CN112774668A - Monoatomic noble metal/graphene catalyst for hydrodechlorination of parachlorophenol and preparation method thereof - Google Patents
Monoatomic noble metal/graphene catalyst for hydrodechlorination of parachlorophenol and preparation method thereof Download PDFInfo
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- 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
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Abstract
The invention particularly relates to a preparation method of a monatomic noble metal/graphene catalyst for hydrodechlorination of parachlorophenol, 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 hydrodechlorination of chlorophenol. According to the monoatomic noble metal/graphene catalyst for the hydrodechlorination of p-chlorophenol prepared by the method, the active component noble metal is highly dispersed and stably loaded on graphene in an atomic form, and the catalyst shows high activity, high selectivity and high stability when used in a reaction of generating methylcyclohexane by selective hydrogenation of toluene.
Description
Technical Field
The invention belongs to the technical field of catalyst synthesis, and particularly relates to a monoatomic noble metal/graphene catalyst for hydrodechlorination of parachlorophenol and a preparation method thereof.
Background
Parachlorophenol is a refractory toxic and harmful organic substance with the characteristics of carcinogenesis, teratogenesis and mutagenesis, and is widely applied to chemical industries such as printing and dyeing, medicines, pesticides and the like as a chemical intermediate, and the environmental problem caused by careless leakage due to the large-scale use of parachlorophenol is increasingly severe. The parachlorophenol has strong toxicity and biological degradation resistance due to the aromatic ring structure of the parachlorophenol and the existence of chlorine atoms, and simultaneously, the existence of the chlorine atoms can inhibit the activity of benzene ring lyase so as to increase the biological resistance of the benzene ring lyase. Therefore, the most important rate-limiting step in the degradation of p-chlorophenol is the removal of chlorine substituents, i.e., dechlorination, in which hydrochloric acid, a by-product, is easily removed and phenol can be recycled. Phenol is an important organic chemical raw material, and the pollution to the environment is small compared with chlorophenol, so that dechlorination of the chlorophenol to form phenol has been an important subject in environmental research for many years. The dechlorination of the parachlorophenol mostly adopts a catalytic hydrogenation reduction technology, and the key point is the selection of a 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 the hydrodechlorination of the chlorophenol, and the most main challenges of the existing synthesis monatomic catalyst are as follows: 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 of a monatomic noble metal/graphene composite material as a catalyst for hydrodechlorination of parachlorophenol exists.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a monatomic noble metal/graphene catalyst for hydrodechlorination of p-chlorophenol, 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 graphene in an atomic scale form, and the catalyst shows high activity and high stability in the reaction of hydrodechlorination of p-chlorophenol to generate methylcyclohexane.
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 hydrodechlorination of parachlorophenol 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 hydrodechlorination of chlorophenol.
Preferably, the preparation method of the monatomic noble metal/graphene catalyst for hydrodechlorination of p-chlorophenol 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 monoatomic noble metal/graphene catalyst for the hydrodechlorination of the parachlorophenol.
Preferably, the noble metal salt in the step (1) is an inorganic salt of Pd, 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 1% 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 monoatomic noble metal/graphene catalyst for the hydrodechlorination of the parachlorophenol, which is prepared by the method, the active component noble metal is highly dispersed and stably loaded on the graphene in an atomic form and can be used for the hydrodechlorination reaction of the parachlorophenol.
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 monatomic metal through microwave radiation to obtain a monatomic noble metal/graphene catalyst for the hydrodechlorination of the parachlorophenol; the large specific surface area of the graphene provides a better place for the dispersion and stability of the noble metal, and meanwhile, the graphene can be better contacted with a reaction substrate p-chlorophenol for reaction; pi electrons in the graphene structure can form a delocalized pi bond, so that the adsorption capacity of the catalyst on chlorophenol as a reaction substrate 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; according to the prepared catalyst, the active component noble metal is loaded on the graphene in an atomic form with high dispersion and high stability, and the catalyst shows high activity and high stability when being used in the reaction of hydrodechlorination of chlorophenol.
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 hydrodechlorination of parachlorophenol 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 hydrodechlorination of chlorophenol.
Preferably, the preparation method of the monatomic noble metal/graphene catalyst for hydrodechlorination of p-chlorophenol 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 monoatomic noble metal/graphene catalyst for the hydrodechlorination of the parachlorophenol.
Preferably, the noble metal salt in step (1) is an inorganic salt of Pd, and may be any one or a mixture of two or more of chloropalladic acid, palladium chloride, palladium nitrate, sodium chloropalladate and potassium chloropalladate, 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 1% 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 monoatomic noble metal/graphene catalyst for hydrodechlorination of parachlorophenol prepared by the method, the active component noble metal is highly dispersed and stably loaded on graphene in an atomic form.
The monoatomic noble metal/graphene catalyst for hydrodechlorination of parachlorophenol prepared by the method can be used in the reaction of hydrodechlorination of parachlorophenol.
The evaluation of the performance of the above catalyst was carried out in a 25mL double-necked round-bottomed flask with hydrogen balloon, which was washed several times with pure haddock to remove air before use, as follows: the reaction temperature was controlled by a water bath at 25 ℃ and 5.0mg of a 1.0g/L aqueous catalyst solution was added to a two-necked round-bottomed flask with a hydrogen balloon, 5.0mL of a 2.5g/L aqueous solution of p-chlorophenol was added to the flask with stirring, and after the addition was completed, the reaction was continued for 1 hour, and the reaction product was quantitatively analyzed by GC (Agilent 7890).
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 sodium chloropalladate, perchloric acid and glacial acetic acid, the concentration of the sodium chloropalladate 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, then radiating the graphene dispersion liquid in 600W microwaves for 10min, washing microwave radiation products, filtering, and carrying out vacuum drying for 12h at 40 ℃ to obtain the monatomic noble metal/graphene catalyst for parachlorophenol hydrodechlorination.
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 sodium chloropalladate, perchloric acid and glacial acetic acid, the concentration of the sodium chloropalladate 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, radiating the graphene dispersion liquid in 1000W of microwave for 1min, washing a microwave radiation product, filtering, and carrying out vacuum drying at 70 ℃ for 6h to obtain the monoatomic noble metal/graphene catalyst for the hydrodechlorination of the parachlorophenol.
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 sodium chloropalladate, perchloric acid and glacial acetic acid, the concentration of the sodium chloropalladate 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 microwaves for 2min, washing microwave radiation products, filtering, and carrying out vacuum drying at 60 ℃ for 12h to obtain the monatomic noble metal/graphene catalyst for the hydrodechlorination of the parachlorophenol.
The results of using the monoatomic noble metal/graphene catalyst for hydrodechlorination of p-chlorophenol according to examples 1 to 3 in the reaction of hydrodechlorination of p-chlorophenol are shown in table 1.
Table 1: catalyst Performance test data
As can be seen from Table 1, the monatomic noble metal/graphene catalyst for the hydrodechlorination of p-chlorophenol shows the characteristic of high activity when being used in the reaction of the hydrodechlorination of p-chlorophenol, and has the characteristics of repeated use, no sintering and agglomeration phenomenon, no obvious reduction of activity and 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 hydrodechlorination of parachlorophenol 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 hydrodechlorination of chlorophenol.
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 monoatomic noble metal/graphene catalyst for the hydrodechlorination of the parachlorophenol.
3. The production method according to claim 2, wherein the noble metal salt in the step (1) is an inorganic salt of Pd, 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 1% 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 monoatomic noble metal/graphene catalyst for hydrodechlorination of parachlorophenol prepared by the preparation method according to any one of claims 1 to 9.
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