CN114345408A - Black phosphorus supported palladium nanoparticle composite material and preparation method thereof - Google Patents
Black phosphorus supported palladium nanoparticle composite material and preparation method thereof Download PDFInfo
- Publication number
- CN114345408A CN114345408A CN202111469716.2A CN202111469716A CN114345408A CN 114345408 A CN114345408 A CN 114345408A CN 202111469716 A CN202111469716 A CN 202111469716A CN 114345408 A CN114345408 A CN 114345408A
- Authority
- CN
- China
- Prior art keywords
- black phosphorus
- composite material
- nanoparticle composite
- supported palladium
- palladium nanoparticle
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention provides a black phosphorus supported palladium nanoparticle composite material and a preparation method thereof, and also provides application of the black phosphorus supported palladium nanoparticle composite material as a catalyst in the technical field of hydrogen peroxide preparation. According to the black phosphorus supported palladium nanoparticle composite material catalyst disclosed by the invention, an N-methyl amine compound is covalently grafted on the surface of a black phosphorus nanosheet in a P-C-N bond mode, and a palladium nanoparticle is combined with the black phosphorus nanosheet through a coordination bond; the problem that black phosphorus is easily oxidized is solved, and meanwhile, the palladium nanoparticles and the black phosphorus are tightly combined and uniformly distributed; and the black phosphorus has larger specific surface area, so that the physical and chemical properties are more excellent. Compared with other catalysts with palladium supported on carriers, the black phosphorus supported palladium nanoparticle composite material disclosed by the application has better catalytic performance, relatively simple production equipment and capability of mass production.
Description
Technical Field
The invention belongs to the field of high-purity chemical manufacturing, and particularly relates to a preparation method of hydrogen peroxide, in particular to a palladium catalyst for producing hydrogen peroxide and a preparation method thereof.
Background
At present, the production method of industrial hydrogen peroxide is mainly an anthraquinone method. The principle of the anthraquinone method is that anthraquinone alkyl derivatives are used as carriers in an organic solvent to be hydrogenated in the presence of a supported palladium catalyst to generate corresponding hydroanthraquinone, and the hydroanthraquinone is oxidized to generate a target product. Compared with other methods, the anthraquinone method has the advantages of mature process, high production capacity, low cost, high safety and the like, but is influenced by a plurality of factors in actual production, and particularly the production efficiency is directly influenced by the use of the anthraquinone hydrogenation catalyst. The prior anthraquinone hydrogenation catalyst generally has the problems of high price of active noble metal, low dispersion degree of active components, lower utilization rate, poorer stability and the like.
U.S. Pat. No. 3, 4,061,598 (published Japanese 1977.12.6) discloses a process for the preparation of a palladium-alumina catalyst. This patent uses gamma-Al 2O3 or delta-or theta-alumina as a carrier, and impregnates the alumina carrier with an appropriate amount of aqueous potassium carbonate solution, but keeps the surface of the carrier from being wetted, and then mixes the finely weighed, ground, dry palladium salt of sodium chloride with the above alumina carrier for 30 minutes and then stands at room temperature for 48 hours. The catalyst was reduced with an aqueous hydrazine solution and washed with deionized water to a wash water pH of 7, dried at 30 ℃ for one night, and then treated at 550 ℃ for 4 hours in an air atmosphere. The catalyst has a palladium content of 0.3 to 5.0% by weight, and is said to have an excellent operating life and a high activity.
Chinese invention CN111589443A (published japanese 20200828) discloses a preparation method of a graphene supported palladium nanoparticle composite catalyst. Putting graphene oxide into a palladium chloride solution for dipping, reducing at high temperature in an H2 atmosphere, dipping again, and chemically reducing: adding phenylboronic acid, bromobenzene and cesium carbonate into the solution in the step (4) according to a certain molar ratio for chemical reduction; and separating and drying to obtain the graphene supported palladium nanoparticle catalyst with the palladium loading of 1.0-2.5 wt%. The process flow is simple, the conditions are mild, and the prepared catalyst is high in activity and can be repeatedly used.
Black phosphorus, an emerging two-dimensional material, has been widely used to prepare catalysts for different electrocatalytic reactions (including but not limited to hydrogen evolution reaction, oxygen evolution reaction, carbon dioxide reduction reaction, nitrogen fixation reaction, etc.) and shows great potential. Chinese invention CN112138690A (published japanese 20201229) discloses a method for catalyzing biomass to convert into high-density liquid fuel, comprising the following steps: s1: preparing black phosphorus quantum dots; s2: PLA-PEG modifies the black phosphorus quantum dots; s3: and (3) preparing a catalyst. According to the nickel catalyst loaded with the black phosphorus quantum dots, the black phosphorus quantum dots have a layered structure and a large specific surface area, and the black phosphorus quantum dots modified by PLA-PEG can be well dispersed in a reaction solution, so that the catalyst can be effectively contacted with reaction raw materials, and the reaction rate is improved. And the catalyst and the reaction solution are not mutually soluble, which is beneficial to the post-reaction treatment and saves the economic cost.
At present, a catalyst prepared from hydrogen peroxide is usually prepared by adopting an impregnation method so that palladium is adsorbed on a carrier, and the problems of uneven distribution of effective catalytic components, weak adsorption of the palladium and the carrier, low catalytic efficiency and the like exist; in addition, no proposal has been reported for using black phosphorus as a carrier to support palladium as a catalyst for the preparation of hydrogen peroxide.
Disclosure of Invention
In view of the above, the invention provides a black phosphorus-supported palladium nanoparticle composite material and a preparation method thereof, and also provides application of the black phosphorus-supported palladium nanoparticle composite material as a catalyst in the technical field of hydrogen peroxide preparation.
In a first aspect, the invention provides a black phosphorus-supported palladium nanoparticle composite material, which is composed of black phosphorus nanosheet-supported palladium nanoparticles with N-methylamines modified on the surface, wherein the N-methylamines are covalently grafted on the surface of the black phosphorus nanosheets by means of P-C-N bonds; the palladium nanoparticles are combined with the black phosphorus nanosheets through coordination bonds.
Preferably, the N-methylamines are compounds containing N-methyl groups and amino groups.
In a second aspect, the invention provides a preparation method of a black phosphorus supported palladium nanoparticle composite material, which comprises the following steps:
the preparation method of the black phosphorus supported palladium nanoparticle composite material is characterized by comprising the following steps of:
(1) dispersing the black phosphorus nanosheets in an organic solvent to prepare an organic solvent dispersion liquid of the black phosphorus nanosheets; dissolving N-methyl amine compounds in an organic solvent to prepare a surface modifier solution; uniformly mixing a palladium salt solution, an aromatic phenol solution and a reducing agent to obtain an organic solution of palladium nanoparticles;
(2) mixing the black phosphorus nanosheet dispersion liquid with a surface modifier to obtain a mixture, placing the mixture in an inert atmosphere, performing heating reflux reaction in a sealed system, cooling after the reaction is finished, and performing liquid-solid separation to obtain a black phosphorus nanosheet with a modified surface;
(3) adding the black phosphorus nanosheet subjected to surface modification into an organic solvent for dispersion; and then adding an organic solution of palladium nanoparticles, uniformly mixing, placing in an inert atmosphere, heating in a sealed system, performing reflux reaction, cooling a mixed solution after the reaction is finished, performing liquid-solid separation, washing, and drying to obtain the black phosphorus supported palladium nanoparticle composite material.
The N-methyl amine compound is a compound containing N-methyl and amino, and is selected from at least one of methylamine, methyl hydrazine, N-methyl ethylenediamine, N-dimethyl ethylenediamine, N-methyl-1, 3-propane diamine and N, N-dimethyl-1, 3-diaminopropane.
In the case where N-methylethylenediamine is not contained in step (1), Pd as a catalyst cannot be supported on black phosphorus, and the technical effects of the present example cannot be achieved.
The aromatic phenol solution is prepared by dissolving one or more than two of aromatic phenols and derivatives thereof, namely phenol, hydroquinone, resorcinol, phloroglucinol, 1-naphthol and 2-naphthol, in absolute ethyl alcohol; the reducing agent is at least one of formaldehyde, sodium borohydride, ethanol and ascorbic acid.
The Pd nanoparticles cannot be prepared without containing aromatic phenol solution and/or reducing agent.
The organic solvent is at least one of amide solvents and alcohol solvents, and the amide solvents are at least one of formamide, dimethylformamide, diethylformamide, dimethylacetamide and diethylacetamide; the alcohol solvent is at least one selected from monohydric alcohol, dihydric alcohol and polyhydric alcohol.
The mass ratio of the black phosphorus nanosheet to the surface modifier to the palladium salt solution can be (0.01-1): 10-100): 0.1-10); the mass ratio of the palladium salt solution to the aromatic phenol solution to the reducing agent is 1: 0.5-10: 1-10.
The reaction temperature in the step (2) is 20-300 ℃, and the reaction time is 0.01-60 h. Preferably, the reaction temperature in the step (2) is 80-160 ℃, and the reaction time is 0.5-50 h.
The reaction temperature in the step (3) is 40-200 ℃, and the reaction time is 1-50 h. Preferably, the reaction temperature in the step (3) is 20-300 ℃, and the reaction time is 0.5-50 h.
The black phosphorus dispersion liquid also contains a surfactant; the surfactant includes at least one of a nonionic surfactant, an anionic surfactant, or a cationic surfactant.
Preferably, the nonionic surfactant includes at least one of polyvinylpyrrolidone, polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer and alkyl polyoxyethylene phenol ether, the anionic surfactant includes at least one of alkyl sulfonate, alkylbenzene sulfonate, fatty alcohol sulfate, fatty alcohol ether sulfate, oleamide methyl taurate and fatty alcohol phosphate surfactant, and the cationic surfactant includes at least one of fatty amine salt, higher fatty amine salt and quaternary ammonium salt surfactant.
The invention also provides a preparation method of hydrogen peroxide, and the application of the black phosphorus supported palladium nanoparticle composite material as a catalyst or the black phosphorus supported palladium nanoparticle composite material prepared by the method as a catalyst in preparing hydrogen peroxide by catalyzing anthraquinone compounds is provided.
Preferably, the anthraquinone compound is 2-alkyl anthraquinone.
Preferably, the anthraquinone compound comprises at least one of 2-ethyl anthraquinone, 2-tertiary amyl anthraquinone and 2-amyl anthraquinone.
The invention provides a black phosphorus supported palladium nanoparticle composite material and a preparation method thereof, and also provides application of the black phosphorus supported palladium nanoparticle composite material as a catalyst in the technical field of hydrogen peroxide preparation. According to the black phosphorus supported palladium nanoparticle composite material catalyst disclosed by the invention, the N-methyl amine compound is covalently grafted on the surface of a black phosphorus nanosheet in a P-C-N bond manner; the palladium nanoparticles and the black phosphorus nanosheets are combined through coordination bonds; the palladium nano particles are tightly combined with the black phosphorus and are uniformly distributed; and because the black phosphorus has a larger specific surface area, the physical and chemical properties are more excellent, and compared with other catalysts with palladium supported on carriers, the black phosphorus supported palladium nanoparticle composite material disclosed by the application has better catalytic performance, the required production equipment is relatively simple, and the mass production can be realized.
Detailed Description
Example 1
1) Dispersing 1g of black phosphorus nanosheets into 50mL of isopropanol (HPLC level) to prepare an organic solvent dispersion liquid of the black phosphorus nanosheets; dissolving 30mL of LN-methyl ethylenediamine into a proper amount of isopropanol to prepare 50mL of surface modifier solution; resorcinol was dissolved in absolute ethanol to make a solution of 22g/L, Na2PdCl4 was made a solution of 0.12 mol/L.
2) Mixing the organic solvent dispersion liquid of the black phosphorus nanosheet and the surface modifier solution to obtain a mixture, placing the mixture at 80 ℃ for refluxing for 1 hour, cooling, centrifuging, and cleaning the solid part by using absolute ethyl alcohol; obtaining a black phosphorus nanosheet with a modified surface;
3) re-dispersing the surface-modified black phosphorus nanosheet prepared in the step 2) in 50mL of absolute ethanol, and adding 45mL of resorcinol solution and 10mL of Na2PdCl4Uniformly mixing the solution and 5mL of formaldehyde solution (35 wt%) to obtain an organic solution of palladium nanoparticles; continuously placing the mixture in a sealed system heated in an inert atmosphere for reflux reaction at 40 ℃ for 24 hours;
4) and cooling the mixed solution, centrifuging for liquid-solid separation, washing the solid part for a plurality of times by the mixed solution of absolute ethyl alcohol and water, and drying in a drying oven at the temperature of 60 ℃ to obtain the black phosphorus supported palladium nanoparticle composite material of the black phosphorus nanosheet supported palladium nanoparticle with the surface modified with dialkyl methylamine.
The activity of the catalyst was tested in an anthraquinone hydrogenation unit in which the gas was 99.99% by mass hydrogen, the liquid was anthraquinone working liquid (2-ethylanthraquinone dissolved in a working liquid formed by a mixed solution of trioctyl phosphate and C9 heavy aromatics at a volume ratio of 1: 3), the reaction temperature was controlled at 80 ℃, the reaction pressure was atmospheric pressure, and the gas mass space velocity was 0.27m3·h-1·kg-1The liquid mass space velocity is 0.0019m3 & h-1 & kg-1, the conversion rate of 2-ethyl anthraquinone is 45.29 percent, and the yield of hydrogen peroxide per unit mass of Pd is 493.20gH2O2/(gPd·hr)。
Example 2
1) Dispersing 0.1g of black phosphorus nanosheets into 50mL of absolute ethyl alcohol to prepare an organic solvent dispersion liquid of the black phosphorus nanosheets; 50mL of methylamine ethanol solution (25wt%) was used as a surface modifier solution; dissolving resorcinol in anhydrous ethanol to obtain 20g/L solution, adding Na2PdCl40.05mol/L solution is prepared.
2) Mixing the mixed black phosphorus nanosheet dispersion liquid with a surface modifier solution to obtain a mixture, placing the mixture at 40 ℃ for refluxing for 5 hours, cooling, centrifuging, and cleaning a solid part with absolute ethyl alcohol; obtaining a black phosphorus nanosheet with a modified surface;
3) re-dispersing the surface-modified black phosphorus nanosheet prepared in the step 2) in 50mL of absolute ethanol, adding 0.2g of Sodium Dodecyl Benzene Sulfonate (SDBS), and uniformly mixing; then add 45mL resorcinol solution, 5mL Na2PdCl4Uniformly mixing the solution and 1mL of formaldehyde solution (35 wt%) to obtain an organic solution of palladium nanoparticles; continuously placing the mixture in a sealed system heated in inert atmosphere for reflux reaction at 80 ℃ for 10 hours;
4) and cooling the mixed solution, centrifuging for liquid-solid separation, washing the solid part for a plurality of times by the mixed solution of absolute ethyl alcohol and water, and drying in a drying oven at the temperature of 60 ℃ to obtain the black phosphorus supported palladium nanoparticle composite material of the black phosphorus nanosheet supported palladium nanoparticle with the surface modified with dialkyl methylamine.
The detection means in example 1 is adopted to detect that the conversion rate of 2-ethylanthraquinone is 40.36% and the yield of hydrogen peroxide per unit mass of Pd is 439.51gH2O2/(gPd hr) in the process of producing hydrogen peroxide from 2-ethylanthraquinone.
Example 3
1) Dispersing 10g of black phosphorus nanosheets into 50mL of absolute ethyl alcohol to prepare organic solvent dispersion liquid of the black phosphorus nanosheets; taking 50mLN, N-dimethyl ethylenediamine as a surface modifier solution; resorcinol is dissolved in absolute ethyl alcohol to prepare a solution of 25g/L, and PdCl2 is prepared into a solution of 0.15 mol/L.
2) Mixing the mixed black phosphorus nanosheet dispersion liquid with a surface modifier solution to obtain a mixture, placing the mixture at 100 ℃ for refluxing for 2 hours, cooling, centrifuging, and cleaning a solid part with absolute ethyl alcohol; obtaining a black phosphorus nanosheet with a modified surface;
3) re-dispersing the surface-modified black phosphorus nanosheet prepared in the step 2) in 50mL of absolute ethanol, adding 1.8g of Sodium Dodecyl Benzene Sulfonate (SDBS), and uniformly mixing; then 25mL of resorcinol solution and 25mL of PdCl are added2Uniformly mixing the solution and 10mL of formaldehyde solution (35 wt%) to adjust the pH value to be neutral to obtain an organic solution of palladium nanoparticles; continuously placing the mixture in a sealed system heated in an inert atmosphere for reflux reaction at 60 ℃ for 24 hours;
4) and cooling the mixed solution, centrifuging for liquid-solid separation, washing the solid part for a plurality of times by the mixed solution of absolute ethyl alcohol and water, and drying in a drying oven at the temperature of 60 ℃ to obtain the black phosphorus supported palladium nanoparticle composite material of the black phosphorus nanosheet supported palladium nanoparticle with the surface modified with dialkyl methylamine.
The detection means in example 1 is adopted to detect that the conversion rate of 2-ethylanthraquinone is 42.15% and the yield of hydrogen peroxide per unit mass of Pd is 459.00gH2O2/(gPd hr) in the process of producing hydrogen peroxide from 2-ethylanthraquinone.
Example 4
The procedure and procedure were as in example 1 except that 30mL of N, N-dimethyl-1, 3-diaminopropane was dissolved in an appropriate amount of isopropyl alcohol to prepare 50mL of a surface modifier solution. Then, the detection means in example 1 is adopted to detect that the conversion rate of 2-ethylanthraquinone is 41.56% and the yield of hydrogen peroxide per unit mass of Pd is 452.58gH2O2/(gPd hr) in the process of producing hydrogen peroxide from 2-ethylanthraquinone.
Example 5
The method and the steps are the same as example 1, only the reducing agent is adjusted to ascorbic acid, and the detection means in example 1 is adopted to detect that the conversion rate of 2-ethyl anthraquinone in the process of producing hydrogen peroxide by 2-ethyl anthraquinone, of the black phosphorus supported palladium nanoparticle composite material obtained in the embodiment, is 38.20%, and the yield of hydrogen peroxide per unit mass of Pd is 415.99gH2O2/(gPd hr).
Example 6
The method and the steps are the same as example 1, only the reducing agent is adjusted to be sodium borohydride, and the detection means in example 1 is adopted to detect that the conversion rate of 2-ethyl anthraquinone is 39.14% and the yield of hydrogen peroxide per unit mass of Pd is 426.23gH2O2/(gPd · hr) in the process of producing hydrogen peroxide from 2-ethyl anthraquinone in the black phosphorus supported palladium nanoparticle composite material obtained in the embodiment.
Example 7
The method and the steps are the same as example 1, only sodium dodecyl benzene sulfonate in step 3) is replaced by tetramethylammonium acetate, and the detection means in example 1 is adopted to detect that the conversion rate of 2-ethylanthraquinone is 36.31% and the yield of hydrogen peroxide per unit mass of Pd is 395.41gH2O2/(gPd · hr) in the process of producing hydrogen peroxide from 2-ethylanthraquinone.
Example 8
The method and the steps are the same as example 1, only sodium dodecyl benzene sulfonate in step 3) is replaced by polyvinylpyrrolidone, and the detection means in example 1 is adopted to detect that the conversion rate of 2-ethylanthraquinone is 50.22% and the yield of hydrogen peroxide per unit mass of Pd is 545.62gH2O2/(gPd · hr) in the process of producing hydrogen peroxide from 2-ethylanthraquinone.
Example 9
The method and the steps are the same as those of example 1, only the aromatic phenol solution is replaced by the hydroquinone ethanol solution, and the detection means of example 1 is adopted to detect that the conversion rate of 2-ethylanthraquinone is 44.32% and the yield of hydrogen peroxide per unit mass of Pd is 482.64gH2O 2/(gPd. hr) in the process of producing hydrogen peroxide from 2-ethylanthraquinone.
Example 10
The method and the steps are the same as those of example 1, only the aromatic phenol solution is replaced by the phenol ethanol solution, and the detection means in example 1 is adopted to detect that the conversion rate of 2-ethyl anthraquinone in the process of producing hydrogen peroxide from 2-ethyl anthraquinone, and the yield of hydrogen peroxide per unit mass of Pd is 475.78gH2O2/(gPd hr).
Claims (10)
1. The black phosphorus-supported palladium nanoparticle composite material is characterized by being composed of black phosphorus nanosheet-supported palladium nanoparticles with N-methyl amine compounds modified on the surfaces, wherein the N-methyl amine compounds are covalently grafted on the surfaces of the black phosphorus nanosheets in a P-C-N bond manner; the palladium nanoparticles are combined with the black phosphorus nanosheets through coordination bonds.
2. The black phosphorus-supported palladium nanoparticle composite material according to claim 1, wherein the N-methyl amine-based compound is a compound containing an N-methyl group and an amino group.
3. A preparation method of a black phosphorus supported palladium nanoparticle composite material is characterized by comprising the following steps:
(1) dispersing the black phosphorus nanosheets in an organic solvent to prepare an organic solvent dispersion liquid of the black phosphorus nanosheets; dissolving N-methyl amine compounds in an organic solvent to prepare a surface modifier solution; uniformly mixing a palladium salt solution, an aromatic phenol solution and a reducing agent to obtain an organic solution of palladium nanoparticles;
(2) mixing the black phosphorus nanosheet dispersion liquid with a surface modifier to obtain a mixture, placing the mixture in an inert atmosphere, performing heating reflux reaction in a sealed system, cooling after the reaction is finished, and performing liquid-solid separation to obtain a black phosphorus nanosheet with a modified surface;
(3) adding the black phosphorus nanosheet subjected to surface modification into an organic solvent for dispersion; and then adding an organic solution of palladium nanoparticles, uniformly mixing, placing in an inert atmosphere, heating in a sealed system, performing reflux reaction, cooling a mixed solution after the reaction is finished, performing liquid-solid separation, washing, and drying to obtain the black phosphorus supported palladium nanoparticle composite material.
4. The method for preparing a black phosphorus-supported palladium nanoparticle composite material according to claim 3, wherein the N-methyl amine compound is a compound containing an N-methyl group and an amino group, and the N-methyl amine compound is at least one selected from the group consisting of methylamine, methylhydrazine, N, -methylethylenediamine, N, -dimethylethylenediamine, N-methyl-1, 3-propanediamine, and N, N-dimethyl-1, 3-diaminopropane.
5. The preparation method of the black phosphorus-supported palladium nanoparticle composite material as claimed in claim 3, wherein the aromatic phenol solution is prepared by dissolving one or more than two of aromatic phenols and derivatives thereof selected from phenol, hydroquinone, resorcinol, phloroglucinol, 1-naphthol and 2-naphthol in absolute ethyl alcohol, and the reducing agent is at least one of formaldehyde, sodium borohydride, ethanol and ascorbic acid.
6. The method for preparing a black phosphorus-supported palladium nanoparticle composite material according to claim 3, wherein the organic solvent is at least one selected from an amide solvent and an alcohol solvent, and the amide solvent is at least one selected from formamide, dimethylformamide, diethylformamide, dimethylacetamide and diethylacetamide; the alcohol solvent is at least one selected from monohydric alcohol, dihydric alcohol and polyhydric alcohol.
7. The preparation method of the black phosphorus-supported palladium nanoparticle composite material as claimed in claim 3, wherein the mass ratio of the black phosphorus nanosheet, the surface modifier and the palladium salt solution is (0.01-1): 10-100): 0.1-10); the mass ratio of the palladium salt solution to the aromatic phenol solution to the reducing agent is 1: 0.5-10: 1-10.
8. The preparation method of the black phosphorus-supported palladium nanoparticle composite material as claimed in claim 3, wherein the reaction temperature in the step (2) is 80-160 ℃, and the reaction time is 0.5-50 h; the reaction temperature in the step (3) is 40-200 ℃, and the reaction time is 1-50 h.
9. The method for preparing the black phosphorus-supported palladium nanoparticle composite material according to claim 3, wherein in the step (3), the surface-modified black phosphorus nanosheet further comprises a surfactant; the surfactant includes at least one of a nonionic surfactant, an anionic surfactant, or a cationic surfactant.
10. A method for preparing hydrogen peroxide, which is characterized by using the black phosphorus supported palladium nanoparticle composite material as described in claim 1 or 2 or the black phosphorus supported palladium nanoparticle composite material prepared by any one of the methods described in claims 3 to 8 as a catalyst to catalyze the application of anthraquinone compounds to prepare hydrogen peroxide; the anthraquinone compound comprises at least one of 2-ethyl anthraquinone, 2-tertiary amyl anthraquinone and 2-amyl anthraquinone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111469716.2A CN114345408A (en) | 2021-12-04 | 2021-12-04 | Black phosphorus supported palladium nanoparticle composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111469716.2A CN114345408A (en) | 2021-12-04 | 2021-12-04 | Black phosphorus supported palladium nanoparticle composite material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114345408A true CN114345408A (en) | 2022-04-15 |
Family
ID=81098188
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111469716.2A Pending CN114345408A (en) | 2021-12-04 | 2021-12-04 | Black phosphorus supported palladium nanoparticle composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114345408A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115172775A (en) * | 2022-07-04 | 2022-10-11 | 郑州大学 | Black phosphorus nanodot modified Pt/C composite material and preparation method and application thereof |
| CN115445644A (en) * | 2022-09-14 | 2022-12-09 | 湖北兴发化工集团股份有限公司 | Preparation method and application of black phosphorus modified alumina carrier |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB859219A (en) * | 1956-11-24 | 1961-01-18 | Fmc Corp | Improvements in or relating to the production of hydrogen peroxide |
| CN106744755A (en) * | 2017-03-24 | 2017-05-31 | 福州大学 | The preparation method of black phosphorus nanometer sheet and noble metal nano particles composite |
| CN107469845A (en) * | 2017-08-04 | 2017-12-15 | 深圳先进技术研究院 | A kind of black phosphorus/noble metal composite-material, its preparation method and application |
| CN111483988A (en) * | 2020-04-17 | 2020-08-04 | 厦门大学 | Preparation method of antioxidant black phosphorus nanosheet |
-
2021
- 2021-12-04 CN CN202111469716.2A patent/CN114345408A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB859219A (en) * | 1956-11-24 | 1961-01-18 | Fmc Corp | Improvements in or relating to the production of hydrogen peroxide |
| CN106744755A (en) * | 2017-03-24 | 2017-05-31 | 福州大学 | The preparation method of black phosphorus nanometer sheet and noble metal nano particles composite |
| CN107469845A (en) * | 2017-08-04 | 2017-12-15 | 深圳先进技术研究院 | A kind of black phosphorus/noble metal composite-material, its preparation method and application |
| CN111483988A (en) * | 2020-04-17 | 2020-08-04 | 厦门大学 | Preparation method of antioxidant black phosphorus nanosheet |
Non-Patent Citations (1)
| Title |
|---|
| YUANYUAN CHEN: """Stable Radicals with Protective Umbrellas Integrated on the Surface of 2D Layered Materials""", 《ADVANCED FUNCTIONAL MATERIALS》, vol. 31, pages 140 - 1411 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115172775A (en) * | 2022-07-04 | 2022-10-11 | 郑州大学 | Black phosphorus nanodot modified Pt/C composite material and preparation method and application thereof |
| CN115445644A (en) * | 2022-09-14 | 2022-12-09 | 湖北兴发化工集团股份有限公司 | Preparation method and application of black phosphorus modified alumina carrier |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114345408A (en) | Black phosphorus supported palladium nanoparticle composite material and preparation method thereof | |
| CN109603819B (en) | Graphene-loaded PdRu bimetallic catalyst and preparation method and application thereof | |
| CN113649004B (en) | Hollow carbon sphere supported metal particle catalyst and preparation method and application thereof | |
| CN106732559A (en) | A kind of palladium catalyst of cherry stone carbon load and preparation method and application | |
| CN101185904A (en) | Selectivity liquid phase hydrogenation catalyst and preparation method and use thereof | |
| CN101947444B (en) | Attapulgite load nano Pd catalyst and method for preparing chloroaniline by catalyzing and deoxidating attapulgite load nano Pd catalyst | |
| CN111036195A (en) | Catalyst and preparation method of 2, 5-furandicarboxylic acid | |
| CN106391000A (en) | Pd(111)/gamma-Al2O3 catalyst for CO dehydrogenation purification reaction and preparation method thereof | |
| CN108654621A (en) | A kind of preparation method of Ni/C core-shell materials | |
| Isaeva et al. | Hydroamination of phenylacetylene in the presence of gold-containing catalytic systems supported on carriers modified by ionic liquids | |
| CN114933535B (en) | Preparation method of membrane reactor and method for co-producing aniline and 4-aminodiphenylamine from nitrobenzene | |
| CN111686726B (en) | Preparation method and application of carbon-based noble metal catalyst | |
| CN114100653B (en) | Nitride supported palladium catalyst and preparation method and application thereof | |
| CN102060656A (en) | Method for preparing cyclohexanone | |
| CN107684930B (en) | Preparation method of catalyst for preparing cyclohexanone by phenol hydrogenation | |
| Chen et al. | Use of amidoxime polyacrylonitrile bead-supported Pd-based nanoparticles as high efficiency catalysts for dehydrogenation of formic acid | |
| CN113649049A (en) | Maleic anhydride selective hydrogenation catalyst, and preparation method and application method thereof | |
| CN107649184B (en) | Perfusion silica gel/nanogold composite microspheres and preparation method and application thereof | |
| CN108654685B (en) | Method for improving catalytic selectivity of organic matter sites | |
| US20220331789A1 (en) | Catalyst for synthesis of hydrogen peroxide and recovery, and method of preparing same | |
| CN113546651B (en) | Phosphorus-modified carbon-based catalyst and preparation method and application thereof | |
| CN113134372B (en) | CO-resistant anthraquinone hydrogenation catalyst and preparation method thereof | |
| CN113135818B (en) | Method for hydrogenating alkyl anthraquinone | |
| CN112657485B (en) | Method for preparing tetrahydrofurfuryl alcohol and pentanediol through furfuryl alcohol hydrogenation | |
| CN114570430B (en) | Single-site gold-loaded covalent organic framework catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |