CN114849750A - Hollow nitrogen-doped carbon sphere supported metal catalyst and preparation method and application thereof - Google Patents
Hollow nitrogen-doped carbon sphere supported metal catalyst and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 106
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 96
- 239000002184 metal Substances 0.000 title claims abstract description 96
- 239000003054 catalyst Substances 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000004793 Polystyrene Substances 0.000 claims abstract description 37
- 229920002223 polystyrene Polymers 0.000 claims abstract description 37
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 32
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229960001149 dopamine hydrochloride Drugs 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims description 83
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 72
- 238000006243 chemical reaction Methods 0.000 claims description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 52
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 48
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- 239000001257 hydrogen Substances 0.000 claims description 45
- 229910052739 hydrogen Inorganic materials 0.000 claims description 45
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 43
- DDRPCXLAQZKBJP-UHFFFAOYSA-N furfurylamine Chemical compound NCC1=CC=CO1 DDRPCXLAQZKBJP-UHFFFAOYSA-N 0.000 claims description 34
- 239000007789 gas Substances 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000009210 therapy by ultrasound Methods 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 24
- 239000002077 nanosphere Substances 0.000 claims description 22
- 238000004108 freeze drying Methods 0.000 claims description 19
- 239000011943 nanocatalyst Substances 0.000 claims description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 238000007710 freezing Methods 0.000 claims description 8
- 230000008014 freezing Effects 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 6
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 229910002094 inorganic tetrachloropalladate Inorganic materials 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 238000010000 carbonizing Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 3
- 150000002431 hydrogen Chemical group 0.000 claims description 2
- 238000001308 synthesis method Methods 0.000 abstract description 22
- 230000000379 polymerizing effect Effects 0.000 abstract description 4
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 42
- 238000010438 heat treatment Methods 0.000 description 31
- 239000003921 oil Substances 0.000 description 31
- 239000000203 mixture Substances 0.000 description 29
- 239000008367 deionised water Substances 0.000 description 24
- 229910021641 deionized water Inorganic materials 0.000 description 24
- 229960003638 dopamine Drugs 0.000 description 21
- 239000000523 sample Substances 0.000 description 19
- 238000004321 preservation Methods 0.000 description 17
- 238000001816 cooling Methods 0.000 description 16
- 238000004817 gas chromatography Methods 0.000 description 12
- 238000007792 addition Methods 0.000 description 11
- 239000003575 carbonaceous material Substances 0.000 description 11
- 239000012295 chemical reaction liquid Substances 0.000 description 11
- 238000001514 detection method Methods 0.000 description 11
- 239000006228 supernatant Substances 0.000 description 11
- 239000012520 frozen sample Substances 0.000 description 10
- 239000011148 porous material Substances 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 238000006268 reductive amination reaction Methods 0.000 description 8
- 239000002082 metal nanoparticle Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- 238000000527 sonication Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910019891 RuCl3 Inorganic materials 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012703 microemulsion polymerization Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- -1 aldehyde ketone Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000012075 bio-oil Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- 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
-
- B01J35/23—
-
- B01J35/61—
-
- 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
- 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)
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/52—Radicals substituted by nitrogen atoms not forming part of a nitro radical
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention provides a hollow nitrogen-doped carbon sphere supported metal catalyst and a preparation method and application thereof. A post-synthesis method comprises the steps of adding dopamine hydrochloride into a prepared hard template to serve as a nitrogen source and a carbon source, polymerizing the nitrogen source and the carbon source on the hard template, roasting to form nitrogen-doped hollow carbon spheres, and adding a metal source on the basis of the nitrogen-doped hollow carbon spheres to enable the metal source to be loaded on the nitrogen-doped hollow carbon spheres. In both methods, the nitrogen-doped hollow carbon spheres are prepared on the basis of taking polystyrene as a hard template, and the nitrogen-doped hollow carbon spheres are taken as a framework structure.
Description
Technical Field
The invention belongs to the technical field of carbon material preparation, and particularly relates to a hollow nitrogen-doped carbon sphere supported metal catalyst, and a preparation method and application thereof.
Background
The carbon material is a porous material having a highly developed pore structure with carbon as a basic skeleton. In addition, the carbon material has a series of characteristics of good chemical stability, fast heat conduction, high temperature resistance, corrosion resistance and the like, can be widely applied to the fields of catalyst carriers, biological reactions, sensors, electrode materials, adsorbents, purified water, gas separation and the like, and is a research focus in the fields of materials, chemical engineering, physics and the like. The nitrogen-doped hollow carbon spheres are greatly concerned by scientific researchers due to the hollow structure, the higher specific surface area, the adjustable pore structure or the chemical properties. The nitrogen-doped carbon material allows nitrogen atoms to enter the interior of the carbon material, and nitrogen in different forms is combined with the carbon atoms, so that the nitrogen-doped carbon material can be used as a catalyst carrier material. The reason is that after nitrogen doping, more active sites are introduced into the carbon material, the nitrogen is uniformly distributed, the high dispersibility of the metal nanoparticles can improve the utilization rate of the catalyst, reduce the cost, reduce the loading capacity and the like, and further enhance the stability and the activity of the catalyst, so that the catalyst is suitable for noble metals and non-noble metals. On the basis, the development of a nitrogen-doped hollow carbon sphere-loaded metal nanoparticle catalyst with high activity, high selectivity and stability, which has a practical application prospect, is urgently needed.
The common methods for preparing the carbon spheres comprise a hard template method, a soft template method, a hydrothermal carbonization method, a microemulsion polymerization method and the like, generally speaking, the hard template method has more steps and needs to remove a template by a strong alkaline solution, and the soft template method has the defects of low yield and high cost; the hydrothermal carbonization method is difficult to control the porosity and size of the carbon spheres, so the wide application of the method is limited; microemulsion polymerization processes suffer from low yields and from the tendency to aggregate.
At present, biomass energy is used for replacing fossil energy to become a hotspot, and bio-oil is processed into fuel and upstream chemical products through catalysis, so that the utilization of the biomass energy is realized.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a hollow nitrogen-doped carbon sphere supported metal catalyst, and a preparation method and application thereof, so as to solve the problems that in the process of preparing furfuryl amine by reductive amination of furfural in the prior art, the reaction condition of a catalyst system is harsh, high-temperature and high-pressure reaction conditions are required, the reaction time is long, the catalyst dosage is high, and the stability is low.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
a preparation method of a hollow nitrogen-doped carbon sphere supported metal catalyst comprises the following steps:
step 1, mixing styrene, methyl methacrylate, acrylic acid and ammonium bicarbonate to prepare polystyrene nanospheres;
step 2, adding the polystyrene nanospheres into water, stirring, adding dopamine hydrochloride to form a reaction system, and adding triaminomethane and concentrated hydrochloric acid to prepare a process sample;
step 3, removing the polystyrene nanospheres from the sample through roasting and carbonizing;
wherein, before the triaminomethane and the concentrated hydrochloric acid are added in the step 2, a metal source is added into a reaction system; or, adding a metal source after step 3; the metal source is ruthenium trichloride, cobalt nitrate hexahydrate, potassium tetrachloropalladate, chloroplatinic acid, nickel nitrate, copper nitrate, rhodium trichloride and chloroauric acid;
finally obtaining the hollow nitrogen-doped carbon sphere supported metal catalyst, wherein the mass ratio of the active metal is 0.5-10 wt%.
The invention is further improved in that:
preferably, in step 2, the mixing ratio of polystyrene to water is 0.1 g: 50 mL; the mass ratio of the dopamine hydrochloride to the polystyrene nanospheres is (0.2-5): 1; adding triaminomethane and concentrated hydrochloric acid, and adjusting the pH value of the mixed system to 8-9;
in the step 3, the roasting temperature is 500-900 ℃, and the roasting time is 0.5-5 h.
Preferably, before adding the triaminomethane and the concentrated hydrochloric acid in the step 2, the specific process of adding the metal source into the reaction system is as follows:
step 2, adding the polystyrene nanospheres into water, stirring, adding dopamine hydrochloride, adding triaminomethane and concentrated hydrochloric acid to adjust the pH value of the mixed system, adding a metal source into the mixed system after the pH value is adjusted, centrifuging, and freeze-drying;
and 3, grinding the product obtained in the step 2 into powder, and roasting in a mixed gas of nitrogen and hydrogen to prepare the nitrogen-doped hollow carbon sphere loaded metal nano catalyst.
Preferably, the specific process of adding the metal source after step 3 is as follows:
step 2, adding the polystyrene nanospheres into water, stirring, adding dopamine hydrochloride to form a reaction system, and adding triaminomethane and concentrated hydrochloric acid;
in the step 3, roasting and carbonizing the product obtained in the step 2 to prepare the nitrogen-doped hollow carbon spheres;
step 4, dispersing the nitrogen-doped hollow carbon spheres in water, adding a metal source, performing ultrasonic treatment, stirring in an oil bath pot, adjusting the pH value of the whole system through NaOH, and adding ice blocks and NaBH 4 And after stirring is kept, carrying out suction filtration and freezing on the system, and drying to obtain the nitrogen-doped hollow carbon sphere loaded metal nano catalyst.
Preferably, in the step 4, the mixing ratio of the nitrogen-doped hollow carbon spheres to the water is 50 mg: 20 mL.
Preferably, in the step 4, the pH value of the whole system is adjusted to 7-9 by NaOH.
Preferably, in step 4, NaBH is added 4 And the molar ratio of the metal in the metal source is 20-30.
A hollow nitrogen-doped carbon sphere supported metal catalyst prepared by the preparation method.
Preferably, the catalyst is used as a catalyst for preparing furfuryl amine from furfural;
mixing the catalyst, furfural, ammonia water and methanol in a reaction kettle for reaction, wherein the reaction atmosphere is hydrogen, the reaction temperature is 70 ℃, the reaction time is 4h, the rotation speed is 500 r, and obtaining furfurylamine through centrifugal separation after the reaction.
Preferably, the mixing ratio of the catalyst, the furfural, the ammonia water and the methanol is as follows: 10 mg: 48 mg: 1.25 mL: 5 mL.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a preparation method of a nitrogen-doped hollow carbon sphere loaded metal nano catalyst, which comprises two methods, wherein one method is a direct synthesis method. A post-synthesis method comprises the steps of firstly, adding dopamine hydrochloride into a prepared hard template to serve as a nitrogen source and a carbon source, polymerizing the nitrogen source and the carbon source on the hard template, and roasting to form nitrogen-doped hollow carbon spheres. And then adding a metal source on the basis of the nitrogen-doped hollow carbon spheres so that the metal source is loaded on the nitrogen-doped hollow carbon spheres. According to the two methods, polystyrene is used as a hard template to prepare the nitrogen-doped hollow carbon spheres, the nitrogen-doped hollow carbon spheres are used as a framework structure, one metal source is added in the synthesis process of the nitrogen-doped hollow carbon spheres, and the other metal source is attached to the nitrogen-doped hollow carbon spheres after the nitrogen-doped hollow carbon spheres are formed; the two-part post-synthesis method is characterized in that: firstly, polymerizing a nitrogen source and a carbon source on polystyrene nanospheres, then roasting at high temperature to form nitrogen-doped hollow carbon spheres, then loading metal, and then synthesizing to prepare the catalyst, wherein metal nanoparticles are arranged on the outer surfaces of the hollow spheres. The nitrogen-doped hollow carbon sphere-loaded metal nano catalyst prepared by the invention has the controllability of macroscopic size and microstructure (dispersion degree, specific surface area, pore diameter and the like); the catalyst can reach the standards of green, environmental protection, sustainable development and the like, and has better industrial application prospect.
Furthermore, the hard template method used in the invention adds the nitrogen source and the carbon source together, thus simplifying the steps, and the template of the polystyrene nanosphere is removed after high-temperature roasting, so that the operation of removing the template by specially using strong alkaline solution is not needed.
The invention also discloses a nitrogen-doped hollow carbon sphere loaded metal nano catalyst, wherein the catalyst is a porous material which takes carbon as a basic skeleton and has a highly developed pore structure, and the carbon material has the advantages of high specific surface area, adjustable pore diameter and the like due to the developed pore structure; in addition, the carbon material has a series of characteristics of good chemical stability, fast heat conduction, high temperature resistance, corrosion resistance and the like, and nitrogen-doped hollow carbon spheres can enable nitrogen atoms to enter a framework of the carbon material and be combined with the carbon atoms in different forms to serve as a carrier material of the supported metal catalyst due to the hollow structure, the higher specific surface area, the adjustable pore structure or the surface chemical property of the nitrogen-doped hollow carbon spheres. Nitrogen doping introduces more active sites into the carbon material that can promote nucleation and kinetic growth of the catalyst nanoparticles, which can promote the formation of smaller metal nanoparticles. The nitrogen-doped hollow carbon sphere-loaded metal nano-catalyst prepared by the invention can reach the standards of environmental protection, sustainable development and the like, and has a good industrial application prospect.
The invention also discloses application of the nitrogen-doped hollow carbon sphere supported metal nano catalyst, the high dispersibility of the catalyst with the structure can improve the utilization rate of active metal components in the catalyst, reduce the production cost and the metal loading capacity, and simultaneously is beneficial to forming stronger metal-carrier interaction so as to enhance the stability and the catalytic activity of the catalyst, and the property is particularly important for noble metal catalysts and non-noble metal catalysts. More importantly, the hollow cavity and the mesoporous shell layer can provide a specific limited-domain space for the metal nanoparticles, can stabilize and disperse the metal nanoparticles in the cavity or in the pore passage of the shell layer, and simultaneously provide a limited-domain reaction environment for the series reaction, so that reactants and intermediates are locally enriched, and the processes of adsorption, reaction and the like of the reactants on the surface of a metal active site are enhanced. The nitrogen-doped hollow carbon sphere-loaded metal nano catalyst has excellent structural properties, and when the nitrogen-doped hollow carbon sphere-loaded metal nano catalyst is applied to the preparation of furfuryl amine through efficient reductive amination of biomass-based furfural, the nitrogen-doped hollow carbon sphere-loaded metal nano catalyst can obviously improve the stability of metal nano particles, and can avoid the inactivation caused by aggregation, growth and loss of the nano metal particles in the catalytic reaction process, so that the stability of the catalyst is ensured. The catalyst is applied to the reaction of preparing primary amine by reductive amination of biomass-based aldehyde ketone, in particular to the reaction of preparing furfuryl amine by catalytic reductive amination of furfural, and has potential application value in the conversion of preparing furfuryl amine by reductive amination of furfural.
Drawings
FIG. 1 is an SEM image of polystyrene nanospheres of the present invention;
FIG. 2 is an SEM image of hollow carbon spheres of the present invention;
Detailed Description
The invention is described in further detail below with reference to the following figures and specific examples:
the embodiment of the invention provides a catalyst for preparing furfuryl amine by furfural reductive amination, which is a nitrogen-doped hollow carbon sphere supported metal nano catalyst M @ NHCS-x-y-z, wherein NHCS is a nitrogen-doped hollow carbon sphere, M is a metal component, x represents the mass ratio of dopamine to polystyrene, and the numerical value is 0.2-5; y represents the roasting temperature, and the value is 500-900 ℃; the z table comprises the mass percentage of the active metal component in the whole carrier, the carrier is a nitrogen-doped hollow carbon sphere, and the active metal component is loaded on the hollow carrier. The hard template of the catalyst is polystyrene nanospheres, a nitrogen source, a carbon source and metal components are loaded on the hard template, active metal is any one or combination of more than two of ruthenium, cobalt, nickel, copper, rhodium, palladium, platinum and gold, and the content of the active metal in the catalyst is 0.5-10 wt% in percentage by mass.
The embodiment of the invention provides a preparation method of a catalyst for preparing furfuryl amine by reductive amination of furfural, which comprises the following steps: (1) preparing a hard template; (2) polymerizing the carbon source and nitrogen source precursors on the surface of the hard template to form a compound; (3) adding a metal precursor; (4) and (4) high-temperature roasting. The steps of (3) and (4) may be reversed according to the sequence of loading the metal precursor.
The embodiment of the invention provides a nitrogen-doped hollow carbon sphere loaded noble metal-based nano catalyst applied to preparation of furfuryl amine by reductive amination of furfural, which comprises the following specific steps:
1. preparing a hard template:
preparing a polystyrene hard template: adding 21mL of styrene, 1.1mL of methyl methacrylate, 0.92mL of acrylic acid and 0.49g of ammonium bicarbonate into 100mL of deionized water, adding the mixture into a round-bottom flask, putting the round-bottom flask into an oil bath pot, heating and stirring, adding 0.53g of ammonium persulfate when the temperature of the round-bottom flask rises to 70 ℃, then heating the round-bottom flask to 80 ℃, stirring for 12 hours, carrying out centrifugal separation after stirring, washing the centrifugal product (twice washing with water and twice washing with ethanol), preparing a polystyrene nanosphere serving as a hard template, wherein the particle size of the prepared polystyrene nanosphere is 200-400 nm, as shown in figure 1, the size of the prepared polystyrene nanosphere is uniform.
2. Direct synthesis method
2.1. Adding carbon and nitrogen sources and metal precursors
Adding 0.1g of hard template into 50mL of deionized water, carrying out ultrasonic treatment for 30min, putting the mixture into an oil bath pot, stirring, and stirring for 30 min; adding dopamine hydrochloride serving as a carbon source and nitrogen source precursor, wherein the mass ratio of the dopamine hydrochloride to the hard template is (0.2-5): 1; adding a metal source according to different metal loading amounts, stirring for 30min, adding triaminomethane and concentrated hydrochloric acid to enable the pH value of the whole mixed system to be 8-9, stirring for 22h, centrifuging, freeze-drying, removing water in the centrifuged sample, and obtaining the sample of the nitrogen-doped solid carbon sphere loaded with the nano metal. The metal source is ruthenium trichloride, cobalt nitrate hexahydrate, potassium tetrachloropalladate, chloroplatinic acid, nickel nitrate, copper nitrate, rhodium trichloride and chloroauric acid, and the corresponding metals are Ru, Co, Pd, Pt, Ni, Cu, Rh and Au respectively.
2.2. Carbonization and template removal
And (3) grinding the sample obtained in the step (2.1) into powder, placing the powder into a mixed gas of nitrogen and hydrogen for roasting, wherein the volume fraction of the hydrogen is 5-50%, the sintering temperatures are respectively 500-900 ℃, the heating rate is 2-10 ℃/min, the heat preservation time is 0.5-5h, and the nitrogen-doped hollow carbon sphere-loaded Ru nano catalyst is obtained after roasting is finished.
3. Post-synthesis method
3.1 addition of carbon and nitrogen sources:
adding 0.1g of hard template into 50mL of deionized water, performing ultrasonic treatment for 30min, and then putting the mixture into an oil bath pot for stirring; and after stirring for 30min, adding dopamine hydrochloride, wherein the mass ratio of the dopamine hydrochloride to the hard template is (0.2-5): 1, adding triaminomethane and concentrated hydrochloric acid to enable the pH value of the whole mixed system to be 8-9, stirring for 15 hours, and putting the stirred sample into a vacuum drying oven, wherein the drying temperature is 70 ℃, and the drying time is 6-8 hours.
3.2 carbonization and template removal:
and (3) putting the sample obtained in the step (3.1) into a mixed gas of nitrogen and hydrogen for roasting, wherein the volume fraction of the hydrogen accounts for 5-50%, the firing temperature is 500-900 ℃, the heating rate is 2-10 ℃/min, the heat preservation time is 0.5-5h, and the nitrogen-doped hollow carbon spheres are obtained after roasting is finished.
3.3 addition of Metal precursor
1) Dispersing 50mg of nitrogen-doped hollow carbon spheres in 20mL of deionized water, carrying out ultrasonic treatment for 30min, and then transferring into an oil bath pot to stir for 30 min;
2) adding a metal source into the flask according to different metal source loading amounts, performing ultrasonic treatment for 30min, and then transferring into an oil bath pot to stir for 30 min;
3) adjusting the pH, dropwise adding a 0.2M NaOH aqueous solution into the flask by using a rubber head dropper, and adjusting the pH to 7-9;
4) adding ice blocks, reducing the temperature to about 0-5 ℃, adding 0.20955g of NaBH4 (adding for multiple times), wherein the molar ratio of NaBH4 to the metal in the metal source is 20-30;
5) changing ice blocks regularly, keeping the temperature and stirring for 12 hours;
6) and carrying out suction filtration, freezing and freeze drying on the obtained sample to obtain the nitrogen-doped hollow carbon sphere loaded metal nano catalyst required by the experiment.
The process of applying the catalyst prepared by the preparation method to preparing furfuryl amine by furfural comprises the following steps: adding 10mg of catalyst, 48mg of furfural, 1.25mL of ammonia water and 5mL of methanol into a lining of a 50mL reaction kettle, introducing high-purity hydrogen to replace gas for 5 times, filling hydrogen to 3MPa, heating to 70 ℃, keeping the temperature for 4h, rotating at the speed of 500 revolutions, after the reaction is finished, rapidly cooling to room temperature, then carrying out centrifugal separation on reaction liquid, and taking supernatant liquid to carry out gas chromatography detection.
The technical solutions of the present invention will be described in detail below with reference to several embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments, and all other embodiments obtained by those skilled in the art without any inventive work based on the embodiments of the present invention belong to the protection scope of the present invention.
The experimental materials used in the examples used below were purchased from conventional biochemical reagent stores, unless otherwise specified.
Example 1
Direct synthesis method, preparation of Ru @ NHCS-1-500-3 catalyst
Adding 0.1g of hard template (polystyrene nanosphere) into 50mL of deionized water, performing ultrasonic treatment for 30min, stirring in an oil bath, stirring for 30min, adding 0.1g of dopamine (multiple additions), adding 17.6mg of RuCl 3 Stirring for 30min, adding 0.30285g of triaminomethane and 61.5. mu.l of concentrated hydrochloric acid, the pH of the entire mixed system being 8.5. After stirring for 22h, it was centrifuged and washed, and then frozen in a refrigerator, followed by freeze-drying. Grinding the frozen sample into powder, putting the powder into a mixed gas of nitrogen and hydrogen for roasting, wherein the roasting temperature is 500 ℃, the heating rate is 10 ℃/min, the heat preservation time is 2h, and the nitrogen-doped hollow carbon sphere-loaded Ru nano catalyst is obtained after roasting is finished.
Example 2
Direct synthesis method, preparation of Ru @ NHCS-1-600-3 catalyst
Adding 0.1g of hard template (polystyrene spheres) into 50mL of deionized water, performing ultrasonic treatment for 30min, putting the mixture into an oil bath pot, stirring, adding 0.1g of dopamine (adding multiple times) after stirring for 30min, and adding 17.6mg of RuCl 3 After stirring for 30min, 0.30285g of triaminomethane and 61.5. mu.l of concentrated hydrochloric acid were added, and the pH of the whole mixed system was 8.5. After stirring for 22h, it was centrifuged and washed, and then frozen in a refrigerator, followed by freeze-drying. Grinding the frozen sample into powder, putting the powder into a mixed gas of nitrogen and hydrogen for roasting, wherein the roasting temperature is 600 ℃, the heating rate is 10 ℃/min, the heat preservation time is 2h, and the nitrogen-doped hollow carbon sphere-loaded Ru nano catalyst is obtained after roasting is finished.
Example 3
Direct synthesis, Ru @ NHCS-1-600-5 catalyst
Adding 0.1g of hard template (polystyrene spheres) into 50mL of deionized water, performing ultrasonic treatment for 30min, putting the mixture into an oil bath pot, stirring, adding 0.1g of dopamine (adding multiple times) after stirring for 30min, and adding 21.6mg of RuCl 3 After stirring for 30min, 0.30285g of triaminomethane and 61.5. mu.l of concentrated hydrochloric acid were added, and the pH of the whole mixed system was 8.5. After stirring for 22h, it was centrifuged and washed, and then frozen in a refrigerator, followed by freeze-drying. Grinding the frozen sample into powder, putting the powder into a mixed gas of nitrogen and hydrogen for roasting, wherein the roasting temperature is 500 ℃, the heating rate is 10 ℃/min, the heat preservation time is 2h, and the nitrogen-doped hollow carbon sphere-loaded Ru catalyst is obtained after roasting is finished.
Example 4
Direct synthesis, Ru @ NHCS-2-500-3 catalyst
0.1g of hard template (polystyrene pellets) is added into 50mL of deionized water, after ultrasonic treatment for 30min, the mixture is placed into an oil bath pot and stirred, after stirring for 30min, 0.2g of dopamine (multiple addition) is added, 19.05mg of RuCl3 is added, after stirring for 30min, 0.30285g of triaminomethane and 61.5 microliters of concentrated hydrochloric acid are added, and the pH value of the whole mixed system is 8.5. After stirring for 22h, it was centrifuged and washed, and then frozen in a refrigerator, followed by freeze-drying. Grinding the frozen sample into powder, putting the powder into a mixed gas of nitrogen and hydrogen for roasting, wherein the roasting temperature is 500 ℃, the heating rate is 10 ℃/min, the heat preservation time is 2h, and the nitrogen-doped hollow carbon sphere-loaded Ru catalyst is obtained after roasting is finished.
Example 5
Direct synthesis method, Ru @ NHCS-2-900-3 catalyst
0.1g of hard template (polystyrene beads) was added to 50mL of deionized water, and after 30min of sonication, the mixture was placed in an oil bath and stirred, after 30min of stirring, 0.2g of dopamine (multiple additions) was added, 19.05mg of RuCl3 was added, and after 30min of stirring, 0.30285g of triaminomethane and 61.5. mu.l of concentrated hydrochloric acid were added. After stirring for 22h, it was centrifuged and washed, and then frozen in a refrigerator, followed by freeze-drying. Grinding the frozen sample into powder, putting the powder into a mixed gas of nitrogen and hydrogen for roasting, wherein the roasting temperature is 900 ℃, the heating rate is 10 ℃/min, the heat preservation time is 2h, and the nitrogen-doped hollow carbon sphere-loaded Ru catalyst is obtained after roasting.
Example 6
Direct synthesis method, Co @ NHCS-0.2-700-0.5 catalyst
Adding 0.1g of hard template (polystyrene spheres) into 50mL of deionized water, performing ultrasonic treatment for 30min, putting the mixture into an oil bath pot, stirring, adding 0.02g of dopamine (adding for multiple times) after stirring for 30min, adding 2.98mg of cobalt nitrate hexahydrate, stirring for 30min, and adding triaminomethane and concentrated hydrochloric acid to enable the pH value of the whole system to be 8. After stirring for 22h, it was centrifuged and washed, and then frozen in a refrigerator, followed by freeze-drying. Grinding the frozen sample into powder, putting the powder into a mixed gas of nitrogen and hydrogen for roasting, wherein the roasting temperature is 700 ℃, the heating rate is 10 ℃/min, the heat preservation time is 5h, and after the roasting is finished, the nitrogen-doped hollow carbon sphere supported Co catalyst is obtained, and the mass ratio of the metal active component to the catalyst is 0.5%.
Example 7
Direct synthesis method, Pd @ NHCS-3-800-2 catalyst
Adding 0.1g of hard template (polystyrene spheres) into 50mL of deionized water, performing ultrasonic treatment for 30min, putting the mixture into an oil bath pot, stirring, adding 0.3g of dopamine (adding for multiple times) after stirring for 30min, adding 25.039mg of potassium tetrachloropalladate, stirring for 30min, and adding triaminomethane and concentrated hydrochloric acid to enable the pH value of the whole system to be 9. After stirring for 22h, it was centrifuged and washed, and then frozen in a refrigerator, followed by freeze-drying. Grinding the frozen sample into powder, putting the powder into a mixed gas of nitrogen and hydrogen for roasting, wherein the roasting temperature is 800 ℃, the heating rate is 10 ℃/min, the heat preservation time is 0.5h, and after the roasting is finished, the catalyst of the nitrogen-doped hollow carbon sphere loaded Pd is obtained, and the mass ratio of the metal active component in the catalyst is 2%.
Example 8
Direct synthesis, Pt @ NHCS-4-500-6 catalyst
Adding 0.1g of hard template (polystyrene spheres) into 50mL of deionized water, performing ultrasonic treatment for 30min, putting the mixture into an oil bath pot, stirring, adding 0.4g of dopamine (adding for multiple times), adding 84.74mg of chloroplatinic acid, stirring for 30min, and adding triaminomethane and concentrated hydrochloric acid to enable the pH value of the whole system to be 8.5. After stirring for 22h, it was centrifuged and washed, and then frozen in a refrigerator, followed by freeze-drying. Grinding the frozen sample into powder, putting the powder into a mixed gas of nitrogen and hydrogen for roasting, wherein the roasting temperature is 500 ℃, the heating rate is 10 ℃/min, the heat preservation time is 4h, and after the roasting is finished, the catalyst of the nitrogen-doped hollow carbon sphere loaded Pt is obtained, and the mass ratio of the metal active component in the catalyst is 6%.
Example 9
Direct synthesis method, Ru @ NHCS-2-900-5 catalyst
0.1g of hard template (polystyrene beads) was added to 50mL of deionized water, and after 30min of sonication, the mixture was put in an oil bath and stirred, after 30min of stirring, 0.2g of dopamine (multiple addition) was added, 42.67mg of ruthenium trichloride was added, and after 30min of stirring, 0.30285g of triaminomethane and 61.5. mu.L of concentrated hydrochloric acid were added. After stirring for 22h, it was centrifuged and washed, and then frozen in a refrigerator, followed by freeze-drying. Grinding the frozen sample into powder, putting the powder into a mixed gas of nitrogen and hydrogen for roasting, wherein the roasting temperature is 600 ℃, the heating rate is 10 ℃/min, the heat preservation time is 3h, and after the roasting is finished, the nitrogen-doped hollow carbon sphere-loaded Ru catalyst is obtained, and the mass ratio of the metal active component in the catalyst is 10%.
Example 10
Post-synthesis, Ru @ NHCS-1-500-3 catalyst
Adding 0.1g of hard template into 50mL of deionized water, carrying out ultrasonic treatment for 30min, putting the mixture into an oil bath pot, stirring the mixture for 30min, adding 0.1g of dopamine (adding the dopamine for multiple times), and stirring the mixture for 15 h. And then placing the sample into a mixed gas of nitrogen and hydrogen for roasting, wherein the roasting temperature is 500 ℃, the heating rate is 10 ℃/min, the heat preservation time is 2h, and the hollow carbon spheres are obtained after roasting is finished. Dispersing 50mg of hollow carbon spheres in 20mL of deionized water, carrying out ultrasonic treatment for 30min, and then transferring into an oil bath pot to stir for 30 min; 3.18mg of RuCl was added 3 Putting metal into a flask, performing ultrasonic treatment for 30min, and stirring in an oil bath kettle for 30 min; adjusting the pH, dropwise adding a 0.2M NaOH aqueous solution into the flask by using a rubber head dropper, and adjusting the pH to about 8; adding ice, cooling to about 0 deg.C, adding 0.20955g NaBH 4 (multiple additions); changing ice blocks regularly, keeping the temperature and stirring for 12 hours; and (3) carrying out suction filtration, freezing and freeze drying on the obtained sample to obtain the nitrogen-doped hollow carbon sphere supported metal Ru catalyst required by the experiment. The structural form of the prepared nitrogen-doped hollow carbon sphere catalyst is shown in fig. 2. It is seen that the nitrogen-and carbon-source-loaded polystyrene nanospheres have been successfully carbonized, and the polystyrene nanospheres have decomposed at high temperature to form nitrogen-doped carbon spheres having hollow structures.
Example 11
Post-synthesis, Ru @ NHCS-1-800-3 catalyst
Adding 0.1g of hard template into 50mL of deionized water, carrying out ultrasonic treatment for 30min, putting the mixture into an oil bath pot, stirring the mixture for 30min, adding 0.1g of dopamine (adding the dopamine for multiple times), and stirring the mixture for 15 h. And then placing the sample into a mixed gas of nitrogen and hydrogen for roasting, wherein the roasting temperature is 800 ℃, the heating rate is 10 ℃/min, the heat preservation time is 2h, and the hollow carbon spheres are obtained after roasting is finished. Dispersing 50mg of hollow carbon spheres in 20mL of deionized water, carrying out ultrasonic treatment for 30min, and then transferring into an oil bath pot to stir for 30 min; 3.18mg of RuCl was added 3 Putting metal into a flask, performing ultrasonic treatment for 30min, and stirring in an oil bath kettle for 30 min; adjusting the pH, dropwise adding a 0.2M NaOH aqueous solution into the flask by using a rubber head dropper, and adjusting the pH to about 8; adding ice blocks, cooling to about 0 ℃, and adding 0.20955g of NaBH4 (adding for multiple times); changing ice blocks regularly, keeping the temperature and stirring for 12 hours; and (3) carrying out suction filtration, freezing and freeze drying on the obtained sample to obtain the nitrogen-doped hollow carbon sphere supported metal Ru catalyst required by the experiment.
Example 12
Direct synthesis, Co @ NHCS-1-500-3 catalyst
0.1g of hard template (polystyrene beads) was added to 50mL of deionized water, and after 30min of sonication, the mixture was put in an oil bath and stirred, after 30min of stirring, 0.1g of dopamine (multiple addition) was added, 30.56mg of cobalt nitrate hexahydrate was added, and after 30min of stirring, 0.30285g of triaminomethane and 61.5. mu.l of concentrated hydrochloric acid were added. After stirring for 22h, it was centrifuged and washed, and then frozen in a refrigerator, followed by freeze-drying. Grinding the frozen sample into powder, putting the powder into a mixed gas of nitrogen and hydrogen for roasting, wherein the roasting temperature is 500 ℃, the heating rate is 10 ℃/min, the heat preservation time is 2h, and obtaining the nitrogen-doped hollow carbon sphere supported Co catalyst after roasting.
Example 13
Post-synthesis, Co @ NHCS-0.2-500-0.5 catalyst
Adding 0.1g of hard template into 50mL of deionized water, carrying out ultrasonic treatment for 30min, putting the mixture into an oil bath pot, stirring the mixture for 30min, adding 0.02g of dopamine (adding the dopamine for multiple times), and stirring the mixture for 15 h. Then the sample is put into the mixture of nitrogen and hydrogenAnd (3) roasting in a gas mixture, wherein the roasting temperature is 500 ℃, the heating rate is 10 ℃/min, the heat preservation time is 5h, and the hollow carbon spheres are obtained after roasting. Dispersing 50mg of hollow carbon spheres in 20mL of deionized water, carrying out ultrasonic treatment for 30min, and then transferring into an oil bath pot to stir for 30 min; adding 1.24mg of cobalt nitrate hexahydrate metal into the flask, carrying out ultrasonic treatment for 30min, transferring into an oil bath pot, and stirring for 30 min; adjusting the pH, dropwise adding 0.2M NaOH aqueous solution into the flask by using a rubber-tipped dropper, and adjusting the pH to about 8; adding ice, cooling to about 0 deg.C, adding 3.22mgNaBH 4 (multiple additions); changing ice blocks regularly, keeping the temperature and stirring for 12 hours; and (3) carrying out suction filtration, freezing and freeze drying on the obtained sample to obtain the nitrogen-doped hollow carbon sphere supported metal Ru catalyst required by the experiment.
Example 14
Post-synthesis, Pd @ NHCS-1-800-8 catalyst
Adding 0.1g of hard template into 50mL of deionized water, carrying out ultrasonic treatment for 30min, putting the mixture into an oil bath pot, stirring the mixture for 30min, adding 0.1g of dopamine (adding the dopamine for multiple times), and stirring the mixture for 15 h. And then placing the sample into a mixed gas of nitrogen and hydrogen for roasting, wherein the roasting temperature is 700 ℃, the heating rate is 10 ℃/min, the heat preservation time is 3h, and the hollow carbon spheres are obtained after roasting is finished. Dispersing 50mg of hollow carbon spheres in 20mL of deionized water, carrying out ultrasonic treatment for 30min, and then transferring into an oil bath pot to stir for 30 min; adding 13.33mg of potassium tetrachloropalladate metal into the flask, carrying out ultrasonic treatment for 30min, transferring into an oil bath pot, and stirring for 30 min; adjusting the pH, dropwise adding a 0.2M NaOH aqueous solution into the flask by using a rubber head dropper, and adjusting the pH to about 8; adding ice, cooling to about 0 deg.C, adding 38.62mg NaBH 4 (multiple additions); changing ice blocks regularly, keeping the temperature and stirring for 12 hours; and (3) carrying out suction filtration, freezing and freeze drying on the obtained sample to obtain the nitrogen-doped hollow carbon sphere supported metal Ru catalyst required by the experiment.
Example 15
Post-synthesis, Pt @ NHCS-5-900-10 catalyst
Adding 0.1g of hard template into 50mL of deionized water, carrying out ultrasonic treatment for 30min, putting the mixture into an oil bath pot, stirring the mixture for 30min, adding 0.5g of dopamine (adding the dopamine for multiple times), and stirring the mixture for 15 h. Rear endAnd (3) putting the sample into a mixed gas of nitrogen and hydrogen for roasting, wherein the roasting temperature is 900 ℃, the heating rate is 10 ℃/min, the heat preservation time is 0.5h, and the hollow carbon spheres are obtained after roasting is finished. Dispersing 50mg of hollow carbon spheres in 20mL of deionized water, carrying out ultrasonic treatment for 30min, and then transferring into an oil bath pot to stir for 30 min; adding 14.75mg of chloroplatinic acid metal into the flask, performing ultrasonic treatment for 30min, and transferring into an oil bath pot to stir for 30 min; adjusting the pH, dropwise adding a 0.2M NaOH aqueous solution into the flask by using a rubber head dropper, and adjusting the pH to about 8; adding ice, cooling to about 0 deg.C, adding 32.32mg NaBH 4 (multiple additions); changing ice blocks regularly, keeping the temperature and stirring for 12 hours; and (3) carrying out suction filtration, freezing and freeze drying on the obtained sample to obtain the nitrogen-doped hollow carbon sphere supported metal Ru catalyst required by the experiment.
Example 16
Adding 10mg of Ru @ NHCS-1-500-3 (prepared by a direct synthesis method) catalyst, 48mg of furfural, 1.25mL of ammonia water and 5mL of methanol into a 50mL reaction kettle lining, introducing high-purity hydrogen to replace gas for 5 times, filling hydrogen to 3MPa, heating to 70 ℃, keeping for 4 hours at the rotating speed of 500 revolutions, after the reaction is finished, rapidly cooling to room temperature, then carrying out centrifugal separation on the reaction liquid, and taking the supernatant for gas chromatography detection.
After the reaction was completed, the content of furfuryl amine in the reaction solution was calculated by the following method.
The reaction product was quantitatively analyzed by gas chromatography (Agilent 7820, Agilent, beijing Agilent limited), the column was KB-5, the specification was 25m × 0.25mm × 1.0 μm. Keeping the temperature at 70 ℃ for 10min, raising the temperature to 250 ℃ at the heating rate of 10 ℃/min, and adjusting the temperature of a sample inlet: 260 ℃, detector temperature: at 260 ℃. FID hydrogen flame ionization detector.
The conversion of furfural, selectivity and yield of furfurylamine were calculated according to the following formulas.
The results showed that the furfural conversion was 100%, the furfurylamine selectivity was 90%, and the furfurylamine yield was 90%.
Example 17
Adding 10mg of Ru @ NHCS-1-600-3 (prepared by a direct synthesis method) catalyst, 48mg of furfural, 1.25mL of ammonia water and 5mL of methanol into a 50mL reaction kettle lining, introducing high-purity hydrogen to replace gas for 5 times, filling hydrogen to 3MPa, heating to 70 ℃, keeping for 4 hours at the rotating speed of 500 revolutions, after the reaction is finished, rapidly cooling to room temperature, then carrying out centrifugal separation on the reaction liquid, and taking the supernatant to carry out gas chromatography detection. The conversion of furfural was 100%, the selectivity of furfurylamine was 85%, and the yield of furfurylamine was 85%.
Example 18
Adding 10mg of Ru @ NHCS-2-600-3 (prepared by a direct synthesis method) catalyst, 48mg of furfural, 1.25mL of ammonia water and 5mL of methanol into a 50mL reaction kettle lining, introducing high-purity hydrogen to replace gas for 5 times, filling hydrogen to 3MPa, heating to 70 ℃, keeping for 4 hours at the rotating speed of 500 revolutions, after the reaction is finished, rapidly cooling to room temperature, then carrying out centrifugal separation on the reaction liquid, and taking the supernatant for gas chromatography detection. It shows that the conversion rate of furfural is 100%, the selectivity of furfuryl amine is 75%, and the yield of furfuryl amine is 75%.
Example 19
Adding 10mg of Ru @ NHCS-2-900-3 (prepared by a direct synthesis method) catalyst, 48mg of furfural, 1.25mL of ammonia water and 5mL of methanol into a 50mL reaction kettle lining, introducing high-purity hydrogen to replace gas for 5 times, charging hydrogen to 3MPa, heating to 70 ℃, keeping for 4 hours at the rotating speed of 500 revolutions, after the reaction is finished, rapidly cooling to room temperature, then carrying out centrifugal separation on reaction liquid, and taking supernatant liquid for gas chromatography detection. It shows that the conversion rate of furfural is 100%, the selectivity of furfuryl amine is 76%, and the yield of furfuryl amine is 76%.
Example 20
Adding 10mg of Ru @ NHCS-2-600-3 (prepared by a direct synthesis method) catalyst, 48mg of furfural, 1.25mL of ammonia water and 5mL of methanol into a 50mL reaction kettle lining, introducing high-purity hydrogen to replace gas for 5 times, filling hydrogen to 3MPa, heating to 70 ℃, keeping for 4 hours at the rotating speed of 500 revolutions, after the reaction is finished, rapidly cooling to room temperature, then carrying out centrifugal separation on the reaction liquid, and taking the supernatant for gas chromatography detection. It was shown that the conversion of furfural was 100%, the selectivity of furfurylamine was 70%, and the yield of furfurylamine was 70%.
Example 21
Adding 10mg of Ru @ NHCS-1-500-3 (prepared by post-synthesis method) catalyst, 48mg of furfural, 1.25mL of ammonia water and 5mL of methanol into a 50mL reaction kettle lining, introducing high-purity hydrogen to replace gas for 5 times, charging hydrogen to 3MPa, heating to 70 ℃, keeping for 4h at the rotating speed of 500 revolutions, after the reaction is finished, rapidly cooling to room temperature, then carrying out centrifugal separation on the reaction liquid, and taking the supernatant for gas chromatography detection. It was shown that the conversion of furfural was 100%, the selectivity of furfurylamine was 80%, and the yield of furfurylamine was 80%.
Example 22
Adding 10mg of Ru @ NHCS-1-500-5 (prepared by post-synthesis method), 48mg of furfural, 1.25mL of ammonia water and 5mL of methanol into a 50mL reaction kettle lining, introducing high-purity hydrogen to replace gas for 5 times, filling hydrogen to 3MPa, heating to 70 ℃, keeping for 4h at the rotating speed of 500 revolutions, after the reaction is finished, rapidly cooling to room temperature, then carrying out centrifugal separation on the reaction liquid, and taking the supernatant for gas chromatography detection. It was shown that the conversion of furfural was 100%, the selectivity of furfurylamine was 70%, and the yield of furfurylamine was 70%.
Example 23
Adding 10mg of Ru @ NHCS-1-800-3 (prepared by post-synthesis method) catalyst, 48mg of furfural, 1.25mL of ammonia water and 5mL of methanol into a lining of a 50mL reaction kettle, introducing high-purity hydrogen to replace gas for 5 times, introducing hydrogen to 3MPa, heating to 70 ℃, keeping for 4 hours at the rotating speed of 500 revolutions, after the reaction is finished, rapidly cooling to room temperature, then carrying out centrifugal separation on the reaction liquid, and taking the supernatant for gas chromatography detection. It shows that the conversion rate of furfural is 100%, the selectivity of furfurylamine is 73%, and the yield of furfurylamine is 73%.
Example 24
Adding 10mg of Pd @ NHCS-1-500-3 (prepared by a direct synthesis method), 48mg of furfural, 1.25mL of ammonia water and 5mL of methanol into a lining of a 50mL reaction kettle, introducing high-purity hydrogen to replace gas for 5 times, introducing hydrogen to 3MPa, heating to 70 ℃, keeping for 4 hours at the rotating speed of 500 revolutions, after the reaction is finished, rapidly cooling to room temperature, then carrying out centrifugal separation on the reaction liquid, and taking the supernatant for gas chromatography detection. It was shown that the conversion of furfural was 100%, the selectivity of furfurylamine was 80%, and the yield of furfurylamine was 80%.
Example 25
Adding 10mg of Cu @ NHCS-1-500-3 (prepared by a direct synthesis method) catalyst, 48mg of furfural, 1.25mL of ammonia water and 5mL of methanol into a lining of a 50mL reaction kettle, introducing high-purity hydrogen to replace gas for 5 times, then introducing hydrogen to 3MPa, heating to 70 ℃, keeping for 4 hours at the rotating speed of 500 revolutions, after the reaction is finished, rapidly cooling to room temperature, then carrying out centrifugal separation on the reaction liquid, and taking the supernatant liquid for gas chromatography detection. It shows that the conversion rate of furfural is 100%, the selectivity of furfuryl amine is 65%, and the yield of furfuryl amine is 65%.
The catalyst can reach the standards of green, environmental protection, sustainable development and the like, and has better industrial application prospect.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of a hollow nitrogen-doped carbon sphere supported metal catalyst is characterized by comprising the following steps:
step 1, mixing styrene, methyl methacrylate, acrylic acid and ammonium bicarbonate to prepare polystyrene nanospheres;
step 2, adding the polystyrene nanospheres into water, stirring, adding dopamine hydrochloride to form a reaction system, and adding triaminomethane and concentrated hydrochloric acid to prepare a process sample;
step 3, removing the polystyrene nanospheres from the sample through roasting and carbonizing;
wherein, before the triaminomethane and the concentrated hydrochloric acid are added in the step 2, a metal source is added into a reaction system; or, adding a metal source after step 3; the metal source is ruthenium trichloride, cobalt nitrate hexahydrate, potassium tetrachloropalladate, chloroplatinic acid, nickel nitrate, copper nitrate, rhodium trichloride and chloroauric acid;
finally obtaining the hollow nitrogen-doped carbon sphere supported metal catalyst, wherein the mass ratio of the active metal is 0.5-10 wt%.
2. The method for preparing the hollow nitrogen-doped carbon sphere-supported metal catalyst according to claim 1, wherein in the step 2, the mixing ratio of the polystyrene to the water is 0.1 g: 50 mL; the mass ratio of the dopamine hydrochloride to the polystyrene nanospheres is (0.2-5): 1; adding triaminomethane and concentrated hydrochloric acid, and adjusting the pH value of the mixed system to 8-9;
in the step 3, the roasting temperature is 500-900 ℃, and the roasting time is 0.5-5 h.
3. The method for preparing a hollow nitrogen-doped carbon sphere-supported metal catalyst according to claim 1, wherein the specific process of adding a metal source to the reaction system before adding the triaminomethane and the concentrated hydrochloric acid in the step 2 is as follows:
step 2, adding the polystyrene nanospheres into water, stirring, adding dopamine hydrochloride, adding triaminomethane and concentrated hydrochloric acid to adjust the pH value of the mixed system, adding a metal source into the mixed system after the pH value is adjusted, centrifuging, and freeze-drying;
and 3, grinding the product obtained in the step 2 into powder, and roasting in a mixed gas of nitrogen and hydrogen to prepare the nitrogen-doped hollow carbon sphere loaded metal nano catalyst.
4. The preparation method of the hollow nitrogen-doped carbon sphere supported metal catalyst according to claim 1, wherein the specific process of adding the metal source after the step 3 is as follows:
step 2, adding the polystyrene nanospheres into water, stirring, adding dopamine hydrochloride to form a reaction system, and adding triaminomethane and concentrated hydrochloric acid;
in the step 3, roasting and carbonizing the product obtained in the step 2 to prepare the nitrogen-doped hollow carbon spheres;
step 4, dispersing the nitrogen-doped hollow carbon spheres in water, adding a metal source, performing ultrasonic treatment, stirring in an oil bath pot, adjusting the pH value of the whole system through NaOH, and adding ice blocks and NaBH 4 And after stirring is kept, carrying out suction filtration and freezing on the system, and drying to obtain the nitrogen-doped hollow carbon sphere loaded metal nano catalyst.
5. The method for preparing a hollow nitrogen-doped carbon sphere-supported metal catalyst according to claim 4, wherein in the step 4, the mixing ratio of the nitrogen-doped hollow carbon sphere to the water is 50 mg: 20 mL.
6. The method for preparing the hollow nitrogen-doped carbon sphere-supported metal catalyst according to claim 4, wherein in the step 4, the pH value of the whole system is adjusted to 7-9 by NaOH.
7. The method for preparing the hollow nitrogen-doped carbon sphere-supported metal catalyst according to claim 4, wherein in the step 4, NaBH is added 4 And the molar ratio of the metal in the metal source is 20-30.
8. A hollow nitrogen-doped carbon sphere-supported metal catalyst prepared by the preparation method of any one of claims 1 to 7.
9. The use of the hollow nitrogen-doped carbon sphere supported metal catalyst according to claim 8, wherein the catalyst is used as a catalyst for preparing furfuryl amine from furfural;
mixing the catalyst, furfural, ammonia water and methanol in a reaction kettle for reaction, wherein the reaction atmosphere is hydrogen, the reaction temperature is 70 ℃, the reaction time is 4h, the rotation speed is 500 r, and obtaining furfurylamine through centrifugal separation after the reaction.
10. The use of claim 9, wherein the catalyst, the furfural, the ammonia water and the methanol are mixed in the following ratio: 10 mg: 48 mg: 1.25 mL: 5 mL.
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