CN114210332A - Preparation method of cobalt metal-nitrogen co-doped carbon material catalyst - Google Patents
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J37/082—Decomposition and pyrolysis
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- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B43/00—Formation or introduction of functional groups containing nitrogen
- C07B43/04—Formation or introduction of functional groups containing nitrogen of amino groups
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- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
- C07C209/365—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst by reduction with preservation of halogen-atoms in compounds containing nitro groups and halogen atoms bound to the same carbon skeleton
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
Abstract
The invention provides a preparation method of a cobalt metal-nitrogen co-doped carbon material catalyst, which comprises the following steps: respectively adding 8-hydroxyquinoline, sodium hydroxide and a solvent into a round-bottom flask, changing the color of a reaction system from light yellow to reddish brown, adding cobalt sulfate heptahydrate, changing the color of the reaction system to yellowish green, stopping the reaction, cooling the reaction to room temperature, filtering, washing a filter cake with water and ethanol for three times respectively, drying to obtain 8-hydroxyquinoline cobalt, stirring the 8-hydroxyquinoline cobalt and a template agent in a mixed solvent uniformly at the room temperature, evaporating the solvent under reduced pressure, pyrolyzing the solid at the temperature of 500 ℃ and 900 ℃ in a nitrogen atmosphere to obtain a black solid, and performing acid treatment on the black solid to obtain the catalyst. The cobalt metal-nitrogen co-doped carbon material catalyst with the pore structure is simple to prepare and has excellent catalytic activity in the reaction of reducing nitro compounds into amine compounds.
Description
Technical Field
The invention belongs to the technical field of catalyst material preparation, and particularly relates to a preparation method of a cobalt metal-nitrogen co-doped carbon material catalyst.
Background
Aromatic amines are important organic intermediates for the synthesis of dyes, agrochemicals and pharmaceuticals. The conventional method is reduction with iron and hydrochloric acid or acetic acid, or other soluble metals such as zinc or tin in the presence of hydrochloric acid, but there are difficulties in separating and purifying the product from the formed metal sludge, resulting in complicated subsequent treatment, and in order to avoid these disadvantages of the conventional method, most of aromatic amines are currently prepared by catalytic reduction of aromatic nitro compounds, and particularly, metal-supported heterogeneous catalysts having high catalytic performance and being environmentally friendly, such as platinum group metal (Pt, Rh, Ru, Pd) catalysts, have been widely studied due to their high activity in the reduction of nitroarenes. However, most of the reported noble metal catalysts have poor chemical selectivity to nitro compounds containing halogens (F, Cl, Br and I), are easy to remove halogens, and the scarcity and price fluctuation of noble metals limit the application scale of the noble metals in the chemical industry.
Therefore, the development of a non-noble metal-supported heterogeneous catalyst with high selectivity and high conversion rate is important for the reduction reaction of nitro compounds.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a method for preparing a cobalt metal-nitrogen co-doped carbon material catalyst, so as to solve the problems in the background art.
In order to solve the technical problems, the invention adopts the technical scheme that: the preparation method of the cobalt metal-nitrogen co-doped carbon material catalyst comprises the following steps:
s1, respectively adding 8-hydroxyquinoline, sodium hydroxide and a solvent into a round-bottom flask, changing the color of a reaction system from light yellow to reddish brown, adding cobalt sulfate heptahydrate, changing the color of the reaction system to yellowish green, and stopping the reaction;
s2, cooling the reaction in the S1 to room temperature, filtering, washing a filter cake with water and ethanol for three times respectively, and drying to obtain a yellow solid;
s3, 2.0g of the yellow solid obtained in S2 was weighed out and mixed with 5.0g of colloidal SiO at room temperature2In CH3CH2OH: of DMF 3:1Stirring the mixed solvent for 4 hours, and evaporating the solvent to dryness under reduced pressure to obtain 4.0g of solid;
s4, pyrolyzing the solid obtained in the S3 at the temperature of 900 ℃ under the protection of nitrogen to obtain a black solid;
s5, the black solid obtained in S4 was treated with an aqueous HF solution to obtain a catalyst.
Further, in S1, 8-hydroxyquinoline: the molar ratio of sodium hydroxide is 1:1, 8-hydroxyquinoline: the molar ratio of cobalt sulfate heptahydrate was 2: 1.
Further, in S1, the reaction is firstly carried out for 4 hours at 80 ℃, the color of the reaction system is changed from light yellow to red brown, cobalt sulfate heptahydrate is added for reaction for 2 hours, the color of the system is changed to yellow green, and the reaction is stopped.
Further, in S1, the solvent is water.
Further, in S4, the pyrolysis conditions are: heating to 500-900 ℃ by a program of 3 ℃/min, and keeping the temperature for 2 hours.
Further, in S5, the treatment is performed with an aqueous HF solution, specifically, an acid washing is performed with a 10 wt% aqueous HF solution at room temperature for 12 hours.
Compared with the prior art, the invention has the following advantages:
according to the invention, 8-hydroxyquinoline cobalt is used as a precursor, silicon dioxide is used as a template agent, pyrolysis and acid washing are carried out, and the cobalt metal-nitrogen co-doped carbon material catalyst with a pore structure is prepared. The catalyst is applied to the reduction reaction of the nitro compound, the reaction condition is mild, the product purification is simple, the cycle can be carried out for 6 times, and the catalyst has good industrial prospect.
Drawings
FIG. 1 is a Raman diagram of Co/NCA-700, Co/NCA-800 and Co/NCA-900 in an example of the present invention.
FIG. 2 is a diagram of Co/NCA-SiO in an example of the present invention2Thermogram of (c).
FIG. 3 shows Co/NCA-SiO in an example of the present invention2-500、Co/NCA-SiO2-600、Co/NCA-SiO2-700、Co/NCA-SiO2800 and Co/NCA-SiO2-XRD pattern of 900.
FIG. 4 is an XRD pattern of Co/NCA-800 in an example of the present invention.
FIGS. 5 a, b and c are scanning electron micrographs of Co/NCA-700, Co/NCA-800 and Co/NCA-900, respectively, in examples of the present invention.
FIGS. 6 a, b and c are transmission electron micrographs of Co/NCA-700, Co/NCA-800 and Co/NCA-900, respectively, in examples of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As shown in fig. 1 to 6, in embodiment 1, the present invention provides a technical solution: a preparation method of a cobalt metal-nitrogen co-doped carbon material catalyst comprises the following steps:
s1, respectively weighing 4.3548g and 30mmol of 8-hydroxyquinoline, 1.2062g and 30mmol of sodium hydroxide, adding 50ml of water, reacting at 80 ℃ for 4 hours until the color of the system changes from light yellow to reddish brown, adding 4.2165g and 15mmol of cobalt sulfate heptahydrate, reacting for 2 hours until the color of the system changes to yellowish green, and stopping the reaction;
s2, cooling to room temperature, filtering, washing a filter cake with water and ethanol for three times respectively, and drying to obtain a yellow solid with the yield of 95%.
S3, 2.0g of the obtained yellow solid is weighed and mixed with 5.0g of colloidal SiO at room temperature2In CH3CH2OH: stirring the mixed solvent of DMF (3: 1) for 4 hours, and evaporating the solvent under reduced pressure to obtain 4.0g of solid;
s4, weighing 2.0g of the obtained solid, annealing in a tube furnace under the protection of nitrogen, raising the temperature to 500 ℃ through a program of 3 ℃/min, keeping the temperature for 2 hours, completing the pyrolysis of the N-doped carbon material, and obtaining 1.56g of black solid marked as Co/NCA-SiO2-500；
S5, weighing 1.0g of the obtained black solid, treating with 10 wt% HF aqueous solution, reacting for 12h at room temperature, and removing SiO2And cobalt nanoparticles to give 0.27g of the target Co/NCA-500 catalyst.
Embodiment 2, the present invention provides a technical solution: a preparation method of a cobalt metal-nitrogen co-doped carbon material catalyst comprises the following steps:
s1, weighing 4.3548g and 30mmol of 8-hydroxyquinoline and 1.2062g and 30mmol of sodium hydroxide respectively, adding 50ml of water, reacting for 4 hours at 80 ℃, adding 4.2165g and 15mmol of cobalt sulfate heptahydrate, reacting for 2 hours, and stopping the reaction, wherein the color of the system is changed from light yellow to reddish brown.
S2, cooling to room temperature, filtering, washing a filter cake with water and ethanol for three times respectively, and drying to obtain a yellow solid with the yield of 95%.
S3, 2.0g of the obtained yellow solid is weighed and mixed with 5.0g of colloidal SiO at room temperature2In CH3CH2OH: stirring the mixed solvent of DMF (3: 1) for 4 hours, and evaporating the solvent under reduced pressure to obtain 4.0g of solid;
s4, weighing 2.0g of the obtained solid, annealing in a tube furnace under the protection of nitrogen, raising the temperature to 600 ℃ through a program of 3 ℃/min, keeping the temperature for 2 hours, completing the pyrolysis of the N-doped carbon material, and obtaining 1.49g of black solid marked as Co/NCA-SiO2-600；
S5, weighing 1.0g of the obtained black solid, treating with 10 wt% HF aqueous solution, reacting for 12h at room temperature, and removing SiO2And cobalt nanoparticles to obtain 0.258g of the target Co/NCA-600 catalyst.
Example 3: the invention provides a technical scheme that: a preparation method of a cobalt metal-nitrogen co-doped carbon material catalyst comprises the following steps:
s1, weighing 4.3548g and 30mmol of 8-hydroxyquinoline and 1.2062g and 30mmol of sodium hydroxide respectively, adding 50ml of water, reacting for 4 hours at 80 ℃, adding 4.2165g and 15mmol of cobalt sulfate heptahydrate, reacting for 2 hours, and stopping the reaction, wherein the color of the system is changed from light yellow to reddish brown.
S2, cooling to room temperature, filtering, washing a filter cake with water and ethanol for three times respectively, and drying to obtain a yellow solid with the yield of 95%.
S3, 2.0g of the obtained yellow solid is weighed and mixed with 5.0g of colloidal SiO at room temperature2In CH3CH2OH: stirring the mixed solvent of DMF (3: 1) for 4 hours, and evaporating the solvent under reduced pressure to obtain 4.0g of solid;
s4, weighing 2.0g of the obtained solid, annealing in a tube furnace under the protection of nitrogen, raising the temperature to 700 ℃ through a program of 3 ℃/min, keeping the temperature for 2 hours, completing the pyrolysis of the N-doped carbon material, and obtaining 1.46g of black solid marked as Co/NCA-SiO2-700；
S5, weighing 1.0g of the obtained black solid, treating with 10 wt% HF aqueous solution, reacting for 12h at room temperature, and removing SiO2And cobalt nanoparticles to obtain 0.23g of the target Co/NCA-700 catalyst.
Example 4: the invention provides a technical scheme that: a preparation method of a cobalt metal-nitrogen co-doped carbon material catalyst comprises the following steps:
s1, weighing 4.3548g and 30mmol of 8-hydroxyquinoline and 1.2062g and 30mmol of sodium hydroxide respectively, adding 50ml of water, reacting for 4 hours at 80 ℃, adding 4.2165g and 15mmol of cobalt sulfate heptahydrate, reacting for 2 hours, and stopping the reaction, wherein the color of the system is changed from light yellow to reddish brown.
S2, cooling to room temperature, filtering, washing a filter cake with water and ethanol for three times respectively, and drying to obtain a yellow solid with the yield of 95%.
S3, 2.0g of the obtained yellow solid is weighed and mixed with 5.0g of colloidal SiO at room temperature2In CH3CH2OH: stirring the mixed solvent of DMF (3: 1) for 4 hours, and evaporating the solvent under reduced pressure to obtain 4.0g of solid;
s4, weighing 2.0g of the obtained solid, annealing in a tube furnace under the protection of nitrogen, raising the temperature to 800 ℃ through a program of 3 ℃/min, keeping the temperature for 2 hours, completing the pyrolysis of the N-doped carbon material, and obtaining 1.43g of black solid marked as Co/NCA-SiO2-800；
S5, weighing 1.0g of the obtained black solid, and usingTreating with 10 wt% HF water solution, reacting at room temperature for 12 hr to remove SiO2And cobalt nanoparticles to obtain 0.22g of the target Co/NCA-800 catalyst.
Example 5: the invention provides a technical scheme that: a preparation method of a cobalt metal-nitrogen co-doped carbon material catalyst comprises the following steps:
s1, weighing 4.3548g and 30mmol of 8-hydroxyquinoline and 1.2062g and 30mmol of sodium hydroxide respectively, adding 50ml of water, reacting for 4 hours at 80 ℃, adding 4.2165g and 15mmol of cobalt sulfate heptahydrate, reacting for 2 hours, and stopping the reaction, wherein the color of the system is changed from light yellow to reddish brown.
S2, cooling to room temperature, filtering, washing a filter cake with water and ethanol for three times respectively, and drying to obtain a yellow solid with the yield of 95%.
S3, 2.0g of the obtained yellow solid is weighed and mixed with 5.0g of colloidal SiO at room temperature2In CH3CH2OH: stirring the mixed solvent of DMF (3: 1) for 4 hours, and evaporating the solvent under reduced pressure to obtain 4.0g of solid;
s4, weighing 2.0g of the obtained solid, annealing in a tube furnace under the protection of nitrogen, raising the temperature to 900 ℃ through a program of 3 ℃/min, keeping the temperature for 2 hours, completing the pyrolysis of the N-doped carbon material, and obtaining 1.42g of black solid marked as Co/NCA-SiO2-900；
S5, weighing 1.0g of the obtained black solid, treating with 10 wt% HF aqueous solution, reacting for 12h at room temperature, and removing SiO2And cobalt nanoparticles to obtain 0.21g of the target Co/NCA-900 catalyst.
Example 6: the invention provides a technical scheme that: a preparation method of a cobalt metal-nitrogen co-doped carbon material catalyst comprises the following steps:
s1, weighing 4.3548g and 30mmol of 8-hydroxyquinoline and 1.2062g and 30mmol of sodium hydroxide respectively, adding 50ml of water, reacting for 4 hours at 80 ℃, adding 4.2165g and 15mmol of cobalt sulfate heptahydrate, reacting for 2 hours, and stopping the reaction, wherein the color of the system is changed from light yellow to reddish brown.
S2, cooling to room temperature, filtering, washing a filter cake with water and ethanol for three times respectively, and drying to obtain a yellow solid with the yield of 95%.
S3, 2.0g of the obtained yellow solid is weighed and mixed with 5.0g of colloidal SiO at room temperature2In CH3CH2OH: stirring the mixed solvent of DMF (3: 1) for 4 hours, and evaporating the solvent under reduced pressure to obtain 4.0g of solid;
s4, weighing 2.0g of the obtained solid, annealing in a tubular furnace under the protection of nitrogen, heating to 800 ℃ by a program of 3 ℃/min, and keeping the temperature for 2 hours to complete the pyrolysis of the N-doped carbon material to obtain 1.42g of black solid;
s5, weighing 1.0g of the obtained black solid, treating with 10 wt% sodium hydroxide aqueous solution, reacting at room temperature for 12h, removing SiO2Thus, 0.82g of the objective Co/NCB-800 catalyst was obtained.
Example 7: the application of the cobalt metal-nitrogen co-doped carbon material catalyst in the nitro reduction reaction is as follows:
weighing 1mmol of p-chloronitrobenzene, 40mg of cobalt metal-nitrogen co-doped carbon material catalyst and 10ml of ethanol in a 30ml autoclave, reacting for 4 hours at the temperature of 120 ℃ and under the hydrogen pressure of 1.5Mpa, centrifuging after the reaction is stopped, filtering, recovering the catalyst, evaporating an organic phase to dryness under reduced pressure to obtain a product,
the following table is an optimization of the catalyst:
example 8: reaction conditions are optimized, p-chloronitrobenzene is used as a template substrate to further optimize the reaction conditions, the influence of factors such as reaction solvent, reaction temperature, reaction pressure and the like on the yield is investigated, and the results are as follows:
note: Co/NCA-800 is used as a catalyst, and the system reacts for 4 hours.
Example 9: 1mmol of substrate, 40mg of Co/NCA-800 catalyst and 10ml of ethanol as solvent, reacting for 6 hours at 120 ℃ under the hydrogen pressure of 1.5Mpa to obtain a product, wherein the conversion rate and the chemical selectivity of the product are shown as follows.
Example 10: circulating reaction, taking 1mmol of p-chloronitrobenzene, 40mg of Co/NCA-800 catalyst and 10ml of ethanol as a solvent, reacting for 4 hours at 120 ℃ under the hydrogen pressure of 1.5Mpa, centrifugally collecting the catalyst after the reaction is finished, detecting the conversion rate of the p-chloronitrobenzene, washing the catalyst, repeating the process, wherein the conversion rate is shown in the following table,
the catalyst of the invention can be circulated for 6 times, and the catalytic activity of the catalyst is basically unchanged.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (6)
1. A preparation method of a cobalt metal-nitrogen co-doped carbon material catalyst is characterized by comprising the following steps: the method comprises the following steps:
s1, respectively adding 8-hydroxyquinoline, sodium hydroxide and a solvent into a round-bottom flask, changing the color of a reaction system from light yellow to reddish brown, adding cobalt sulfate heptahydrate, changing the color of the reaction system to yellowish green, and stopping the reaction;
s2, cooling the reaction in the S1 to room temperature, filtering, washing a filter cake with water and ethanol for three times respectively, and drying to obtain a yellow solid;
s3, 2.0g of the yellow solid obtained in S2 was weighed out and mixed with 5.0g of colloidal SiO at room temperature2In CH3CH2OH: stirring the mixed solvent of DMF (3: 1) for 4 hours, and evaporating the solvent under reduced pressure to obtain 4.0g of solid;
s4, pyrolyzing the solid obtained in the S3 at the temperature of 900 ℃ under the protection of nitrogen to obtain a black solid;
s5, the black solid obtained in S4 was treated with an aqueous HF solution to obtain a catalyst.
2. The method for preparing a cobalt metal-nitrogen co-doped carbon material catalyst according to claim 1, wherein in S1, the ratio of 8-hydroxyquinoline: the molar ratio of sodium hydroxide is 1:1, 8-hydroxyquinoline: the molar ratio of cobalt sulfate heptahydrate was 2: 1.
3. The method for preparing a cobalt metal-nitrogen co-doped carbon material catalyst according to claim 1, wherein in S1, the reaction is firstly carried out at 80 ℃ for 4h, the color of the reaction system is changed from light yellow to red brown, cobalt sulfate heptahydrate is added, the reaction is carried out for 2h, the color of the system is changed to yellow green, and the reaction is stopped.
4. The method of preparing a cobalt metal-nitrogen co-doped carbon material catalyst according to claim 1, wherein the solvent is water in S1.
5. The method of preparing a cobalt metal-nitrogen co-doped carbon material catalyst according to claim 1, wherein in S4, the pyrolysis conditions are: heating to 500-900 ℃ by a program of 3 ℃/min, and keeping the temperature for 2 hours.
6. The method for preparing a cobalt metal-nitrogen co-doped carbon material catalyst according to claim 1, wherein in S5, HF aqueous solution is treated, specifically, acid-washed with 10 wt% HF aqueous solution at room temperature for 12 h.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106513028A (en) * | 2016-10-28 | 2017-03-22 | 中南民族大学 | Catalyst, preparation method thereof and application in reducing nitryl compound |
| AU2020101504A4 (en) * | 2019-10-23 | 2020-09-10 | Hunan University Of Science And Technology | Preparation of nitrogen-cobalt-phosphorus co-doped hollow carbon sphere composite and product and use thereof |
| CN112916033A (en) * | 2019-12-06 | 2021-06-08 | 上海大学 | Carbon-nitrogen-doped silicon dioxide-loaded Co catalyst and preparation method and application thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106513028A (en) * | 2016-10-28 | 2017-03-22 | 中南民族大学 | Catalyst, preparation method thereof and application in reducing nitryl compound |
| AU2020101504A4 (en) * | 2019-10-23 | 2020-09-10 | Hunan University Of Science And Technology | Preparation of nitrogen-cobalt-phosphorus co-doped hollow carbon sphere composite and product and use thereof |
| CN112916033A (en) * | 2019-12-06 | 2021-06-08 | 上海大学 | Carbon-nitrogen-doped silicon dioxide-loaded Co catalyst and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
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| XIN QIN ET AL.: "Magnetic MxOy@N-C as heterogeneous catalysts for the catalytic oxidation of aniline solution with sulfate radicals", 《J NANOPART RES》, vol. 19, pages 1 - 15 * |
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