CN111408392A - Cobalt-nitrogen co-doped porous carbon material catalyst and preparation method and application thereof - Google Patents
Cobalt-nitrogen co-doped porous carbon material catalyst and preparation method and application thereof Download PDFInfo
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 39
- YDVGDXLABZAVCP-UHFFFAOYSA-N azanylidynecobalt Chemical compound [N].[Co] YDVGDXLABZAVCP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
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- 238000005886 esterification reaction Methods 0.000 claims abstract description 19
- 230000003647 oxidation Effects 0.000 claims abstract description 18
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
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- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
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- 230000032050 esterification Effects 0.000 claims abstract description 6
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- 239000000203 mixture Substances 0.000 claims abstract description 4
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- 238000000034 method Methods 0.000 claims description 11
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- 238000001354 calcination Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
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- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical group [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical group [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- GBOVPZFEODYRSR-UHFFFAOYSA-N 2-(hydroxymethyl)-3h-furan-2-carbaldehyde Chemical compound OCC1(C=O)CC=CO1 GBOVPZFEODYRSR-UHFFFAOYSA-N 0.000 abstract description 27
- 229910000510 noble metal Inorganic materials 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 239000002243 precursor Substances 0.000 abstract description 5
- 229910052737 gold Inorganic materials 0.000 abstract description 3
- 229910052763 palladium Inorganic materials 0.000 abstract description 3
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract 2
- 125000003172 aldehyde group Chemical group 0.000 abstract 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract 1
- 239000010931 gold Substances 0.000 abstract 1
- 238000006709 oxidative esterification reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- LARLSBWABHVOTC-UHFFFAOYSA-N 1,1-bis(4-chlorophenyl)-2,2,2-trifluoroethanol Chemical compound C=1C=C(Cl)C=CC=1C(C(F)(F)F)(O)C1=CC=C(Cl)C=C1 LARLSBWABHVOTC-UHFFFAOYSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- HSSJULAPNNGXFW-UHFFFAOYSA-N [Co].[Zn] Chemical compound [Co].[Zn] HSSJULAPNNGXFW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000013249 bimetallic zeolitic imidazolate framework Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 1
- 239000013153 zeolitic imidazolate framework Substances 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
-
- B01J35/60—
-
- 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
- C07D307/56—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a cobalt-nitrogen co-doped porous carbon material catalyst, a preparation method thereof and application thereof in 2-hydroxymethylfurfural oxidation esterification reaction. The catalyst is prepared by taking chitosan as a precursor, stirring and mixing the chitosan with zinc salt and cobalt salt, and then pyrolyzing the mixture at high temperature. The cobalt-nitrogen co-doped porous carbon material is used as a catalyst, methanol is used as a solvent, an aldehyde group protection reagent and an esterification reagent, and oxygen at normal pressure is used as an oxidant, so that the conversion of HMF to furan-2, 5-methyl diformate can be realized at 50 ℃. The catalyst is cheap and easy to obtain, noble metal catalysts such as gold and palladium do not need to be added, the catalytic reaction condition is mild, the oxidation and esterification of HMF can be realized at low temperature and normal pressure in an oxygen atmosphere, the catalytic reaction can be carried out at high concentration, and the catalyst is suitable for industrial application.
Description
Technical Field
The invention belongs to the technical field of metal organic catalysis, and relates to a cobalt-nitrogen co-doped porous carbon material catalyst for 2-hydroxymethylfurfural oxidation esterification reaction and a preparation method thereof.
Background
The cobalt-nitrogen co-doped carbon material is widely applied to the fields of organic catalysis, electrocatalysis and energy storage. The common method for synthesizing the material generally uses organic ligand to coordinate with cobalt salt, then adds active carbon to load, and prepares (A) by high-temperature pyrolysisGreenchemistry 2018,20(1), 266-; ChemUSchem 2014,7(12), 3334-3340). However, the carbon material prepared by the method has smaller specific surface area, and the metal active sites of the carbon material are coated by carbon, so the catalytic performance is poorer. Addition of sacrificial agents, such as SiO, in the preparation of carbon materials2And inorganic metal salt, and the porous carbon material with high specific surface area can be prepared through the subsequent etching process, but the etching process is complicated and strong acid and strong alkali solution is generally needed (Science Advances 2018,4(7), eaat 0788). Cobalt-nitrogen co-doped porous carbon material can be obtained by taking cobalt-zinc bimetallic ZIF material as precursor through self-sacrifice template method, but the yield of the ZIF precursor is low (<10%) and the higher cost, and is not suitable for large-scale production (advanced materials 2015,27(34), 5010-.
2-Hydroxymethylfurfural (HMF) is an important chemical group generated by dehydration of biomass such as glucose, fructose, cellulose and the like, which can be used to convert into various commercial chemicals, wherein FDMC generated by oxidative esterification of HMF is an important unit for synthesizing PEF plastics and thus has received wide attention from the industry and academia. The conventional HMF oxidative esterification method mainly includes the following two methods: (1) HMF oxidation esterification reaction catalyzed by noble metals such as Pd, Au and the like (ChemSus chem2008,1, 75-78; J.Catal.2015,326, 1-8; Green chem.2018,20, 3050-3058.); (2) the catalyst is used for HMF oxidation esterification reaction (ChemSusChem 2014,7, 3334-3340; ChemCisChem 2016,8, 2907-2911; Catal. Commun.2017,90,91-94.) which is catalyzed by non-noble metals such as Co, Cu and the like.
However, the above methods have some disadvantages, for example, the use of noble metal catalysts such as Pd, Au, etc. increases the reaction cost, which is not favorable for industrial application; the use of sodium methoxide, potassium carbonate and other alkalis can cause water pollution, which is not favorable for environmental protection; additives such as K-OMS-2 and the like are additionally added in the reaction; the temperature and pressure required by the reaction are high, side reactions can be caused, and potential safety hazards exist.
Disclosure of Invention
The invention aims to provide a cobalt-nitrogen co-doped porous carbon material catalyst and a preparation method thereof, wherein the catalyst has excellent catalytic performance for an oxidation esterification reaction of HMF.
The technical scheme for realizing the purpose of the invention is as follows:
the preparation method of the cobalt-nitrogen co-doped porous carbon material catalyst comprises the following steps of preparing the cobalt-nitrogen co-doped porous carbon material catalyst by taking chitosan as a precursor:
step 1, sequentially adding zinc salt, cobalt salt and chitosan into a solvent, fully stirring and uniformly mixing, carrying out reduced pressure distillation to remove the solvent, and drying, wherein the solvent is any one of methanol, ethanol, water and a mixed solution of methanol and water, and the mass ratio of zinc to cobalt is 4-16: 1;
and 2, heating the mixture obtained in the step 1 to 700-900 ℃ at a heating rate of 5-10 ℃/min in an argon atmosphere, and calcining to obtain the cobalt-nitrogen Co-doped porous carbon material Co @ CN-ZnX-Y.
Preferably, in step 1, the zinc salt is zinc acetate, zinc nitrate or zinc sulfate.
Preferably, in step 1, the cobalt salt is cobalt chloride, cobalt nitrate or cobalt acetate.
Preferably, in the step 1, the mass ratio of the zinc to the cobalt is 8-12: 1.
Preferably, in the step 1, the drying is vacuum drying, the drying temperature is 80-100 ℃, and the drying time is 12-24 hours.
Preferably, in the step 1, the stirring and mixing temperature is 25-80 ℃, and the stirring time is 12-48 hours.
Preferably, in the step 2, the heat preservation time during the calcination is 1-4 h.
The invention provides a cobalt-nitrogen co-doped porous carbon material catalyst prepared by the preparation method.
The invention also provides an application of the cobalt-nitrogen co-doped porous carbon material catalyst in HMF oxidation esterification, wherein the cobalt-nitrogen co-doped porous carbon material is used as the catalyst to catalyze the HMF oxidation esterification under low-temperature and normal-pressure oxygen under the condition of not adding alkali and noble metal, and the specific method comprises the following steps:
mixing the HMF and cobalt-nitrogen co-doped porous carbon material catalyst with methanol, reacting at 50-60 ℃ under the condition of normal pressure oxygen, cooling after the reaction is finished, separating the catalyst from a reaction liquid, removing the methanol from an organic phase through rotary evaporation, and recrystallizing to obtain a reaction product.
Preferably, the reaction time is 16-18 h.
Compared with the prior art, the invention has the following advantages:
(1) the catalyst takes cheap biomass chitosan as a precursor, has low cost, simple preparation process, environmental protection and high production possibility;
(2) the cobalt-nitrogen co-doped porous carbon material is used as a catalyst to catalyze the oxidation esterification of HMF, the reaction condition is mild, any alkali, strong oxidant or noble metal catalyst is not needed, the yield is high, the selectivity is good, the product is easy to separate, the reaction can be carried out at high concentration (2M), and the possibility of production amplification is realized.
Drawings
Fig. 1 is an SEM image of the cobalt-nitrogen co-doped porous carbon material catalyst of the present invention.
FIG. 2 is a graph showing the effect of different temperature rising rates on the specific surface area of the cobalt-nitrogen co-doped porous carbon material and the yield of the oxidation esterification reaction of HMF.
FIG. 3 is a graph showing the effect of mass ratios of Zn and Co on the specific surface area of a cobalt-nitrogen Co-doped porous carbon material and the yield of an oxidation esterification reaction of HMF.
Detailed Description
The present invention will be described in more detail with reference to the following examples and the accompanying drawings.
Example 1: preparation of cobalt-nitrogen co-doped porous carbon material
Zinc acetate dihydrate (338mg), cobalt chloride hexahydrate (100mg) and chitosan (500mg) were added to a mixed solution of methanol and water (10 g of methanol, 10g of water), respectively, and the mixture was thoroughly stirred and mixed at 50 ℃ and the solvent was distilled off under reduced pressure, followed by drying in a vacuum oven at 80 ℃ for 12 hours. Calcining the obtained solid in a tube furnace under the argon atmosphere of 900 ℃ (the heating rate is 5 ℃/min, and the heat preservation time is 2h), and obtaining black powder, namely the cobalt-nitrogen Co-doped porous carbon material Co @ CN-Zn 4-5. A series of cobalt-nitrogen doped porous carbon materials Co @ CN-ZnX-Y can be obtained by changing the mass ratio X of Zn to Co (wherein the mass of Co is kept unchanged) and the pyrolysis temperature rise rate Y.
Example 2: oxidative esterification of HMF
The reaction route is as follows:
adding 0.3mmol of HMF, 15mg of Co @ CN-ZnX-Y (Co 10 mol%) and 3m L% methanol into a reaction container, reacting for 16h at 50 ℃ under the condition of normal pressure and oxygen, separating the catalyst and reaction liquid after the reaction is finished and the temperature is reduced, removing the solvent by rotary evaporation of the organic phase, and recrystallizing to obtain a reaction product, wherein the specific surface area of the catalyst Co @ CN-ZnX-Y can be adjusted by changing the mass ratio X of Zn and Co and the pyrolysis temperature rise rate Y, and is in direct proportion to the yield of HMF oxidative esterification, and the specific result is shown in figure 2, wherein the catalyst Co @ CN-ZnX 12-5 has the maximum specific surface area 658m2The yield of the target product obtained by the catalytic reaction is also highest (94%).
Example 3: oxidative esterification of high concentration HMF (2M)
Adding 4mmol of HMF, 200mg of Co @ CN-Zn12-5(Co 10 mol%) and 2m L of methanol into a reaction vessel, reacting at 50 ℃ under the condition of normal pressure and oxygen for 24 hours, cooling after the reaction is finished, separating a catalyst and a reaction liquid, removing a solvent from an organic phase through rotary evaporation, and recrystallizing to obtain a reaction product, wherein the separation yield is 85%.
FIG. 1 is an SEM picture of a cobalt nitrogen Co-doped porous carbon material catalyst, wherein (a) Co @ CN-Zn0-5(b) Co @ CN-Zn4-5(c) Co @ CN-Zn8-5(d) Co @ CN-Zn 12-5. FIG. 2 is a graph showing the effect of different temperature rising rates on the specific surface area of the cobalt-nitrogen co-doped porous carbon material and the yield of the oxidation esterification reaction of HMF. As can be seen from FIG. 2, when the temperature rise rate is too low (2.5 ℃/min) or too high (15 ℃/min), the specific surface area of the prepared cobalt-nitrogen co-doped porous carbon material is relatively low, and the corresponding yield of the HMF oxidation esterification reaction is also obviously reduced. When the temperature rise rate is 5-10 ℃/min, the specific surface area of the prepared cobalt-nitrogen co-doped porous carbon material and the corresponding HMF oxidation esterification reaction yield are high. FIG. 3 is a graph showing the effect of mass ratios of Zn and Co on the specific surface area of a cobalt-nitrogen Co-doped porous carbon material and the yield of an oxidation esterification reaction of HMF. As can be seen from fig. 3, when the mass ratio of Zn to Co is too low (0 or 2), the specific surface area of the prepared cobalt-nitrogen Co-doped porous carbon material is relatively low, and the corresponding HMF oxidative esterification reaction yield is also obviously reduced. When the mass ratio of Zn to Co is 4-16: 1, the specific surface area of the prepared cobalt-nitrogen Co-doped porous carbon material and the corresponding HMF oxidation esterification reaction yield are high, and when the mass ratio is 8-12, the specific surface area of the prepared cobalt-nitrogen Co-doped porous carbon material and the corresponding HMF oxidation esterification reaction yield are highest.
Claims (10)
1. The preparation method of the cobalt-nitrogen co-doped porous carbon material catalyst is characterized by comprising the following specific steps of:
step 1, sequentially adding zinc salt, cobalt salt and chitosan into a solvent, fully stirring and uniformly mixing, carrying out reduced pressure distillation to remove the solvent, and drying, wherein the solvent is any one of methanol, ethanol, water and a mixed solution of methanol and water, and the mass ratio of zinc to cobalt is 4-16: 1;
and 2, heating the mixture obtained in the step 1 to 700-900 ℃ at a heating rate of 5-10 ℃/min in an argon atmosphere, and calcining to obtain the cobalt-nitrogen Co-doped porous carbon material Co @ CN-ZnX-Y.
2. The method according to claim 1, wherein in step 1, the zinc salt is zinc acetate, zinc nitrate or zinc sulfate, and the cobalt salt is cobalt chloride, cobalt nitrate or cobalt acetate.
3. The preparation method according to claim 1, wherein in the step 1, the mass ratio of the zinc to the cobalt is 8-12: 1.
4. The preparation method according to claim 1, wherein in the step 1, the drying is vacuum drying, the drying temperature is 80-100 ℃, and the drying time is 12-24 hours.
5. The preparation method according to claim 1, wherein in the step 1, the stirring and mixing temperature is 25-80 ℃ and the stirring time is 12-48 h.
6. The preparation method according to claim 1, wherein in the step 2, the heat preservation time during the calcination is 1-4 h.
7. The cobalt-nitrogen co-doped porous carbon material catalyst prepared by the preparation method according to any one of claims 1 to 6.
8. The cobalt-nitrogen co-doped porous carbon material catalyst according to claim 7, which is applied to oxidation esterification of HMF.
9. The use according to claim 8, characterized in that the specific method is as follows:
mixing an HMF and cobalt-nitrogen co-doped porous carbon material catalyst with methanol, reacting at 50-60 ℃ under the condition of normal pressure oxygen, cooling after the reaction is finished, separating the catalyst from a reaction liquid, removing the methanol from an organic phase through rotary evaporation, and recrystallizing to obtain a reaction product.
10. The use according to claim 9, wherein the reaction time is 16 to 18 hours.
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Cited By (5)
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| CN113559914A (en) * | 2021-08-23 | 2021-10-29 | 四川轻化工大学 | Metal/nitrogen-doped porous carbon catalyst for treating organic wastewater and preparation method thereof |
| CN113649053A (en) * | 2021-08-31 | 2021-11-16 | 浙江工业大学 | Cobalt (II) -doped chitosan carbon material, preparation method thereof and application thereof in catalytic oxidation of ethylbenzene and derivatives thereof |
| CN113649013A (en) * | 2021-08-31 | 2021-11-16 | 浙江工业大学 | Co (II), Zn (II) bimetal doped carbon material and preparation method and application thereof |
| CN114507200A (en) * | 2020-11-14 | 2022-05-17 | 中国科学院大连化学物理研究所 | Method for preparing 2, 5-furan diformate by heterogeneous catalysis |
| CN115845892A (en) * | 2022-06-27 | 2023-03-28 | 海南华瑞医药有限公司 | N and S co-doped carbon material loaded zinc monoatomic atom and preparation method and application thereof |
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| CN114507200A (en) * | 2020-11-14 | 2022-05-17 | 中国科学院大连化学物理研究所 | Method for preparing 2, 5-furan diformate by heterogeneous catalysis |
| CN113559914A (en) * | 2021-08-23 | 2021-10-29 | 四川轻化工大学 | Metal/nitrogen-doped porous carbon catalyst for treating organic wastewater and preparation method thereof |
| CN113559914B (en) * | 2021-08-23 | 2023-10-13 | 四川轻化工大学 | Metal/nitrogen doped porous carbon catalyst for treating organic wastewater and preparation method thereof |
| CN113649053A (en) * | 2021-08-31 | 2021-11-16 | 浙江工业大学 | Cobalt (II) -doped chitosan carbon material, preparation method thereof and application thereof in catalytic oxidation of ethylbenzene and derivatives thereof |
| CN113649013A (en) * | 2021-08-31 | 2021-11-16 | 浙江工业大学 | Co (II), Zn (II) bimetal doped carbon material and preparation method and application thereof |
| CN115845892A (en) * | 2022-06-27 | 2023-03-28 | 海南华瑞医药有限公司 | N and S co-doped carbon material loaded zinc monoatomic atom and preparation method and application thereof |
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