation of the cinnamaldehyde.
3. The production method according to claim 2, wherein the noble metal salt in the step (1) is an inorganic salt of Pt, and the concentration of the noble metal salt in the electrolyte solution is 0.0001 to 0.01 mol/L.
4. The method according to claim 2, wherein the acidic substance in step (1) is any one or a mixture of two or more of concentrated sulfuric acid, perchloric acid and glacial acetic acid, the concentration of the acidic substance in the electrolyte solution is 3-15 mol/L, preferably the acidic substance is composed of perchloric acid and glacial acetic acid, the concentration of perchloric acid is 2.5-10 mol/L, and the concentration of glacial acetic acid is 2.5-10 mol/L.
5. The production method according to claim 2, wherein the concentration of the electrolyte solution in the step (1) is 30 to 70 wt%, and the noble metal salt is added in such an amount that the noble metal is finally contained in the finally produced catalyst in an amount of 0.01 to 2% by atom based on the weight of the catalyst.
6. The method according to claim 2, wherein the current density of the electrolysis in the step (1) is 20 to 70mA/cm2, the temperature of the electrolysis is 10 to 60 ℃, and the time of the electrolysis is 20 to 120 min.
7. The preparation method according to claim 2, wherein the solvent in the step (2) is any one or a mixture of two or more of ethanol, ethylene glycol, isopropanol, N-dimethylformamide, tetrahydrofuran, N-methylpyrrolidone and benzyl benzoate, the power of the ultrasonic wave is 20-30W, and the time of the ultrasonic wave is 1-6 h.
8. The method according to claim 2, wherein the power of the microwave radiation in step (3) is 600-1000 w, and the time of the microwave radiation is 1-10 min.
9. The preparation method according to claim 2, wherein the drying temperature in the step (1) and the drying time in the step (3) are 40-70 ℃ and 6-12 h.
10. The monatomic noble metal/graphene catalyst for hydrogenation of cinnamaldehyde, which is produced by the production method according to any one of claims 1 to 9.
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