CN113385214A - Method for preparing Co/3DNG catalyst and applying Co/3DNG catalyst to catalytic oxidation of lignin and beta-O-4 model compound thereof - Google Patents
Method for preparing Co/3DNG catalyst and applying Co/3DNG catalyst to catalytic oxidation of lignin and beta-O-4 model compound thereof Download PDFInfo
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- 229920005610 lignin Polymers 0.000 title claims abstract description 33
- 150000001875 compounds Chemical class 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 22
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 15
- 230000003647 oxidation Effects 0.000 title claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000006185 dispersion Substances 0.000 claims abstract description 18
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 9
- 238000000197 pyrolysis Methods 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 7
- 238000004108 freeze drying Methods 0.000 claims abstract description 6
- 238000007598 dipping method Methods 0.000 claims abstract description 3
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
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- 238000002360 preparation method Methods 0.000 claims description 6
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 9
- 150000007529 inorganic bases Chemical class 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 36
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- 238000005336 cracking Methods 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 239000012263 liquid product Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 4
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- 239000002131 composite material Substances 0.000 description 3
- 238000000502 dialysis Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 229920001732 Lignosulfonate Polymers 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010812 external standard method Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- BVWTXUYLKBHMOX-UHFFFAOYSA-N methyl vanillate Chemical compound COC(=O)C1=CC=C(O)C(OC)=C1 BVWTXUYLKBHMOX-UHFFFAOYSA-N 0.000 description 2
- 229940067107 phenylethyl alcohol Drugs 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OLBNOBQOQZRLMP-UHFFFAOYSA-N 2,6-dimethoxy-p-benzoquinone Chemical compound COC1=CC(=O)C=C(OC)C1=O OLBNOBQOQZRLMP-UHFFFAOYSA-N 0.000 description 1
- GSBICRJXEDSPTE-UHFFFAOYSA-N 2-phenoxy-1-phenylethanol Chemical compound C=1C=CC=CC=1C(O)COC1=CC=CC=C1 GSBICRJXEDSPTE-UHFFFAOYSA-N 0.000 description 1
- 235000018185 Betula X alpestris Nutrition 0.000 description 1
- 235000018212 Betula X uliginosa Nutrition 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- PVRDAVSDHWPSOF-UHFFFAOYSA-N Vanillic acid methyl ester Natural products COC(=O)C(=O)C1=CC=C(O)C(OC)=C1 PVRDAVSDHWPSOF-UHFFFAOYSA-N 0.000 description 1
- 229930003779 Vitamin B12 Natural products 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- AGVAZMGAQJOSFJ-WZHZPDAFSA-M cobalt(2+);[(2r,3s,4r,5s)-5-(5,6-dimethylbenzimidazol-1-yl)-4-hydroxy-2-(hydroxymethyl)oxolan-3-yl] [(2r)-1-[3-[(1r,2r,3r,4z,7s,9z,12s,13s,14z,17s,18s,19r)-2,13,18-tris(2-amino-2-oxoethyl)-7,12,17-tris(3-amino-3-oxopropyl)-3,5,8,8,13,15,18,19-octamethyl-2 Chemical compound [Co+2].N#[C-].[N-]([C@@H]1[C@H](CC(N)=O)[C@@]2(C)CCC(=O)NC[C@@H](C)OP(O)(=O)O[C@H]3[C@H]([C@H](O[C@@H]3CO)N3C4=CC(C)=C(C)C=C4N=C3)O)\C2=C(C)/C([C@H](C\2(C)C)CCC(N)=O)=N/C/2=C\C([C@H]([C@@]/2(CC(N)=O)C)CCC(N)=O)=N\C\2=C(C)/C2=N[C@]1(C)[C@@](C)(CC(N)=O)[C@@H]2CCC(N)=O AGVAZMGAQJOSFJ-WZHZPDAFSA-M 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
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- 238000001514 detection method Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011715 vitamin B12 Substances 0.000 description 1
- 235000019163 vitamin B12 Nutrition 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- 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
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/32—Freeze drying, i.e. lyophilisation
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms
- C07C37/52—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms by splitting polyaromatic compounds, e.g. polyphenolalkanes
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Abstract
A method for preparing a Co/3DNG catalyst and applying the catalyst to catalytic oxidation of lignin and a beta-O-4 model compound thereof comprises the steps of mixing Graphene Oxide (GO) dispersion liquid with ammonia water, carrying out hydrothermal treatment to obtain three-dimensional nitrogen-doped graphene (3DNG), dipping the 3DNG into a Co salt solution, and carrying out freeze drying and pyrolysis on a dipped product to obtain the Co/3 DNG. The catalyst is used for catalyzing the oxidative depolymerization of lignin and a beta-O-4 model compound thereof, and shows excellent catalytic activity and selectivity under the condition of not adding any inorganic base.
Description
Technical Field
The invention relates to a technology in the field of catalyst preparation and biomass conversion, in particular to a three-dimensional nitrogen-doped graphene-loaded cobalt nanoparticle (Co/3DNG) catalyst prepared by a hydrothermal-impregnation-pyrolysis method and application thereof in oxidative conversion of lignin and a beta-O-4 model compound thereof.
Background
The lignin is a biomass resource which is second to cellulose in nature and contains a natural aromatic ring structure, and can be used for obtaining a monomer compound with multiple functional groups through oxidative depolymerization, so that functionalized monomer and oligomer raw materials are provided for the organic chemical industry and the pharmaceutical industry. For many years, people strive to realize high additional utilization of lignin by selecting a proper catalyst and breaking a beta-O-4 connection structure. In the catalytic oxidative depolymerization of lignin and a beta-O-4 model compound thereof, the non-metal cobalt-based catalyst has the advantages of low cost, rich resources and the like, and has relatively good corrosion resistance under alkaline conditions, and is expected to become one of potential catalysts for catalyzing oxidative degradation of lignin. Luo et al (Luo H., Wang L., Li G., et al. Nitrogen-doped carbon-modified cobalt-nanoparticles-catalyzed oxidative consumption of lignin beta-O-4 model composites under mill conditioners [ J. ]]ACS susteable chem. eng, 2018, 6: 14188 and 14196)) is prepared by cracking vitamin B12 loaded on activated carbon to obtain the nitrogen-doped carbon material loaded Co nano-particle catalyst which is added with inorganic alkali K2CO3Under the condition of being used as an auxiliary agent, the catalyst shows good catalytic activity on the catalytic oxidation of a beta-O-4 model compound (2-phenoxy-1-phenethyl alcohol), and the conversion rate of the beta-O-4 model compound and the yield of the product phenol are 96 percent. However, this is not adding K2CO3Under the conditions of (1), the conversion rate and the phenol yield of the beta-O-4 model compound are only 19 percent.
Disclosure of Invention
Aiming at the defects and shortcomings in the prior art, the invention provides a method for preparing a Co/3DNG catalyst and applying the Co/3DNG catalyst to catalytic oxidation of lignin and a beta-O-4 model compound thereof, which is used for carrying out oxidative depolymerization of the lignin and the beta-O-4 model compound thereof under the condition of not adding any inorganic alkali and shows excellent catalytic activity and selectivity.
The invention is realized by the following technical scheme:
the invention relates to a preparation method of a Co/3DNG catalyst, which comprises the steps of mixing Graphene Oxide (GO) dispersion liquid with ammonia water, carrying out hydrothermal treatment to obtain three-dimensional nitrogen-doped graphene (3DNG), dipping the 3DNG into a Co salt solution, and carrying out freeze drying and pyrolysis on a dipped product to prepare Co/3 DNG.
The concentration of the graphene oxide dispersion liquid is 2-5mg/mL, and the dosage is 20 mL.
The concentration of the ammonia water is 25-28%, and the proportion of the ammonia water to the graphene oxide is (0.5-2) mL (40-100) mg.
The hydrothermal method specifically comprises the following steps: and (3) sequentially heating the GO dispersion liquid and ammonia water in a water kettle, fully stirring, transferring the water kettle to an oven, heating to 180 ℃, preserving heat for 12 hours, and naturally cooling to room temperature.
The hydrothermal process, preferably after cooling, centrifuges the product system and washes with deionized water to pH 7.
The impregnation specifically comprises the following steps: deionized water and absolute ethyl alcohol are sequentially added into the cobalt salt and fully stirred, and then 3DNG is immersed into the solution and stands for 2-24 h.
The soaking time is preferably 12-24 h.
The impregnation is preferably carried out by centrifuging the product system after standing, and alternately washing with de-ethanol and ionized water, preferably 3 times.
The volume ratio of the deionized water to the absolute ethyl alcohol is 1:0-1:7, preferably 1:0-1: 3.
The cobalt salt is Co (CH)3COO)2·4H2O、Co(NO3)2·6H2O、CoCl2·6H2O or CoSO4·7H2O, preferably Co (CH)3COO)2·4H2O, the dosage is 10-60 mg.
The freeze drying is that: cooling the impregnated product to-80 ℃, specifically: freezing the impregnated product to-25 ℃, further cooling to-80 ℃ by a freeze dryer, and drying for 12 h.
The pyrolysis refers to that: the freeze-dried product is added in N2Heating and heat preservation under atmosphereThe method specifically comprises the following steps: placing the dried sample in a quartz tube heating zone of a tube furnace, sealing, vacuumizing, and introducing N2Replacing several times and charging N2Then, the temperature is raised to 600-1000 ℃ at the temperature rise rate of 5 ℃/min and the temperature is kept for 60 min.
The Co/3DNG catalyst prepared by the method has a three-dimensional network structure, and Co nanoparticles are uniformly distributed on the surface of three-dimensional graphene.
The invention relates to application of the Co/3DNG catalyst, which is used for catalytic oxidation of lignin and model compounds thereof, and specifically comprises the following steps: and (3) carrying out high-pressure heating reaction on the Co/3DNG catalyst, lignin or lignin model compound and methanol in an oxygen environment to realize catalytic oxidation, and carrying out product analysis.
The oxygen environment is characterized in that after the polytetrafluoroethylene container is sealed, oxygen is introduced for replacing for a plurality of times, and oxygen is filled until the initial reaction pressure is 0.1-0.3MPa, preferably 0.2 MPa.
The high-pressure heating reaction is carried out under the oxygen environment, the temperature is raised to 80-120 ℃ while stirring, the reaction is carried out for 1-12h, and the reaction temperature is preferably 120 ℃.
The lignin is solvent lignin, alkaline lignin or lignosulfonate, preferably solvent lignin.
The lignin beta-O-4 model compound is 2-phenoxy-1-phenethyl alcohol.
The ratio of the Co/3DNG catalyst, lignin or lignin model compound and methanol is (20-50) mg: (50-100) mg of (5-10) mL or (0.5-3) mg of (0.01-0.05) mmol of (2-5) mL.
After the reaction is finished and the temperature is reduced to the room temperature, the catalyst Co/3DNG is directly recovered by using a magnet, and after the liquid product is collected, qualitative and quantitative detection is respectively carried out on the obtained liquid product by using a liquid chromatography-mass spectrometer and a liquid chromatograph, and the method specifically comprises the following steps: and making a standard curve of each product by an external standard method, calculating according to the standard curve to finally obtain the concentration distribution of each product, and further calculating the conversion rate and the yield.
Technical effects
The invention integrally solves the problem that the existing catalyst can effectively catalyze and oxidize the conversion of lignin and model compounds thereof only under the condition of adding inorganic base, and fills the technical blank that the Co/3DNG catalyst is obtained by taking three-dimensional nitrogen-doped graphene as a carrier and a Co salt precursor through an impregnation-cracking method and is used for the oxidative depolymerization of the lignin and the beta-O-4 model compounds thereof.
Compared with the prior art, the invention adopts a hydrothermal-impregnation-cracking method, and can simply and quickly prepare the Co/3DNG catalyst. Under the condition of not adding any alkali, O is 0.2MPa2Under the reaction conditions of 120 ℃ and 6 hours, the conversion rate of the lignin beta-O-4 model compound 2-phenoxy-1-phenethyl alcohol is up to 97 percent, the yield of the main product phenol is 97 percent, and the selectivity is 100 percent. The Co/3DNG catalyst prepared by the method has good magnetism, and can be directly recycled by utilizing the magnet.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of Co/3DNG obtained by the preparation of example;
FIG. 2 is a Scanning Electron Microscope (SEM) image of Co/3DNG prepared by example;
in fig. 2: abcd is for each example in turn.
Detailed Description
Example 1
The embodiment specifically comprises the following steps:
step 1, adding 20mL of GO dispersion liquid with concentration of 2mg/mL into a 40mL hydrothermal kettle, and measuring 0.5mL of NH3·H2Add O to GO dispersion and mix thoroughly for 5 min. Then, the reaction kettle was transferred to an oven, heated to 180 ℃, and held for 12 hours. After the reaction is finished, naturally cooling the reaction kettle, performing centrifugal separation on a product system, washing the product system by using deionized water until the pH value is 7, and storing the product system in the deionized water for later use. The resulting product was named 3 DNG.
Step 3, placing the freeze-dried sample in a heating area of a tube furnace, sealing, vacuumizing and introducing N2Permute 3 times and then fill in N2Raising the temperature to 600 ℃ at the heating rate of 5 ℃/min, and preserving the temperature for 60 min. And after the reaction is finished, taking the sample out of the tube furnace after the system is naturally cooled. The resulting product was named Co/3 DNG-600.
As shown in FIG. 1, XRD results show that a wide diffraction peak appearing at 44.39 degrees in Co/3DNG-600 corresponds to a (111) crystal face of metal Co (JCPDS No.15-0806) except for a wide (002) diffraction peak of graphene, and the graphene-supported Co nanoparticle composite material is prepared experimentally.
As shown in fig. 2, SEM results show that the composite material has a three-dimensional network structure, and the Co nanoparticles are uniformly distributed on the surface of the three-dimensional graphene material, and the Co/3DNG is obtained through experimental preparation.
Example 2
The embodiment specifically comprises the following steps:
step one, adding 20mL of GO dispersion liquid with the concentration of 3mg/mL into a 40mL hydrothermal kettle, and measuring 1.0mL of NH3·H2Add O to GO dispersion and mix thoroughly for 5 min. The reaction vessel was then transferred to an oven, heated to 180 ℃ and held at this temperature for 12 h. After the reaction is finished and the reaction kettle is naturally cooled, the product is transferred into deionized water for dialysis until the pH value of the deionized water is 7, and the obtained product is named as 3 DNG.
Second, 20mg of Co (CH) is weighed3COO)2·4H2And O, sequentially measuring 7mL of deionized water and 7mL of absolute ethyl alcohol, and fully stirring for 10 min. The 3DNG was then immersed in a Co salt solution and allowed to stand for 24 h. Then, after the impregnated 3DNG was washed in a mixed solution of ethanol and water (1:1) for a plurality of times, the product was frozen in a refrigerator (-25 ℃) for 12 hours, and finally the product was dried in a freeze-dryer at-80 ℃ for 12 hours.
Thirdly, placing the sample after freeze drying onThe heating area of the tube furnace is sealed, and then is vacuumized and N is introduced2Permute 3 times and then fill in N2Raising the temperature to 700 ℃ at the heating rate of 5 ℃/min, and preserving the temperature for 60 min. And after the reaction is finished, taking the sample out of the tube furnace after the system is naturally cooled. The resulting product was named Co/3 DNG-700.
As shown in FIGS. 1 and 2, the XRD and SEM results for this example are similar to those of example 1, indicating that Co/3DNG was experimentally prepared.
This example differs from example 1 in that the GO dispersion concentration is increased from 2mg/mL to 3mg/mL, the ammonia dosage is increased from 0.5mg/mL to 1mg/mL, Co (CH)3COO)2·4H2The O dosage is increased from 10mg to 20mg, and the cracking temperature is increased from 600 ℃ to 700 ℃.
Example 3
The embodiment specifically comprises the following steps:
step 1, adding 20mL of GO dispersion liquid with concentration of 4mg/mL into a 40mL hydrothermal kettle, and measuring 1.5mL of NH3·H2Add O to GO dispersion and mix thoroughly for 5 min. The reaction vessel was then transferred to an oven, heated to 180 ℃ and held at this temperature for 12 h. After the reaction is finished and the reaction kettle is naturally cooled, the product is transferred into deionized water for dialysis until the pH value of the deionized water is 7, and the obtained product is named as 3 DNG.
Step 3, placing the freeze-dried sample in a heating area of a tube furnace, sealing, vacuumizing and introducing N2Displacing 3 times and then charging N2Raising the temperature to 800 ℃ at the heating rate of 5 ℃/min, and keeping the temperature for 60 min. And after the reaction is finished, taking the sample out of the tube furnace after the system is naturally cooled. The resulting product was named Co/3 DNG-800.
The XRD results showed an increase in the intensity of the (111) diffraction peak at 44.39 ℃ for Co/3DNG-800 compared to Co/3DNG-600 and Co/3 DNG-700. SEM results show that similar to examples 1 and 2, the Co/3DNG-800 has a three-dimensional network structure, and Co nanoparticles are uniformly distributed on the surface of three-dimensional graphene, so that Co/3DNG is obtained through experimental preparation.
This example differs from example 1 in that the GO dispersion concentration is increased from 2mg/mL to 4mg/mL, the ammonia dosage is increased from 0.5mg/mL to 1.5mg/mL, Co (CH)3COO)2·4H2The O dosage is increased from 10mg to 30mg, and the cracking temperature is increased from 600 ℃ to 800 ℃.
Example 4
The embodiment specifically comprises the following steps:
step one, adding 20mL of GO dispersion liquid with the concentration of 5mg/mL into a 40mL hydrothermal kettle, and measuring 2mL of NH3·H2Add O to GO dispersion and mix thoroughly for 5 min. The reaction vessel was then transferred to an oven, heated to 180 ℃ and held at this temperature for 12 h. After the reaction is finished and the reaction kettle is naturally cooled, the product is transferred into deionized water for dialysis until the pH value of the deionized water is 7, and the obtained product is named as 3 DNG.
Second, weigh 40mg Co (CH3COO)2·4H2And O, sequentially measuring 7mL of deionized water and 7mL of absolute ethyl alcohol, and fully stirring for 10 min. The 3DNG was then immersed in a Co salt solution and allowed to stand for 24 h. Then, after the impregnated 3DNG was washed in a mixed solution of ethanol and water (1:1) for a plurality of times, the product was frozen in a refrigerator (-25 ℃) for 12 hours, and finally the product was dried in a freeze-dryer at-80 ℃ for 12 hours.
Thirdly, placing the freeze-dried sample in a tube furnace, sealing, vacuumizing and introducing N2Displacing 3 times and then charging N2Raising the temperature to 900 ℃ at the heating rate of 5 ℃/min, and preserving the temperature for 60 min. And after the reaction is finished, taking the sample out of the tube furnace after the system is naturally cooled. The resulting product was named Co/3 DNG-900.
XRD results show that the intensity of a (111) diffraction peak of the Co/3DNG-900 is remarkably increased at 44.4 degrees, and diffraction peaks appear at 51.8 degrees and 76.2 degrees compared with that of the Co/3DNG-600, the Co/3DNG-700 and the Co/3DNG-800, which correspond to (200) and (220) crystal planes of metal Co respectively, and show that the Co/3DNG-900 has better crystallization performance. SEM results show that the Co nanoparticles on Co/3DNG-900 are larger in size compared with Co/3DNG-600, Co/3DNG-700 and Co/3DNG-800, and the Co/3DNG is prepared through experiments.
This example differs from example 1 in that the GO dispersion concentration is increased from 2mg/mL to 5mg/mL, the ammonia dosage is increased from 0.5mg/mL to 2mg/mL, Co (CH)3COO)2·4H2The O dosage is increased from 10mg to 40mg, and the cracking temperature is increased from 600 ℃ to 900 ℃.
Example 5
The embodiment relates to a test of oxidation activity of a lignin model compound 2-phenoxy-1-phenethyl alcohol catalyzed by the four Co/3DNG catalysts, which specifically comprises the following steps:
in a 10mL Teflon container, 2mg of Co/3DNG, 0.01mM of 2-phenoxy-1-phenylethyl alcohol and 3.0mL of methanol were added. And then placing the reaction system in a micro high-pressure reaction, sealing, introducing oxygen for 3 times of replacement, introducing oxygen until the initial reaction pressure is 0.2MPa, stirring at the speed of 400rpm, heating to 120 ℃, reacting for 6 hours, cooling to room temperature after the reaction is finished, directly recovering the catalyst Co/3DNG by using a magnet, and collecting a liquid product. The conversion rate of 2-phenoxy-1-phenethyl alcohol and the yield of each product are calculated by a liquid chromatography-mass spectrometer and a liquid chromatograph by adopting an external standard method. The results of the oxidation of 2-phenoxy-1-phenylethanol catalyzed by four Co/3DNG are shown in Table 1.
TABLE 1 comparison of different catalysts
| Catalyst and process for preparing same | Conversion ratio (%) | Phenol yield (%) |
| Example 1 | 47.0 | 46.3 |
| Example 2 | 60.4 | 60.4 |
| Example 3 | 81.6 | 81.6 |
| Example 4 | 97.0 | 97.0 |
As can be seen from Table 1, the Co/3DNG catalyst prepared by the method has higher catalytic oxidation performance than the existing catalyst (without adding K)2CO3Under the condition, the conversion rate of the 2-phenoxy-1-phenethyl alcohol is 19 percent, and the yield of the phenol is 19 percent), which shows that the catalyst prepared by the method has high activity. Example 4 catalytic 2-phenoxy-1-phenylethyl alcohol conversion rate up to 97.0%, phenol yield 97.0%, shows that the catalyst not only has the highest activity, but also has excellent selectivity.
Example 6
The embodiment relates to an oxidative depolymerization activity test of the Co/3DNG-900 catalyst (embodiment 4) for catalyzing solvent-based lignin, which takes birch wood chips as primary lignin and is prepared by a reference, wherein the activity test specifically comprises the following steps:
in a 20mL Teflon container, 40mg Co/3DNG, 50mg solvent-based lignin and 10mL methanol were added. And then placing the reaction system in a micro high-pressure reaction, sealing, introducing oxygen for 3 times of replacement, introducing oxygen until the initial reaction pressure is 0.2MPa, stirring at the speed of 400rpm, heating to 120 ℃, reacting for 12 hours, cooling to room temperature after the reaction is finished, directly recovering the catalyst Co/3DNG by using a magnet, then centrifugally separating solid precipitates, and collecting liquid products. Each product was analyzed by liquid chromatography-mass spectrometer and liquid chromatograph.
Aromatic compound monomers in the product comprise 2, 6-dimethoxy-1, 4-benzoquinone, phenol, 4-methyl hydroxybenzoate and vanillic acid methyl ester. From this, it is understood that the catalyst of example 4 is effective in catalyzing the oxidative depolymerization of the solvent-based lignin to produce the aromatic monomer compound.
Compared with the prior art, the Co/3DNG catalyst is prepared simply and rapidly by adopting a hydrothermal-impregnation-cracking method, can efficiently catalyze and oxidize lignin and model compounds thereof under the condition of not adding any alkali, and has the characteristics of high selectivity, reusability, stability and the like.
The foregoing embodiments may be modified in many different ways by those skilled in the art without departing from the spirit and scope of the invention, which is defined by the appended claims and all changes that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (10)
1. A preparation method of a Co/3DNG catalyst is characterized by comprising the steps of mixing graphene oxide dispersion liquid with ammonia water, carrying out hydrothermal treatment to obtain three-dimensional nitrogen-doped graphene, dipping 3DNG into a Co salt solution, and carrying out freeze drying and pyrolysis on a dipped product to prepare Co/3DNG, wherein: the cobalt salt being Co (CH)3COO)2·4H2O、Co(NO3)2·6H2O、CoCl2·6H2O or CoSO4·7H2O；
The impregnation is as follows: sequentially adding deionized water and absolute ethyl alcohol into cobalt salt, fully stirring, and immersing 3DNG into the solution for standing; the freeze drying is that: freezing the impregnated product to-25 ℃, and then further cooling to-80 ℃; the pyrolysis refers to that: the freeze-dried product is added in N2Heating and heat preservation under atmosphere。
2. The method for preparing a Co/3DNG catalyst according to claim 1, wherein the graphene oxide dispersion solution has a concentration of 2-5mg/mL and a dosage of 20 mL; the concentration of the ammonia water is 25-28%, and the proportion of the ammonia water to the graphene oxide is (0.5-2) mL (40-100) mg.
3. The method of claim 1, wherein the hydrothermal reaction comprises: and (3) sequentially heating the GO dispersion liquid and ammonia water in a water kettle, fully stirring, transferring the water kettle to an oven, heating to 180 ℃, preserving heat for 12 hours, and naturally cooling to room temperature.
4. The method of claim 1, wherein the impregnation is specifically as follows: deionized water and absolute ethyl alcohol are sequentially added into the cobalt salt and fully stirred, and then 3DNG is immersed into the solution and stands for 2-24 h.
5. The method of claim 4, wherein the volume ratio of the deionized water to the absolute ethyl alcohol is 1:0 to 1: 7.
6. The method of claim 1, wherein the cobalt salt is Co (CH)3COO)2·4H2O, the dosage is 10-60 mg.
7. The method of claim 1, wherein the pyrolysis is: the freeze-dried product is added in N2Heating and heat preservation under the atmosphere, specifically: placing the dried product in a quartz tube heating zone of a tube furnace, sealing, vacuumizing, and introducing N2Replacing several times and charging N2Then, the temperature is raised to 600-1000 ℃ at the temperature rise rate of 5 ℃/min and the temperature is kept for 60 min.
8. The Co/3DNG catalyst prepared by the method of any one of claims 1 to 7, which is characterized by having a three-dimensional network structure, and Co nanoparticles are uniformly distributed on the surface of three-dimensional graphene.
9. Use of a Co/3DNG catalyst prepared by the method according to any one of claims 1 to 7 or according to claim 8 for the catalytic oxidation of lignin and its model compounds, in particular: and (3) carrying out high-pressure heating reaction on the Co/3DNG catalyst, lignin or lignin model compound and methanol in an oxygen environment to realize catalytic oxidation.
10. The use of claim 9, wherein the oxygen environment is prepared by sealing a polytetrafluoroethylene container, introducing oxygen for replacement for several times, and introducing oxygen until the initial reaction pressure is 0.1-0.3 MPa;
the high-pressure heating reaction is carried out, under the oxygen environment, the mixture is stirred and heated to 80-120 ℃ at the same time, and the reaction lasts for 1-12 hours.
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