CN113509948A - Nitrogen-doped mesoporous carbon supported platinum catalyst and preparation method and application thereof - Google Patents
Nitrogen-doped mesoporous carbon supported platinum catalyst and preparation method and application thereof Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 151
- 239000003054 catalyst Substances 0.000 title claims abstract description 68
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 27
- 238000005187 foaming Methods 0.000 claims abstract description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 23
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000001704 evaporation Methods 0.000 claims abstract description 21
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 21
- 239000011777 magnesium Substances 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 19
- 230000009467 reduction Effects 0.000 claims abstract description 18
- 230000008020 evaporation Effects 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 238000011068 loading method Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 10
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 9
- 150000002828 nitro derivatives Chemical class 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 28
- 229940091250 magnesium supplement Drugs 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 238000005554 pickling Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 10
- 229960005336 magnesium citrate Drugs 0.000 claims description 10
- 235000002538 magnesium citrate Nutrition 0.000 claims description 10
- 239000004337 magnesium citrate Substances 0.000 claims description 10
- PLSARIKBYIPYPF-UHFFFAOYSA-H trimagnesium dicitrate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O PLSARIKBYIPYPF-UHFFFAOYSA-H 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 230000001681 protective effect Effects 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- 229960003035 magnesium gluconate Drugs 0.000 claims description 4
- 239000001755 magnesium gluconate Substances 0.000 claims description 4
- 235000015778 magnesium gluconate Nutrition 0.000 claims description 4
- IAKLPCRFBAZVRW-XRDLMGPZSA-L magnesium;(2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanoate;hydrate Chemical compound O.[Mg+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O IAKLPCRFBAZVRW-XRDLMGPZSA-L 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 17
- 239000000126 substance Substances 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 20
- 239000011148 porous material Substances 0.000 description 17
- 239000006260 foam Substances 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000013335 mesoporous material Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- IYQJAGXFXWIEJE-UHFFFAOYSA-H trimagnesium;2-hydroxypropane-1,2,3-tricarboxylate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Mg+2].[Mg+2].[Mg+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O IYQJAGXFXWIEJE-UHFFFAOYSA-H 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- 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
Abstract
The invention belongs to the technical field of catalysts, and particularly relates to a nitrogen-doped mesoporous carbon supported platinum catalyst and a preparation method and application thereof. The preparation method of the nitrogen-doped mesoporous carbon supported platinum catalyst provided by the invention comprises the following steps of: mixing the magnesium source solution with a nitrogen source, and then sequentially performing evaporation and foaming treatment to obtain a foaming body; sequentially crushing and calcining the foaming body to obtain a calcined material; sequentially carrying out acid washing, water washing and drying on the calcined material to obtain a nitrogen-doped porous carbon material; and sequentially carrying out Pt loading and reduction treatment on the nitrogen-doped porous carbon material to obtain the nitrogen-doped mesoporous carbon loaded platinum catalyst. Experimental data show that the nitrogen-doped mesoporous carbon supported platinum catalyst provided by the invention has a mesoporous structure, and when the catalyst is used in a hydrogenation reaction of a nitro compound, the catalytic activity is high, the chemical selectivity is as high as 99.9%, the catalytic selectivity is high, and the catalyst has a good catalytic effect.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a nitrogen-doped mesoporous carbon supported platinum catalyst and a preparation method and application thereof.
Background
As can be seen from the definition given by the international association of pure and applied chemistry (IUPAC) on porous materials, they can be classified into three categories according to their pore diameter: the pore diameter of the microporous materials is less than 2 nm; the aperture of the mesoporous material (mesoporus materials) is 2-50 nm; macroporous materials (macroporous materials) have a pore size greater than 50 nm. The mesoporous material has the characteristics of extremely high specific surface area, regular and ordered pore channel structure, narrow pore size distribution, continuously adjustable pore size and the like, so that the mesoporous material plays a role in the adsorption and separation of macromolecules, particularly catalytic reaction, which are difficult to complete by a plurality of microporous zeolite molecular sieves. The mesoporous carbon material has huge specific surface area (up to 2500 m)2(g) and pore volume (up to 2.25cm3/g), have found important applications in catalyst supports, hydrogen storage materials, electrode materials, and the like. However, the method for preparing the mesoporous carbon material is generally complicated, has high operation difficulty and is not beneficial to industrial production. Meanwhile, in order to further improve the application of the mesoporous carbon material in these aspects, a heteroatom (such as N, B or S) or a group containing a heteroatom (such as an amino group, a nitro group, or a sulfonic group) is usually doped into the surface or the structure of the porous carbon material, so that various properties of the porous carbon material are improved and enhanced. However, the catalyst prepared by the traditional simple impregnation method is easy to generate unfavorable results such as particle agglomeration, loss of catalytic active substances and the like, and the catalyst is low in catalytic activity and catalytic selectivity and cannot meet the requirements of catalytic conditions.
Disclosure of Invention
In view of the above, the present invention provides a nitrogen-doped mesoporous carbon supported platinum catalyst. The nitrogen-doped mesoporous carbon supported platinum catalyst provided by the invention has the characteristics of high catalytic activity and high catalytic selectivity, and has an excellent catalytic effect in a hydrogenation reaction of nitro compounds; the invention also provides a preparation method of the nitrogen-doped mesoporous carbon supported platinum catalyst, which has simple steps and is easy to operate; the invention also provides application of the nitrogen-doped mesoporous carbon supported platinum catalyst.
In order to achieve the purpose of the invention, the invention provides the following technical scheme:
the invention provides a preparation method of a nitrogen-doped mesoporous carbon supported platinum catalyst, which comprises the following steps:
mixing the magnesium source solution with a nitrogen source, and then sequentially performing evaporation and foaming treatment to obtain a foaming body;
sequentially crushing and calcining the foaming body to obtain a calcined material;
sequentially carrying out acid washing, water washing and drying on the calcined material to obtain a nitrogen-doped porous carbon material;
and sequentially carrying out Pt loading and reduction treatment on the nitrogen-doped porous carbon material to obtain the nitrogen-doped mesoporous carbon loaded platinum catalyst.
Preferably, the magnesium source in the magnesium source solution is magnesium citrate and/or magnesium gluconate; the concentration of the magnesium source solution is 2-10 mol/L.
Preferably, the nitrogen source is urea or melamine; the molar ratio of the magnesium source to the nitrogen source in the magnesium source solution is (2-10): 1.
preferably, the evaporation temperature is 60-90 ℃; the foaming treatment temperature is 90-140 ℃, and the time is 4-6 h.
Preferably, the calcining temperature is 600-800 ℃, and the time is 2-3 h.
Preferably, the pickling temperature is 60-85 ℃, and the pickling time is 6-8 h; the pickling solution for pickling is hydrochloric acid; the concentration of the hydrochloric acid is 2-3 mol/L.
Preferably, when the Pt loading is performed, the mass ratio of the nitrogen-doped porous carbon material to the Pt aqueous solution is 3: (0.03-0.15); the mass concentration of the Pt aqueous solution is 2%.
Preferably, the reduction temperature is 200-400 ℃, and the time is 2-3 h; the heating rate of heating to the reduction temperature is 2-3 ℃/min; the reducing atmosphere is a mixed atmosphere of hydrogen and protective gas; the volume ratio of the hydrogen to the protective gas is 1: (1-3); the protective gas is nitrogen or inert gas.
The invention also provides the nitrogen-doped mesoporous carbon supported platinum catalyst prepared by the preparation method in the technical scheme.
The invention also provides the application of the nitrogen-doped mesoporous carbon supported platinum catalyst in the technical scheme in the hydrogenation reaction of nitro compounds.
The invention provides a preparation method of a nitrogen-doped mesoporous carbon supported platinum catalyst, which comprises the following steps: mixing the magnesium source solution with a nitrogen source, and then sequentially performing evaporation and foaming treatment to obtain a foaming body; sequentially crushing and calcining the foaming body to obtain a calcined material; sequentially carrying out acid washing, water washing and drying on the calcined material to obtain a nitrogen-doped porous carbon material; and sequentially carrying out Pt loading and reduction treatment on the nitrogen-doped porous carbon material to obtain the nitrogen-doped mesoporous carbon loaded platinum catalyst. The invention ensures the nitrogen doping effect by using the nitrogen source; initially forming a gel system by evaporation, and then producing a foam having pores and a foam structure by a foaming treatment; the shaping of the pore and bubble structure is ensured through calcination, thereby being beneficial to obtaining the mesoporous structure; removing MgO through acid washing, and further providing a load position for the Pt load; reduction treatment is carried out after Pt is loaded, so that the reduction performance of the catalyst is ensured, and the catalytic performance is further ensured. The nitrogen-doped mesoporous carbon supported platinum catalyst prepared by the preparation method provided by the invention has a mesoporous structure under the nitrogen-doped condition, and the specific surface area is large; the platinum is uniformly loaded, and the catalytic activity area is large. In addition, the interaction between the nitrogen-doped mesoporous carbon supported platinum catalyst and Pt provided by the invention enables the Pt content to be higher than that of a non-nitrogen-doped mesoporous carbon supported platinum catalyst, and the interaction enables Pt particles to be smaller and the specific surface area to be larger, so that the nitrogen-doped mesoporous carbon supported platinum catalyst provided by the invention can show good catalytic activity and selectivity.
Experimental data show that when the nitrogen-doped mesoporous carbon supported platinum catalyst provided by the invention is used in a hydrogenation reaction of nitro compounds, the catalytic activity is high, the chemical selectivity is as high as 99.9%, the catalytic selectivity is high, and a good catalytic effect is achieved.
Drawings
FIG. 1 is an SEM image of a nitrogen-doped mesoporous carbon supported platinum catalyst obtained in example 1 of the present invention;
FIG. 2 is an XRD pattern of the nitrogen-doped mesoporous carbon supported platinum catalyst obtained in example 1 of the present invention;
FIG. 3 is a BET diagram of the nitrogen-doped mesoporous carbon supported platinum catalyst obtained in example 1 of the present invention.
Detailed Description
The invention provides a preparation method of a nitrogen-doped mesoporous carbon supported platinum catalyst, which comprises the following steps:
mixing the magnesium source solution with a nitrogen source, and then sequentially performing evaporation and foaming treatment to obtain a foaming body;
sequentially crushing and calcining the foaming body to obtain a calcined material;
sequentially carrying out acid washing, water washing and drying on the calcined material to obtain a nitrogen-doped porous carbon material;
and sequentially carrying out Pt loading and reduction treatment on the nitrogen-doped porous carbon material to obtain the nitrogen-doped mesoporous carbon loaded platinum catalyst.
In the present invention, the components are commercially available products well known to those skilled in the art, unless otherwise specified.
The method comprises the steps of mixing a magnesium source solution with a nitrogen source, and then sequentially carrying out evaporation and foaming treatment to obtain the foam.
In the present invention, the magnesium source in the magnesium source solution is preferably magnesium citrate and/or magnesium gluconate, more preferably magnesium citrate. In the invention, the concentration of the magnesium source solution is preferably 2-10 mol/L, more preferably 3-8 mil/L, still more preferably 4-7 mol/L, and most preferably 5 mol/L.
In the present invention, the nitrogen source is preferably urea or melamine. In the invention, the molar ratio of the magnesium source to the nitrogen source in the magnesium source solution is preferably (2-10): 1, more preferably (3-8): 1, and preferably (4-7): 1, most preferably 5: 1.
in the invention, the evaporation temperature is preferably 60-90 ℃, more preferably 65-85 ℃, and further preferably 70-80 ℃; the time is preferably 6 to 8 hours, and more preferably 6.5 to 7.5 hours. In the present invention, the evaporation is preferably carried out under the condition of stirring in a water bath; the stirring speed of the water bath stirring is not particularly limited in the invention, and the stirring speed of the water bath stirring known to those skilled in the art can be adopted. The present invention removes most of the water by evaporation to give a colloidal system.
In the invention, the foaming treatment temperature is preferably 90-140 ℃, more preferably 100-130 ℃, and further preferably 110-120 ℃; the time is preferably 4 to 6 hours, more preferably 4.1 to 5.5 hours, and still more preferably 4.2 to 5 hours. In the present invention, the apparatus for the foaming treatment is preferably an oven. The present invention produces a foam having pores and bubbles by a foaming process.
After the foaming body is obtained, the foaming body is sequentially crushed and calcined to obtain a calcined material.
In the present invention, the particle size of the pulverization is not particularly limited, and the pulverization of the foam is carried out without lumping. In the invention, the calcination temperature is preferably 600-800 ℃, more preferably 650-750 ℃, and further preferably 680-720 ℃; the time is preferably 2 to 3 hours, more preferably 2.1 to 2.8 hours, and still more preferably 2.2 to 2.6 hours. In the present invention, the atmosphere of the calcination is preferably nitrogen. The invention ensures the shaping of the pore and bubble structure by calcination, thereby being beneficial to the obtaining of the mesoporous structure.
After the calcined material is obtained, the calcined material is sequentially subjected to acid washing, water washing and drying to obtain the nitrogen-doped porous carbon material.
In the invention, the pickling temperature is preferably 60-85 ℃, more preferably 65-83 ℃, and further preferably 70-80 ℃; the time is preferably 6 to 8 hours, more preferably 6 to 7.5 hours, and still more preferably 6 to 7 hours. In the present invention, the pickling acid solution is preferably hydrochloric acid; the concentration of the hydrochloric acid is preferably 2-3 mol/L, more preferably 2.2-3 mol/L, and still more preferably 2.5-3 mol/L. In the present invention, the pickling method is preferably reflux pickling using a pickling solution. The method removes MgO through acid washing, and further provides a loading position for Pt loading. The washing with water is not particularly limited in the present invention, and the washing with water of the acid-washed product is carried out until the acid-washed product is neutral. In the present invention, the drying temperature is preferably 100 ℃ and the drying time is preferably 12 hours.
After the nitrogen-doped porous carbon material is obtained, the nitrogen-doped porous carbon material is sequentially subjected to Pt loading and reduction treatment to obtain the nitrogen-doped mesoporous carbon loaded platinum catalyst.
In the present invention, when the Pt loading is performed, the mass ratio of the nitrogen-doped porous carbon material to the Pt aqueous solution is preferably 3: (0.03 to 0.15), more preferably 3: (0.04 to 0.10), more preferably (0.05 to 0.08), most preferably 3: 0.06; the mass concentration of the aqueous Pt solution is preferably 2%. In the present invention, the aqueous solution of Pt is preferably chloroplatinic acid (H)2PtCl6) An aqueous solution of (a). In the invention, the preparation method of the Pt load preferably comprises the steps of dipping, ultrasonic treatment, water bath stirring and evaporation to dryness and drying which are sequentially carried out. In the present invention, the impregnation is preferably mixing the nitrogen-doped porous carbon material, the Pt aqueous solution, and water; the water is preferably deionized water; the dosage ratio of the nitrogen-doped porous carbon material to water is preferably 3 g: 20 mL. In the present invention, the time of the ultrasound is preferably 3 min; the frequency of the ultrasound is not particularly limited in the invention, and the ultrasound frequency known to those skilled in the art can be adopted; the invention enables the components to be dissolved uniformly by the ultrasound. In the invention, the temperature of the water bath stirring and drying is preferably 40 ℃, and the time is preferably 10-12 h; the stirring rate of the stirring evaporation of the water bath is not particularly limited in the present invention, and the stirring rate is known to those skilled in the art. The invention realizes the uniform mixing of all components by stirring and evaporating in a water bath. In the present invention, the temperature of the drying is preferably 100 ℃ and the time is preferably 12 hours.
In the invention, the reduction temperature is preferably 200-400 ℃, more preferably 200-350 ℃, and further preferably 200-300 ℃; the time is preferably 2 to 3 hours, more preferably 2 to 2.8 hours, and still more preferably 2 to 2.6 hours. The invention preferably reaches the reduction temperature by raising the temperature; the heating rate for heating to the reduction temperature is preferably 2-3 ℃/min, more preferably 2-2.8 ℃/min, and still more preferably 2-2.5 ℃/min. In the present invention, the reduction apparatus is preferably a temperature programmed furnace. In the present invention, the reducing atmosphere is preferably a mixed atmosphere of hydrogen and a protective gas; the volume ratio of the hydrogen gas to the protective gas is preferably 1: (1-3), more preferably 1: (1.3-2.7), and more preferably 1: (1.7-2.2), most preferably 1: 2. in the present invention, the protective gas is preferably nitrogen or an inert gas. The invention carries out reduction treatment after Pt is loaded, thereby ensuring the reduction performance of the catalyst and further being beneficial to ensuring the catalytic performance.
The invention also provides the nitrogen-doped mesoporous carbon supported platinum catalyst prepared by the preparation method in the technical scheme. In the invention, the platinum loading amount of the nitrogen-doped mesoporous carbon supported platinum catalyst is preferably 1-4 wt.%. In the invention, the specific surface area of the nitrogen-doped mesoporous carbon supported platinum catalyst is preferably 2500-3000 m2The preferred pore volume is 1.5-2.0 cm3In terms of the pore diameter is preferably,/g
The invention also provides the application of the nitrogen-doped mesoporous carbon supported platinum catalyst in the technical scheme in the hydrogenation reaction of nitro compounds. According to the invention, the nitrogen-doped porous carbon supported platinum catalyst is preferably used as a catalyst in a hydrogenation reaction of nitro compounds. The specific method of the present invention is not particularly limited, and a method known in the art may be selected.
In order to further illustrate the present invention, the nitrogen-doped mesoporous carbon supported platinum catalyst provided by the present invention, the preparation method and the application thereof are described in detail below with reference to the examples, but they should not be construed as limiting the scope of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. 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.
Example 1
703.4g of magnesium citrate nonahydrate (100mmol) was dissolved in 20mL of deionized water to obtain a magnesium citrate solution; mixing the obtained magnesium citrate solution with 1.2012g urea (20mmol), stirring for 10min, then stirring and evaporating in a water bath at 90 ℃ for 6-8 h to remove most of water, and then keeping the temperature in an oven at 140 ℃ for 4h to fully foam to obtain a foam body; grinding the obtained foaming body, and calcining for 4 hours at 700 ℃ in a nitrogen atmosphere to obtain a calcined material; refluxing the obtained calcined material with 3mol/L hydrochloric acid solution at 85 ℃ for 6h to remove MgO in the calcined material, washing the product to be neutral with distilled water, and drying in a 100 ℃ drying oven for 12h to obtain the nitrogen-doped porous carbon material;
carrying out ultrasonic treatment on 3g of nitrogen-doped porous carbon material, 0.06g of Pt aqueous solution (the mass concentration of Pt is 2%) and 20mL of deionized water for 3min to uniformly dissolve the materials, then carrying out water bath stirring and evaporation drying at the temperature of 40 ℃ for 10-12 h, and drying in a drying oven at the temperature of 100 ℃ for 12h to obtain a primary nitrogen-doped mesoporous carbon supported platinum catalyst; at a hydrogen to nitrogen flow rate ratio of 40: and in the atmosphere of 80, heating the obtained nitrogen-doped mesoporous carbon supported platinum catalyst to 200 ℃ in a programmed temperature control furnace at the heating rate of 2 ℃/min, preserving the heat for 2 hours at the temperature of 200 ℃, and finally, rapidly cooling to the room temperature to obtain the nitrogen-doped mesoporous carbon supported platinum catalyst.
SEM test of the nitrogen-doped mesoporous carbon supported platinum catalyst obtained in example 1 is carried out, and the obtained test chart is shown in figure 1.
As can be seen from fig. 1, the nitrogen-doped mesoporous carbon supported platinum catalyst provided by the present invention has a mesoporous structure.
XRD test was performed on the nitrogen-doped mesoporous carbon supported platinum catalyst obtained in example 1, and the obtained test results are shown in FIG. 2.
As can be seen from fig. 2, the diffraction peak of the crystal plane of the carbon material (002) is evident at about 26 ° 2 θ, and the diffraction peak of the crystal plane of the graphite layer (100) is relatively weak at about 43 ° 2 θ, indicating that the prepared carbon material has a certain degree of graphitization.
The nitrogen-doped mesoporous carbon supported platinum catalyst obtained in example 1 was subjected to BET test, and the test results are shown in fig. 3.
As can be seen from FIG. 3, nitrogen doping has an influence on the pore structure, pore size distribution and pore volume of the catalyst, and as shown in the right graph, the sample is a typical IV-type isotherm and has an extremely obvious H1-type hysteresis loop, which shows the characteristics of an obvious mesoporous material and is consistent with the XRD test result.
Example 2
703.4g of magnesium citrate nonahydrate (100mmol) was dissolved in 20mL of deionized water to obtain a magnesium citrate solution; mixing the obtained magnesium citrate solution with 1.2012g urea (20mmol), stirring for 10min, then stirring and evaporating in a water bath at 70 ℃ for 6-8 h to remove most of water, and then keeping the temperature in an oven at 140 ℃ for 4h to fully foam to obtain a foam body; grinding the obtained foaming body, and calcining for 4h at 900 ℃ in a nitrogen atmosphere to obtain a calcined material; refluxing the obtained calcined material with 3mol/L hydrochloric acid solution at 85 ℃ for 6h to remove MgO in the calcined material, washing the product to be neutral with distilled water, and drying in a 100 ℃ drying oven for 12h to obtain the nitrogen-doped porous carbon material;
carrying out ultrasonic treatment on 3g of nitrogen-doped porous carbon material, 0.06g of Pt aqueous solution (the mass concentration of Pt is 2%) and 20mL of deionized water for 3min to uniformly dissolve the materials, then carrying out water bath stirring and evaporation drying at the temperature of 40 ℃ for 10-12 h, and drying in a drying oven at the temperature of 100 ℃ for 12h to obtain a primary nitrogen-doped mesoporous carbon supported platinum catalyst; at a hydrogen to nitrogen flow rate ratio of 40: and in the atmosphere of 80, heating the obtained nitrogen-doped mesoporous carbon supported platinum catalyst to 200 ℃ in a programmed temperature control furnace at the heating rate of 2 ℃/min, preserving the heat for 2 hours at the temperature of 200 ℃, and finally, rapidly cooling to the room temperature to obtain the nitrogen-doped mesoporous carbon supported platinum catalyst.
Example 3
703.4g of magnesium citrate nonahydrate (100mmol) was dissolved in 20mL of deionized water to obtain a magnesium citrate solution; mixing the obtained magnesium citrate solution and 2.52g of melamine (20mmol), stirring for 10min, then stirring and evaporating in a water bath at 80 ℃ for 6-8 h to remove most of water, and then keeping the temperature in a drying oven at 140 ℃ for 4h to fully foam to obtain a foam body; grinding the obtained foaming body, and calcining for 4 hours at 800 ℃ in a nitrogen atmosphere to obtain a calcined material; refluxing the obtained calcined material with 3mol/L hydrochloric acid solution at 85 ℃ for 6h to remove MgO in the calcined material, washing the product to be neutral with distilled water, and drying in a 100 ℃ drying oven for 12h to obtain the nitrogen-doped porous carbon material;
carrying out ultrasonic treatment on 3g of nitrogen-doped porous carbon material, 0.06g of Pt aqueous solution (the mass concentration of Pt is 2%) and 20mL of deionized water for 3min to uniformly dissolve the materials, then carrying out water bath stirring and evaporation drying at the temperature of 40 ℃ for 10-12 h, and drying in a drying oven at the temperature of 100 ℃ for 12h to obtain a primary nitrogen-doped mesoporous carbon supported platinum catalyst; at a hydrogen to nitrogen flow rate ratio of 40: and in the atmosphere of 80, heating the obtained nitrogen-doped mesoporous carbon supported platinum catalyst to 200 ℃ in a programmed temperature control furnace at the heating rate of 2 ℃/min, preserving the heat for 2 hours at the temperature of 200 ℃, and finally, rapidly cooling to the room temperature to obtain the nitrogen-doped mesoporous carbon supported platinum catalyst.
Example 4
The mass concentration of Pt is 1%, and the rest steps are the same as those in the example 1, so that the nitrogen-doped mesoporous carbon supported platinum catalyst is obtained.
Example 5
The mass concentration of Pt is 3%, and the rest steps are the same as those in the example 1, so that the nitrogen-doped mesoporous carbon supported platinum catalyst is obtained.
Comparative example 1
The same procedures as in example 3 were repeated except for using 41.46g of magnesium gluconate (100mmol) in place of 703.4g of magnesium citrate nonahydrate (100mmol) in example 3 to obtain a nitrogen-doped mesoporous carbon supported platinum catalyst.
Application examples 1 to 16
And respectively carrying out catalysis of hydrogenation reaction of nitro compounds by using the nitrogen-doped mesoporous carbon supported platinum catalysts obtained in examples 1-5 and comparative example 1.
The method specifically comprises the following steps: and (2) putting the nitrogen-doped mesoporous carbon supported platinum catalyst, o-chloronitrobenzene and absolute ethyl alcohol into a reaction kettle, and carrying out hydrogenation reaction at the temperature of 40 ℃ for 0.5 h. The conversion and selectivity were obtained by gas chromatography analysis. The cycling test was carried out, and the specific experimental amounts and test results are shown in table 1.
TABLE 1 application examples 1-7 Experimental dosages and test results
Test results show that the nitrogen-doped mesoporous carbon supported platinum catalyst provided by the invention has good stability and recyclability.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a nitrogen-doped mesoporous carbon supported platinum catalyst is characterized by comprising the following steps:
mixing the magnesium source solution with a nitrogen source, and then sequentially performing evaporation and foaming treatment to obtain a foaming body;
sequentially crushing and calcining the foaming body to obtain a calcined material;
sequentially carrying out acid washing, water washing and drying on the calcined material to obtain a nitrogen-doped porous carbon material;
and sequentially carrying out Pt loading and reduction treatment on the nitrogen-doped porous carbon material to obtain the nitrogen-doped mesoporous carbon loaded platinum catalyst.
2. The method according to claim 1, wherein the magnesium source in the magnesium source solution is magnesium citrate and/or magnesium gluconate; the concentration of the magnesium source solution is 2-10 mol/L.
3. The process according to claim 1, wherein the nitrogen source is urea or melamine; the molar ratio of the magnesium source to the nitrogen source in the magnesium source solution is (2-10): 1.
4. the preparation method according to claim 1, wherein the temperature of the evaporation is 60-90 ℃; the foaming treatment temperature is 90-140 ℃, and the time is 4-6 h.
5. The preparation method according to claim 1, wherein the calcining temperature is 600-800 ℃ and the calcining time is 2-3 h.
6. The preparation method according to claim 1, wherein the pickling temperature is 60-85 ℃ and the pickling time is 6-8 h; the pickling solution for pickling is hydrochloric acid; the concentration of the hydrochloric acid is 2-3 mol/L.
7. The production method according to claim 1, wherein the Pt loading is performed such that the mass ratio of the nitrogen-doped porous carbon material to the Pt aqueous solution is 3: (0.03-0.15); the mass concentration of the Pt aqueous solution is 2%.
8. The preparation method according to claim 1, wherein the temperature of the reduction is 200-400 ℃ and the time is 2-3 h; the heating rate of heating to the reduction temperature is 2-3 ℃/min; the reducing atmosphere is a mixed atmosphere of hydrogen and protective gas; the volume ratio of the hydrogen to the protective gas is 1: (1-3); the protective gas is nitrogen or inert gas.
9. The nitrogen-doped mesoporous carbon supported platinum catalyst prepared by the preparation method of any one of claims 1 to 8.
10. The use of the nitrogen-doped mesoporous carbon supported platinum catalyst of claim 9 in hydrogenation reactions of nitro compounds.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114849756A (en) * | 2022-05-23 | 2022-08-05 | 衢州学院 | Catalyst for synthesizing vinyl trichlorosilane, preparation method, use method and application thereof |
| CN115350721A (en) * | 2022-10-21 | 2022-11-18 | 农业农村部环境保护科研监测所 | Nickel-based double-active-domain catalyst and preparation method and application thereof |
| CN115852388A (en) * | 2022-11-12 | 2023-03-28 | 中国石油大学(华东) | Nitrogen-doped hollow mesoporous carbon sphere loaded nano platinum electro-catalysis hydrogen evolution material for cathode of PEM (proton exchange membrane) electrolytic cell, preparation and application |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102741160A (en) * | 2009-11-30 | 2012-10-17 | 独立行政法人产业技术综合研究所 | Nitrogen-containing porous carbon material, method for producing same, and electric double layer capacitor using the nitrogen-containing porous carbon material |
| CN106622327A (en) * | 2016-12-20 | 2017-05-10 | 中国科学院青岛生物能源与过程研究所 | N-doped porous carbon supported metal catalyst, and preparation method and application thereof |
| EP3249669A1 (en) * | 2016-05-25 | 2017-11-29 | Universiteit van Amsterdam | Supercapacitor and nitrogen-doped porous carbon material |
| CN108328599A (en) * | 2018-01-30 | 2018-07-27 | 东莞理工学院 | A method of nitrogen-doped porous carbon material is prepared based on citric acid transition/alkali metal complex salt |
| CN109678131A (en) * | 2018-12-21 | 2019-04-26 | 上海大学 | A kind of preparation method of the mesoporous carbon carrier of nitrating |
| CN110451507A (en) * | 2019-07-30 | 2019-11-15 | 深圳大学 | Preparation method, electrode of super capacitor and the supercapacitor of porous carbon materials |
-
2020
- 2020-04-10 CN CN202010278899.9A patent/CN113509948A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102741160A (en) * | 2009-11-30 | 2012-10-17 | 独立行政法人产业技术综合研究所 | Nitrogen-containing porous carbon material, method for producing same, and electric double layer capacitor using the nitrogen-containing porous carbon material |
| EP3249669A1 (en) * | 2016-05-25 | 2017-11-29 | Universiteit van Amsterdam | Supercapacitor and nitrogen-doped porous carbon material |
| CN106622327A (en) * | 2016-12-20 | 2017-05-10 | 中国科学院青岛生物能源与过程研究所 | N-doped porous carbon supported metal catalyst, and preparation method and application thereof |
| CN108328599A (en) * | 2018-01-30 | 2018-07-27 | 东莞理工学院 | A method of nitrogen-doped porous carbon material is prepared based on citric acid transition/alkali metal complex salt |
| CN109678131A (en) * | 2018-12-21 | 2019-04-26 | 上海大学 | A kind of preparation method of the mesoporous carbon carrier of nitrating |
| CN110451507A (en) * | 2019-07-30 | 2019-11-15 | 深圳大学 | Preparation method, electrode of super capacitor and the supercapacitor of porous carbon materials |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114849756A (en) * | 2022-05-23 | 2022-08-05 | 衢州学院 | Catalyst for synthesizing vinyl trichlorosilane, preparation method, use method and application thereof |
| CN115350721A (en) * | 2022-10-21 | 2022-11-18 | 农业农村部环境保护科研监测所 | Nickel-based double-active-domain catalyst and preparation method and application thereof |
| CN115852388A (en) * | 2022-11-12 | 2023-03-28 | 中国石油大学(华东) | Nitrogen-doped hollow mesoporous carbon sphere loaded nano platinum electro-catalysis hydrogen evolution material for cathode of PEM (proton exchange membrane) electrolytic cell, preparation and application |
| CN115852388B (en) * | 2022-11-12 | 2024-02-20 | 中国石油大学(华东) | Nitrogen-doped hollow mesoporous carbon sphere loaded nano platinum electrocatalytic hydrogen evolution material for cathode of PEM (proton exchange membrane) electrolytic cell, preparation and application |
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