CN114784298B - Preparation method of porous carbon-loaded metal-organic framework ZIF-67 composite material - Google Patents
Preparation method of porous carbon-loaded metal-organic framework ZIF-67 composite material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 25
- 239000002131 composite material Substances 0.000 title claims abstract description 16
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000004570 mortar (masonry) Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- SLCITEBLLYNBTQ-UHFFFAOYSA-N CO.CC=1NC=CN1 Chemical compound CO.CC=1NC=CN1 SLCITEBLLYNBTQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims 2
- 238000010298 pulverizing process Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 10
- 239000002028 Biomass Substances 0.000 abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 230000003213 activating effect Effects 0.000 abstract description 6
- 230000009467 reduction Effects 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 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 abstract description 2
- 244000046052 Phaseolus vulgaris Species 0.000 abstract description 2
- 235000010627 Phaseolus vulgaris Nutrition 0.000 abstract description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 abstract description 2
- 235000011613 Pinus brutia Nutrition 0.000 abstract description 2
- 241000018646 Pinus brutia Species 0.000 abstract description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 2
- 239000008103 glucose Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000000498 ball milling Methods 0.000 abstract 1
- 238000001354 calcination Methods 0.000 abstract 1
- 238000007796 conventional method Methods 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- 238000010335 hydrothermal treatment Methods 0.000 abstract 1
- 238000000967 suction filtration Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 8
- 238000003763 carbonization Methods 0.000 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 description 5
- 239000010411 electrocatalyst Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000005539 carbonized material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8689—Positive electrodes
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
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Abstract
The invention discloses a preparation method of a porous carbon supported metal organic framework ZIF-67, which comprises the following steps of firstly preparing a porous carbon material: ball milling biomass carbon material (such as bark, pine needle, bean dregs, glucose, etc.) into powder, performing hydrothermal treatment at 160-180 ℃, performing suction filtration on the obtained solution, drying, activating with activating agent (such as KOH, znCl2, naCl, etc.), uniformly mixing the two powders in a certain proportion, calcining in a tube furnace at 800 ℃, preserving heat for 3 hours, washing the obtained powder with deionized water to neutrality, and drying to obtain porous carbon powder. Preparation of porous carbon supported metal organic framework ZIF-67: mixing porous carbon and ZIF-67 in a certain proportion, heating to 800-1000 ℃ in a tube furnace, and preserving heat for 3 hours to obtain the porous carbon supported metal organic framework ZIF-67 composite material. The method has the advantages of simple process, strong operability, easily available raw materials and low cost, and overcomes the defects of complex process, high cost and the like of the conventional method for preparing the ORR oxygen reduction catalyst.
Description
Technical Field
The invention relates to the technical field of electrocatalytic materials of clean energy, in particular to a preparation method of a porous carbon-loaded metal-organic framework ZIF-67 composite material.
Background
With the continuous consumption of fossil energy, leading to a continuous reduction of non-renewable energy sources, people are prompted to find sustainable, environmentally friendly clean energy sources for high density energy storage electronic devices. In recent years, metal-air batteries have attracted considerable attention as a new energy source for use in small devices such as watches and hearing aids. Because the metal-air battery takes oxygen in the air as the positive electrode and metal as the negative electrode, the oxygen is extremely easy to obtain, and the oxygen diffuses to the electrochemical reaction interface to react with the metal for discharging, and the metal-air battery is safe and environment-friendly, and has great advantages compared with heavy metal batteries, such as lithium batteries, and the like, which seriously pollute the environment. However, the catalyst in the cathode can greatly affect the rate of oxygen reduction and oxygen evolution reactions in the cell, thereby affecting the stability of the cell and its energy density.
The cathode catalysts currently used are mainly noble metal catalysts: such as Pt, au, ir, ru, etc., but they are poor in stability, high in cost, and scarce in reserves, greatly limit the development of metal-air batteries. Therefore, the preparation of the non-noble metal catalyst becomes a main way for improving the catalyst performance and reducing the production cost. The carbon material catalyst has excellent conductivity and stable chemical property, but has lower catalytic activity, the catalytic performance is usually improved by adopting a mode of doping metal oxide and the like, the structure of the transition metal doped carbon material can be regulated and controlled, and the preparation process is simple and has strong repeatability, so the catalyst is widely used for preparing oxygen reduction electrocatalyst.
The biomass material is rich in C element, is a sustainable and renewable clean energy source in nature, and is applied to preparation of electrocatalysts in recent years to replace the traditional carbon nano tube, graphene and other materials as conductive substrates. Chen et al used soybean dregs to prepare oxygen-reducing electrocatalysts, which were more excellent than commercial noble metal catalysts Pt/C. The metal organic framework material ZIF-67 is rich in Co element, so that the ORR performance is excellent, and the metal organic framework material ZIF-67 is widely used for preparing electrocatalysts. But ZIF-67 itself conductivity is poor, and the structure is easy to collapse after pyrolysis, so ZIF-67 is compounded with biomass material to adjust the morphology and further improve the electrocatalytic activity.
Disclosure of Invention
The invention aims to solve the problems, and provides a preparation method of a porous carbon supported metal-organic framework ZIF-67 composite material, which comprises the following steps:
s1: preparing fir bark powder, comprising the steps of:
s11: drying fir bark in a 70 ℃ oven for 12h;
s12: cutting the dried fir bark into blocks, putting into a ball mill, and grinding for 4 hours at a rotating speed of 300 r/min;
S13: collecting the ground powder, and drying in an oven for 12 hours to obtain fir bark powder;
S2: carrying out hydrothermal carbonization on the biomass charcoal material powder to form a solid, filtering and drying the solid to obtain a biomass charcoal material precursor;
s3: activating the biomass carbon material precursor by using an activating agent to prepare a porous carbon material;
S4: preparing a ZIF-67 product;
S5: and mixing the ZIF-67 product with the porous carbon material to obtain the porous carbon-supported ZIF-67 composite material.
Further, in the step S2, the filtering specifically includes: washing with deionized water and ethanol for multiple times; setting the temperature of the drying at 70 ℃ and the time at 12 hours, and drying to obtain the fir bark precursor; the specific steps of the hydrothermal carbonization comprise:
S21: extracting 1.5g of the fir bark powder, dissolving in 50ml of deionized water, and uniformly stirring;
s22: and (3) placing the uniformly stirred mixed solution into a reaction kettle for reaction to obtain brown solid, and finishing hydrothermal carbonization.
Further, in the step S3, the activating agent is KOH, and the specific steps of activating the fir bark precursor with the KOH to obtain the porous carbon material include:
S31: thoroughly crushing the fir bark precursor in a mortar by KOH, mixing and grinding for 30min in the mortar;
s32: placing the ground and mixed powder into a tube furnace, and introducing N 2 gas;
S33: heating the tube furnace filled with the N 2 gas to 800 ℃ at a heating rate of 5 ℃/min, and preserving heat for 3 hours to obtain an activated sample;
S34: fully washing the activated sample with deionized water after the activated sample is cooled until the solution formed after the deionized water and the activated sample are mixed is neutral;
S35: and drying the fully washed activated sample in a 70 ℃ oven for 12 hours to obtain the porous carbon material.
Further, in the step S4, the preparation of the ZIF-67 product specifically comprises the following steps:
S41: dissolving 2mmol of Co (NO 3) 2.6H2O and 8mmol of 2-methylimidazole (2-MelM) in 50ml of methanol respectively, uniformly dispersing by using an ultrasonic cleaner, and stirring to obtain a 2-methylimidazole methanol solution and a Co (NO 3) 2.6H2O methanol solution;
S42: pouring the 2-methylimidazole methanol solution into the Co (NO 3) 2.6H2O methanol solution rapidly, and magnetically stirring for 24 hours at normal temperature;
s43: centrifuging the mixed solution subjected to magnetic stirring at 8000rpm for 10min to obtain a purple precipitate;
s44: performing three methanol washes on the purple precipitate, and sequentially performing ethanol washes;
S45: the washed purple precipitate is dried for 12 hours at 70 ℃ to obtain a ZIF-67 product.
Further, the step S5 specifically includes: and (3) putting the porous carbon material and the ZIF-67 into a mortar for uniform mixing, putting into a crucible, heating to 900 ℃ in a tube furnace at a heating rate of 5 ℃/min, and preserving heat for 3 hours to obtain the porous carbon-loaded ZIF-67 composite material.
Further, in the step S5, the porous carbon material and the ZIF-67 are uniformly mixed in a mortar in a ratio of 5:1.
Further, in the step S22, the time of the hydrothermal reaction kettle is set to be 12-24 hours, and the temperature is set to be 160-180 ℃.
Further, the time of the hydrothermal reaction kettle is set to 12 hours, and the temperature is set to 160 ℃.
Further, in the step S31, a mass ratio of the fir bark precursor to the KOH in the mortar is 1:3.
Compared with the prior art, the invention has the beneficial effects that:
1. the green sustainable renewable biological energy source fir bark is adopted to provide a carbon source, the raw materials are easy to obtain, the cost is low, and the environment is friendly.
2. The invention combines the porous carbon with ZIF-67, thereby improving the electrochemical performance.
Drawings
FIG. 1 is an XRD pattern of ZIF-67 and ZIF-67/C produced by the method of producing a porous carbon supported metal organic framework ZIF-67 composite according to the present invention;
FIG. 2 is an SEM image of ZIF-67 and ZIF-67/C prepared by the method of preparing a porous carbon supported metal organic framework ZIF-67 composite according to the present invention;
FIG. 3 is a LSV graph of ZIF-67 and ZIF-67/C produced by the method of producing a porous carbon supported metal organic framework ZIF-67 composite according to the present invention.
Detailed Description
The following description will be made in more detail regarding a method for preparing a porous carbon-supported metal-organic framework ZIF-67 composite material according to the present invention, illustrating a preferred embodiment of the present invention, with the understanding that the present invention described herein may be modified by those skilled in the art while still achieving the advantageous effects of the present invention, and thus the following description should be construed as broadly known to those skilled in the art and not as limiting the present invention.
A preparation method of a ZIF-67 sample comprises the following specific steps:
1): 2mmol (291 mg) of Co (NO 3) 2.6H2O and 8mmol (328 mg) of 2-methylimidazole (2-MelM) are respectively dissolved in 50ml of methanol, uniformly dispersed by an ultrasonic cleaner, respectively obtained by stirring, and then quickly poured into Co (NO 3) 2.6H2O methanol solution, and magnetically stirred at normal temperature for 24 hours;
2): centrifuging at 8000rpm for 10min to obtain purple precipitate, washing with methanol for three times, washing with ethanol once, and baking at 70deg.C for 12 hr to obtain ZIF-67 product of about 60mg.
3): And (3) placing the ZIF-67 obtained in the steps into a crucible, heating to 900 ℃ in a tube furnace at a heating rate of 5 ℃/min, and preserving heat for 3 hours to obtain the ZIF-67.
A preparation method of a porous carbon-loaded metal-organic framework ZIF-67 composite material comprises the following steps:
1): drying biomass carbon material fir bark in a baking oven at 70 ℃ for 12 hours, cutting into small blocks, putting into a ball mill, grinding for 4 hours at a rotating speed of 300r/min, collecting obtained powder, and drying in the baking oven for 12 hours to obtain fir bark powder;
2): dissolving 1.5g of fir bark powder obtained in 1) in 50ml of deionized water, uniformly stirring, putting into a reaction kettle, reacting for 12 hours at 160 ℃, filtering the obtained brown solid (hydrothermal carbonization precursor), washing for a plurality of times with deionized water and ethanol, and drying for 12 hours at 70 ℃ to obtain fir bark precursor;
3): thoroughly crushing carbonized precursor in a mortar by using KOH (the mass ratio of KOH/fir bark precursor is about 3:1), grinding the carbonized precursor in the mortar for 30min after mixing, putting the mixture into a tube furnace, introducing N2 gas into the tube furnace, heating to 800 ℃ at the heating rate of 5 ℃/min, preserving heat for 3h, cooling, fully washing an activated sample with deionized water until the solution is neutral, and drying the solution in a baking oven at 70 ℃ for 12h to obtain the porous carbon material;
4): uniformly mixing the ZIF-67 and the porous carbon material in a mortar in a ratio of 1:5, placing the mixture into a crucible, heating to 900 ℃ in a tube furnace at a heating rate of 5 ℃/min, and preserving heat for 3 hours to obtain the porous carbon-loaded ZIF-67 composite material.
As shown in the first graph, the XRD patterns of the prepared ZIF-67 and the prepared ZIF-67/C sample are mainly composed of cellulose after being activated, the wide dispersion peak appearing at the angle of 18-34 degrees is mainly (002) of the cellulose, the relatively sharp diffraction peak appearing at the original angle of 20-26 degrees disappears, and instead, the relatively wide dispersion diffraction peak appearing at the angle of 18-34 degrees shows that after the biological carbon is carbonized, the biological carbon is changed into microcrystalline carbon with a finer grain graphitization structure by an organic crystallization compound through carbonization, so that the wide diffraction peak of graphitized microcrystalline carbon in carbonized materials is enhanced after carbonization. And the crystal faces (111), (200) and (220) of Co are respectively corresponding to 44.22 DEG, 51.52 DEG and 75.85 DEG, which proves that Co exists in the prepared ZIF-67 and ZIF-67/C.
SEM images of ZIF-67 prepared by the invention and ZIF-67/C samples prepared by the invention are shown in FIG. 2, the left image is the prepared ZIF-67, regular dodecahedron morphology can be seen, successful synthesis of the ZIF67 is proved, the right image can be seen that the ZIF-67 is supported on porous carbon, and the porous carbon is formed by an irregular nano-sheet structure.
The Linear Sweep Voltammograms (LSV) of the ZIF-67 and ZIF-67/C samples prepared by the invention are shown in FIG. 3, the rotating speed of the ring-disk electrode is 1600rpm, the sweep rate is 10mV/s, and the catalyst loading is 0.51mg/cm2. As can be seen from the LSV curve, the prepared ZIF-67 has poorer performance compared with ZIF-67/C, the cut-off current density is 3.2mA/cm < 2 >, the half-wave potential is 0.78V, and the initial potential is 0.87V; the prepared ZIF-67/C has a cut-off current density of 3.8mA/cm < 2 >, a half-wave potential of 0.79V and an initial potential of 0.87V.
It is worth mentioning that the biomass carbon material can also be bark, pine needles, bean dregs, glucose and the like; the activator can also be ZnCl 2, naCl and the like, and the same technical effect can be achieved.
The foregoing is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Any person skilled in the art will make any equivalent substitution or modification to the technical solution and technical content disclosed in the invention without departing from the scope of the technical solution of the invention, and the technical solution of the invention is not departing from the scope of the invention.
Claims (1)
1. The preparation method of the porous carbon-loaded metal-organic framework ZIF-67 composite material is characterized by comprising the following steps of:
s1: preparing ZIF-67 comprising:
S11: dissolving 2mmol of Co (NO 3）2∙6H2 O and 8mmol of 2-methylimidazole in 50ml of methanol respectively, uniformly dispersing by using an ultrasonic cleaner, stirring to obtain 2-methylimidazole methanol solution and Co (NO 3）2∙6H2 O methanol solution respectively, rapidly pouring the 2-methylimidazole methanol solution into Co (NO 3）2∙6H2 O methanol solution, and magnetically stirring at normal temperature for 24 h);
S12: centrifuging the mixed solution stirred in the step S11 at 8000rpm for 10min to obtain a purple precipitate, cleaning the purple precipitate with methanol for three times, cleaning the purple precipitate with ethanol for one time, and finally drying at 70 ℃ for 12 hours to obtain a ZIF-67 product;
S13: putting the ZIF-67 into a crucible, heating to 900 ℃ in a tube furnace at a heating rate of 5 ℃/min, and preserving heat for 3 hours to obtain the ZIF-67;
s2: preparing a porous carbon supported ZIF-67 composite comprising:
S21: drying fir bark in a 70 ℃ oven for 12 hours, cutting, putting into a ball mill, grinding for 4 hours at a rotating speed of 300r/min to obtain powder, collecting the powder, and drying in the oven for 12 hours to obtain fir bark powder;
S22: dissolving 1.5g of fir bark powder obtained in S21 in 50ml of deionized water, uniformly stirring, putting into a reaction kettle, reacting for 12 hours at 160 ℃ to obtain brown solid, filtering the brown solid, washing the brown solid for multiple times by using deionized water and ethanol, and finally drying for 12 hours at 70 ℃ to obtain fir bark precursor;
S23: thoroughly pulverizing the carbonized precursor with KOH in a mortar, wherein KOH: the proportion of fir bark precursor is 3:1, grinding for 30min in a mortar after mixing, putting into a tube furnace, introducing N 2 gas into the tube furnace, heating to 800 ℃ at a heating rate of 5 ℃/min, preserving heat for 3h, cooling, fully washing an activated sample with deionized water until the solution is neutral, and drying in a 70 ℃ oven for 12h to obtain a porous carbon material;
S34: uniformly mixing the ZIF-67 obtained in the step S13 and the porous carbon material obtained in the step S23 in a mortar in a ratio of 1:5, placing the mixture into a crucible, heating to 900 ℃ in a tube furnace at a heating rate of 5 ℃/min, and preserving heat for 3 hours to obtain the porous carbon-loaded ZIF-67 composite material.
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| CN113908874A (en) * | 2021-09-30 | 2022-01-11 | 华中科技大学 | Nitrogen-rich porous composite carbon material, and preparation method and application thereof |
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| WO2016027123A1 (en) * | 2014-08-17 | 2016-02-25 | University Of The Western Cape | A method for producing non-precious metal catalysts from nitrogen-rich biomass |
| CN112028052B (en) * | 2020-09-18 | 2022-03-29 | 西北大学 | Preparation method and application of biomass carbon-based Fe monatomic-N doped porous carbon material |
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| CN109019598A (en) * | 2018-07-18 | 2018-12-18 | 华南农业大学 | A kind of mixing biomass prepares the method and manufactured three-dimensional porous carbon material and its application of the three-dimensional porous carbon material of high specific capacitance |
| CN113908874A (en) * | 2021-09-30 | 2022-01-11 | 华中科技大学 | Nitrogen-rich porous composite carbon material, and preparation method and application thereof |
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