CN106904596A - The nano structural material of the CNT assembling prepared based on metal organic framework compound low temperature pyrogenation and its preparation and application - Google Patents

The nano structural material of the CNT assembling prepared based on metal organic framework compound low temperature pyrogenation and its preparation and application Download PDF

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CN106904596A
CN106904596A CN201710128763.8A CN201710128763A CN106904596A CN 106904596 A CN106904596 A CN 106904596A CN 201710128763 A CN201710128763 A CN 201710128763A CN 106904596 A CN106904596 A CN 106904596A
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organic framework
framework compound
structural material
metal organic
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麦立强
孟甲申
牛朝江
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Wuhan University of Technology WUT
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Abstract

The present invention relates to a kind of method of the nanostructured based on the assembling of metal organic framework compound low temperature preparation CNT, comprise the following steps：S1 weighs appropriate slaine and organic ligand respectively, by liquid phase synthesis, makes metal ion and organic ligand in solvent that complexation reaction to occur, and forms metal organic framework compound, by washing, obtains metal organic framework compound powder；S2 dries 5~10h during 80~100 DEG C of baking ovens are positioned over to the powder that step S1 is obtained；The metal organic framework compound powder that S3 will be obtained in step S2, under an inert atmosphere, heats up at a slow speed and is incubated, you can obtain the nano structural material of CNT assembling.The beneficial effects of the invention are as follows：The characteristics of raw material is cheap, process is simple is environmentally friendly, yield is big, material electrochemical performance is excellent.There is provided a kind of pervasive strategy for preparing CNT, and the potentiality with large-scale application.

Description

Based on receiving that CNT prepared by metal organic framework compound low temperature pyrogenation is assembled Rice structural material and its preparation and application
Technical field
The invention belongs to nano material and electrochemical device technical field, and in particular to one kind is based on metal organic frame The method of the nanostructured of compound low temperature preparation CNT assembling, the material can be used as the material in energy storage and switching device Material, and with greatly promoting universality.
Background technology
CNT was found in 1991, was a kind of important allotrope of carbon material, with cylindrical-shaped structure, its , from several nanometers to several tens of nanometers, its length can be from several microns to several centimetres for diameter.Therefore, between in the past few decades, because Its unique electricity, mechanics and architectural characteristic, CNT are deposited in logic circuit, gas storage, bio-imaging, catalysis and the energy The fields such as storage show great potentiality.Researcher has also put into significant effort in terms of the synthesis of CNT, some ratios More effective synthesis strategy is invented, such as arc discharge method, laser ablation method, chemical vapour deposition technique etc..Although these sides Method achieves greatly success, but cost and energy consumption high high still limits further applying for they.Further, since its Harsh synthesis condition, above method also is difficult to the uniform scattered CNT of synthesis.Recently, organic synthesis from bottom to top It is a kind of potential method, the CNT with precise control diameter and length is synthesized under mild conditions.Wherein The organic molecule of selection forms expected CNT as elementary cell by polymerisation.However, this accurate synthesis Method is severely limited to the building-up process of low yield and complexity.Additionally, introducing external foreign atom, energy in CNT Produce unique characteristic.Therefore, a kind of gentle pervasive synthetic method is developed to prepare high yield, low cost and mix Miscellaneous controllable CNT forwardly needs in actual applications.
Metal organic framework compound as a kind of new porous crystalline material, due to its specific surface area high, adjustable Pore structure and controllable structure, in the past twenty years between cause greatly concern.By regulating and controlling metal ion or group Cluster and organic ligand, difference in functionality metal organic framework compound can be with strong formation of chemical bond.Recently, metal organic frame Compound has become a kind of very potential candidate to synthesize carbon-based material, and shows excellent chemical property. However, current carbon-based material is but limited to high temperature pyrolysis and structure is simpler.Therefore, it is based on not by the pervasive method of low temperature The structure that the metal organic framework compound of same type obtains complicated CNT assembling is still faced with huge challenge.
The content of the invention
It is an object of the invention to provide a kind of process is simple, it is easy to promote, the carbon nanometer with excellent electrochemical performance The controllable method for preparing of the nanostructured of pipe assembling.The nanostructured of CNT assembling is applied in oxygen reduction, is realized Efficient oxygen diffusion, the transmission of quick ion and electrical conductivity high；The CNT assembling nanostructured apply lithium from In sub- battery, using the teaching of the invention it is possible to provide effective Stress Release and the diffusion of enhanced lithium ion and electrical conductivity high, while having high shaking Real density.
To achieve these goals, the technical scheme is that：Based on metal organic framework compound low temperature pyrogenation system The method of the nano structural material of standby CNT assembling, comprises the following steps：
S1 weighs appropriate slaine and organic ligand respectively, and is completely dissolved in solvent, forms homogeneous transparent solution, By liquid phase synthesis, make metal ion and organic ligand in solvent that complexation reaction to occur, form metal organic framework compound, By washing, metal organic framework compound powder is obtained；
S2 dries 5~10h during 80~100 DEG C of baking ovens are positioned over to the powder that step S1 is obtained；
The metal organic framework compound powder that S3 will be obtained in step S2, under an inert atmosphere, with 1~2 DEG C of min-1Slowly Speed heats up 420~450 DEG C and 8~10h of insulation, you can obtain the nano structural material of CNT assembling.
By such scheme, the nano structural material of the CNT assembling for being obtained is also by atmosphere 280 DEG C~320 DEG C insulation 3~5h heat treatment.
By such scheme, described slaine is any one in the inorganic salts of cobalt, nickel and iron or their mixing.
By such scheme, described slaine is cobalt nitrate, any one or they in nickel nitrate and ferric nitrate it is mixed Close.
By such scheme, described organic ligand is terephthalic acid (TPA), 2-methylimidazole or trimesic acid.
By such scheme, described slaine and the mol ratio of organic ligand is 1:1~1:4.
The above method obtains a kind of receiving for CNT assembling prepared based on metal organic framework compound low temperature pyrogenation Rice structural material, its by CNT or the CNT of N doping end coated metal or metal oxide nanoparticles simultaneously Assemble, the length of described CNT is 200~500nm, and internal diameter is 3~5nm, and external diameter is 10~20nm.
By such scheme, the nano structural material of described CNT assembling is hollow dodecahedron structure, microballoon, micro- Rice piece or nanometer rods.
The nano structural material of described CNT assembling is used as electro catalytic activity material.
The nano structural material of described CNT assembling is used as lithium ion battery anode active material.
The present invention is organic by designing a kind of gentle pervasive low temperature pyrogenation technology, the metal to different type and pattern Framework compound is sintered, and obtains the structure of the CNT assembling for keeping original pattern, including in CNT assembling Empty dodecahedron structure, the microballoon of CNT assembling, the micron film of CNT assembling, the nanometer rods of CNT assembling Deng.The realization of the strategy be the metal organic framework compound with different type and pattern as presoma, carry out controllable low temperature Heat treatment process, obtains the nanostructured of high-quality CNT assembling.This strategy process is simple, with low cost, product It is controllable, promoted beneficial to large-scale production and the marketization.
The beneficial effects of the invention are as follows：The present invention by the use of metal organic framework compound as unique presoma, by can The heat treatment process of control prepares the nano structural material of the CNT assembling of high-quality different-shape.The CNT group The nano structural material of dress as electro-catalysis and the material of energy storage, with excellent chemical property.The present invention is by adjusting The metal organic framework compound of control different type and pattern, with reference to Low Temperature Pyrolysis Process, is obtained high-quality as presoma The nano structural material of CNT assembling, the present invention is with raw material is cheap, process is simple is environmentally friendly, yield is big, material electrochemical The characteristics of excellent performance.This method provide a kind of pervasive strategy for preparing CNT, and the potentiality with large-scale application.
Brief description of the drawings
Fig. 1 is that the formation mechenism figure and process of the nano structural material of the nitrogen-doped carbon nanometer pipe assembling of embodiment 1 are characterized： A, formation mechenism figure；B-d, the corresponding SEM figures of different phase；
Fig. 2 is SEM and the TEM figure of the hollow dodecahedron of the nitrogen-doped carbon nanometer pipe assembling of embodiment 1：A-b, SEM scheme； C-f, TEM scheme；
Fig. 3 is the pattern and structural characterization of the ZIF-67 presomas of embodiment 1：A, XRD；B, SEM scheme；C-d, respectively Nitrogen adsorption desorption curve and pore size distribution curve；The thermogravimetric of e-f, respectively ZIF-67 presomas under air and nitrogen atmosphere is bent Line；
Fig. 4 is sign of the ZIF presomas of embodiment 1 in pyrolytic process：A, thermogravimetric and differential scanning calorimetric curve；B, Mass spectrometry profile in corresponding process；
Fig. 5 is the pattern and structural characterization of the hollow dodecahedron of the nitrogen-doped carbon nanometer pipe assembling of embodiment 1：A, XRD Collection of illustrative plates；B, SEM scheme；C, EDS mapping scheme；D, Raman collection of illustrative plates；E-f, respectively nitrogen adsorption desorption curve and pore-size distribution are bent Line；G, XPS are composed entirely；H, the XPS essences of high-resolution N 1s sweep collection of illustrative plates；I, the corresponding three kinds contents of different nitrogen；
Fig. 6 is the hollow dodecahedron of the nitrogen-doped carbon nanometer pipe assembling by different temperatures subsequent treatment of embodiment 1 Shape appearance figure：A-d, the SEM figures and TEM of the hollow dodecahedron of the nitrogen-doped carbon nanometer pipe assembling after 550 DEG C are heat-treated Figure；E-h, the SEM figures and TEM figures of the hollow dodecahedron of the nitrogen-doped carbon nanometer pipe assembling after 650 DEG C are heat-treated；I-l, The SEM figures and TEM figures of the hollow dodecahedron of the nitrogen-doped carbon nanometer pipe assembling after 750 DEG C are heat-treated；
Fig. 7 is the hydrogen reduction performance of the hollow dodecahedron of the nitrogen-doped carbon nanometer pipe assembling of embodiment 1：A, in supersaturation The linear sweep voltammetry curve of the different samples under oxygen 0.1M KOH and 1600 revolutions per minute；B, the nitrogen after 650 DEG C are heat-treated Linear sweep voltammetry curve under the different rotating speeds of the hollow dodecahedron of doped carbon nanometer pipe assembling；C, at 650 DEG C of heat The K-L curves under different voltages of the hollow dodecahedron of the nitrogen-doped carbon nanometer pipe assembling after reason；D, by 650 DEG C of heat treatments Rotating ring of the hollow dodecahedron of nitrogen-doped carbon nanometer pipe assembling afterwards under supersaturated oxygen 0.1M KOH and 1600 revolutions per minute Disc electrode curve；E, the yield and electron transfer number of peroxide under the different voltages based on the ring disk；F, in supersaturated oxygen 0.1M KOH, the hollow dodecahedron of the nitrogen-doped carbon nanometer pipe assembling under 1600 revolutions per minute and 0.7V after 650 DEG C are heat-treated and business The cyclical stability of industry platinum carbon electrode；
Fig. 8 is the structural characterization of the hollow dodecahedron of the nitrogen-doped carbon nanometer pipe assembling of embodiment 1：A, different N dopings The C of the hollow dodecahedron of CNT assembling, N, H content analysis；B, hollow the 12 of different nitrogen-doped carbon nanometer pipe assemblings The XPS analysis of the high-resolution N 1s of face body；C, the middle different type of the hollow dodecahedron of different nitrogen-doped carbon nanometer pipe assemblings Nitrogen type content analysis；D, the hollow dodecahedron and cobalt of the nitrogen-doped carbon nanometer pipe assembling after 650 DEG C are heat-treated The XPS analysis of the high-resolution Co 2p3/2 of nano particle；E, the hollow dodecahedron of different nitrogen-doped carbon nanometer pipe assemblings UPS is analyzed；F, the structural representation of the nitrogen-doped carbon nanometer pipe hydrogen reduction process of cobalt confinement；
Fig. 9 is the Density function theory analysis of embodiment 1：A, the structural representation of SWCN；B, pure carbon The work content of nanotube and different nitrogen contents and the CNT of nitrogen type doping summarizes figure；C, pure nano-carbon tube, graphite N doping CNT, the CNT of pyridine N doping and pyrroles's N doping CNT fermi level near the density of states it is bent Line；D, Co4The structural representation of the CNT of confinement；The CNT of e, pure nano-carbon tube and Co4 confinements is perpendicular to c-axis On calculating rest potential curve；The density of states near the fermi level of the CNT of f, pure nano-carbon tube and Co4 confinements is bent Line；
Figure 10 is Co3O4Particle is wrapped in the SEM figures and TEM figures of the hollow dodecahedron of nitrogen-doped carbon nanometer pipe assembling；
Figure 11 is Co3O4Particle is wrapped in the structural characterization of the hollow dodecahedron of nitrogen-doped carbon nanometer pipe assembling：A, XRD Collection of illustrative plates；B, thermogravimetric curve；C-d, respectively nitrogen adsorption desorption curve and pore-size distribution；
Figure 12 is Co3O4Particle is wrapped in the performance of lithium ion battery of the hollow dodecahedron of nitrogen-doped carbon nanometer pipe assembling： A, in 0.4mV s-1The cyclic voltammetry curve swept under speed；B, the high rate performance under different current densities；C, in 0.1Ag-1Electric current Cycle performance under density；D, the charging and discharging curve under different cycle-indexes；E, in 2Ag-1Cycle performance under current density；
Figure 13 is structural representation of the hollow dodecahedron of CNT assembling in oxygen reduction reaction and lithium ion battery Figure；
Figure 14 is embodiment 2 based on Co, the microballoon of the CNT assembling that Fe-ZIF presomas are formed：A, Co, Fe- The shape appearance figure of ZIF presomas；The XRD spectrum of b, Co, Fe-ZIF presoma；C, the XRD spectrum of the microballoon of CNT assembling；d- E, the SEM figures of the microballoon of CNT assembling；F, the EDS mapping figures of the microballoon of CNT assembling；
Figure 15 is the microballoon of the CNT assembling formed based on Ni-ZIF presomas of embodiment 3：A, Ni-ZIF forerunner The shape appearance figure of body；The XRD spectrum of b, Ni-ZIF presoma；C, the XRD spectrum of the microballoon of CNT assembling；D-e, CNT The SEM figures of the microballoon of assembling；F, the EDS mapping figures of the microballoon of CNT assembling；
Figure 16 is the hollow microsphere of the CNT assembling formed based on Ni-BTC presomas of embodiment 4：A-b, Ni- The shape appearance figure of BTC presomas；The XRD spectrum of c, Ni-BTC presoma；D-e, the SEM figures of the hollow microsphere of CNT assembling； F, the XRD spectrum of the hollow microsphere of CNT assembling；G-i, the EDS mapping figures of the hollow microsphere of CNT assembling；
Figure 17 is the micron film of the CNT assembling formed based on Co-BTC presomas of embodiment 5：A-b, Co-BTC The shape appearance figure of presoma；The XRD spectrum of c, Co-BTC presoma；D-e, the SEM figures of the micron film of CNT assembling；F, carbon is received The XRD spectrum of the micron film of mitron assembling；G-i, the EDS mapping figures of the micron film of CNT assembling；
Figure 18 is the nanometer rods of the CNT assembling formed based on Co-MOF presomas of embodiment 6：Before a, Co-MOF Drive the shape appearance figure of body；The XRD spectrum of b, Co-MOF presoma；C, the XRD spectrum of the nanometer rods of CNT assembling；D-f, carbon is received The EDS mapping figures of the nanometer rods of mitron assembling.
Specific embodiment
For a better understanding of the present invention, it is with reference to the embodiment content that the present invention is furture elucidated but of the invention Content is not limited solely to the following examples.
Embodiment 1：
1) cobalt nitrate hexahydrate for weighing 1mmol is dissolved in the methyl alcohol of 25mL；The 2-methylimidazole of 4mmol is weighed in addition It is dissolved in the methyl alcohol of 25mL, is subsequently poured into the former pink solution, mixed solution stirring 24h.Use methanol solution centrifuge washing Obtain violet solid, as metal organic framework compound Co-ZIF-67 powders for three times；
2) to step 1) obtain powder be positioned over 80 DEG C of baking ovens in dry 5h；
3) by step 2) the middle metal organic framework compound Co-ZIF-67 powders for obtaining, under an argon atmosphere, with 2 DEG C min-1Heat up at a slow speed and 435 DEG C and be incubated 8h, you can the hollow dodecahedron structure material for obtaining nitrogen-doped carbon nanometer pipe assembling (is produced Product).
The forming process of the hollow dodecahedron structure of nitrogen-doped carbon nanometer pipe assembling of the invention：As shown in figure 1, different The formation mechenism figure of process and corresponding SEM scheme.First, uniform pattern, high-crystallinity and Gao Bibiao are synthesized at ambient temperature The ZIF-67 (as shown in Figure 2) of area.Then, ZIF-67 dodecahedrons are heat-treated under the conditions of 435 DEG C and argon gas.It is therein Covalent bond between metal ion and organic ligand is preferentially broken, and whole pyrolytic process can be by thermogravimetric analysis and mass spectrometry Technical monitoring, change and the release (NH of gas along with energy3And H2) (as shown in Figure 3).These gases can be metal from Son is reduced into metal simple-substance, beneficial to the formation of nanocatalyst.After being pyrolyzed 0.5h, ZIF-67 dodecahedrons surface becomes thick It is rough, show the formation of nanocatalyst.And the organic moiety of remnants is not with volatilization, but it is centered around nanocatalyst week Enclose.The pyrolysis direction is from outside to inside, to cause hollow inner structure.Finally, by after pyrolysis cmpletely, obtaining hollow ten Dihedron, is made up of very thin CNT.In brief, the low-temperature epitaxy mechanism includes the heat of metal organic framework compound Solution, the formation of nanocatalyst and the growth of CNT, can be generalized to various different organic frame compounds.
Pattern and structure to the hollow dodecahedron structure of nitrogen-doped carbon nanometer pipe of the invention assembling are characterized：Such as Shown in Fig. 4, SEM and TEM figures confirm that what is obtained is the hollow dodecahedron structure of CNT assembling, and overall pattern is more equal It is even, about 1 μm, it is made up of much very thin CNT.The length of wherein CNT is about 200nm, and internal diameter is about 5nm, 10 between 20nm, carbon-coating is spaced about external diameterAnd in CNT end Encapsulation nanoparticle.Such as Fig. 5 institutes Show, XRD spectrum shows that product thing is mutually pure cobalt simple substance；EDS mapping collection of illustrative plates shows the distribution of uniform Co, N, C element； Raman collection of illustrative plates shows the degree of graphitization of part；Nitrogen adsorption desorption curve is shown with specific surface area (268m higher2g-1)； Element in XPS atlas analysis structure, the especially content of different type nitrogen.
The hollow dodecahedron structure of nitrogen-doped carbon nanometer pipe assembling prepared by the present invention is applied in oxygen as active material In gas reduction reaction.In former report, the species and content of the nitrogen that adulterates have very important effect to carbon material.In order to This influence is verified, different heat treatment temperatures further are carried out to sample.By testing its electrocatalysis characteristic, such as Fig. 6 institutes Show, the hollow dodecahedron of the nitrogen-doped carbon nanometer pipe assembling after 650 DEG C are heat-treated has more excellent electrocatalysis Energy.Such as Fig. 7, from linear sweep voltammetry curve comparison, by hollow ten of the nitrogen-doped carbon nanometer pipe assembling after 650 DEG C of heat treatment Dihedron has more positive half wave potential (0.85V), higher than other samples；There is the electric current more increased and very flat simultaneously Carrying current.Rotating disk electrode (r.d.e) test under different rotating speeds is used for the kinetics of Electrode material.Based on K-L equations The electron transfer number of calculating is 3.93, shows that the process is obvious 4e-Reaction.Rotating ring disk electrode (r.r.d.e) test is used for testing activity The electron transfer number of material and the yield of peroxide.In the range of 0.25 to 0.8V voltage ranges, after 650 DEG C are heat-treated Nitrogen-doped carbon nanometer pipe assembling hollow dodecahedron yields of hydrogen peroxide below 4%, and calculate electron transfer number It is 3.94.And then, the hollow dodecahedron of the nitrogen-doped carbon nanometer pipe assembling after 650 DEG C are heat-treated has stabilization higher Property, electric current conservation rate is 95% after 40000s, higher than commercialized platinum carbon electrode (78%).
In order to further study excellent electrocatalysis characteristic, the structure and composition of different samples are characterized in detail.Such as Shown in Fig. 8, by the nitrogen content in the hollow dodecahedron of the nitrogen-doped carbon nanometer pipe assembling after different heat treatment with temperature Raise and reduce, and by the XPS collection of illustrative plates of high-resolution N 1s, analyze wherein different types of nitrogen content.It is high-resolution The XPS collection of illustrative plates of Co 2p3/2 indicates the transfer for having electronics between the cobalt of confinement and the CNT of outer layer covers.UPS collection of illustrative plates point The hollow dodecahedron for having analysed the nitrogen-doped carbon nanometer pipe assembling after 650 DEG C are heat-treated has minimum work content, is conducive to Electronics accelerates electro-catalysis process from carbon nano tube surface to the molecular oxygen of absorption.Therefore, the superiority of chemical property is attributed to Cooperative effect between nitrogen-doped carbon nanometer pipe and the metal nanoparticle of confinement.And then, as shown in figure 9, a series of density Functional Theory calculates and is used to confirm cooperative effect.
The nano structural material of the nitrogen-doped carbon nanometer pipe assembling of the parcel Co simple substance obtained to embodiment 1 passes through in sky In gas under 280 DEG C of heat treatments of insulation 3h, parcel Co can be obtained3O4The nanostructured that the nitrogen-doped carbon nanometer pipe of particle is assembled into Material.
Co prepared by the present invention3O4Particle is wrapped in the hollow dodecahedron of nitrogen-doped carbon nanometer pipe assembling as active matter Matter, as shown in Figure 10, SEM and TEM figures confirm complete structure, are made up of many CNTs.As shown in figure 11, XRD Stave understands the Co of pure phase3O4, nitrogen-doped carbon content therein is about 15%, and the structure has up to 185m2g-1Specific surface Product.According to active material：Acetylene black：The mass ratio of PVDF (binding agent) is 8:1:1, assemble lithium ion battery.As shown in figure 12, The electrode material is in 0.1Ag-1Current density under, by 250 times circulation still have up to 1030mAh g-1Discharge capacity and Close to 100% capability retention；Response rate by still having 100% after the test of different current densities.Even in 2Ag-1's Under high current density, by 1000 circulations, still with stability high.
Result above shows, as shown in figure 13, the hollow dodecahedron structure of nitrogen-doped carbon nanometer pipe assembling it is excellent Chemical property has close relationship with unique texture.This structure electro-catalysis and field of batteries have great potentiality and Actual application value.
Embodiment 2：
1) cobalt nitrate hexahydrate and the water ferric nitrates of 0.3mmol nine for weighing 2mmol are dissolved in the N of 20mL, N- dimethyl formyls In amine；Then, the DMF solution with the methylimidazole of 20mL 0.2M is mixed, and is sufficiently stirred for, and is transferred to In 50mL reactors 24h is incubated at 180 DEG C.Metal organic framework compound Co, Fe- are obtained for three times with methanol solution centrifuge washing ZIF powders；
2) to step 1) obtain powder be positioned over 80 DEG C of baking ovens in dry 5h；
3) by step 2) the middle metal organic framework compound Co for obtaining, Fe-ZIF powders, under an argon atmosphere, with 2 DEG C min-1Heat up at a slow speed and 435 DEG C and be incubated 8h, you can obtain the micro-sphere structure material (product) of CNT assembling.
With the micro-sphere structure material that the CNT obtained by the present embodiment is assembled, as shown in figure 14, presoma has more Uniform pattern and crystallinity high；The micro-sphere structure pattern of the bright CNT assembling of SEM charts is uniform.
Embodiment 3：
1) the six water nickel nitrates for weighing 1mmol are dissolved in the methyl alcohol of 20mL；The 2-methylimidazole of 4mmol is weighed in addition It is dissolved in the methyl alcohol of 20mL, is subsequently poured into former solution, be sufficiently stirred for, is transferred in 50mL reactors in 140 DEG C of insulations 12h.Metal organic framework compound Ni-ZIF powders are obtained for three times with methanol solution centrifuge washing；
2) to step 1) obtain powder be positioned over 80 DEG C of baking ovens in dry 5h；
3) by step 2) the middle metal organic framework compound Ni-ZIF powders for obtaining, under an argon atmosphere, with 2 DEG C of min-1 Heat up at a slow speed and 435 DEG C and be incubated 8h, you can obtain the micro-sphere structure material (product) of CNT assembling.
With the micro-sphere structure material that the CNT obtained by the present embodiment is assembled, as shown in figure 15, presoma has more Uniform pattern and crystallinity high；The micro-sphere structure pattern of the bright CNT assembling of SEM charts is uniform.
Embodiment 4：
1) cobalt nitrate hexahydrate and 2mmol trimesic acids for weighing 1mmol are dissolved in the N,N-dimethylformamide of 35mL In, it is sufficiently stirred for, it is then transferred into being incubated 24h at 120 DEG C in 50mL reactors.Gold is obtained with methanol solution centrifuge washing three times Category organic frame compound Co-BTC powders；
2) to step 1) obtain powder be positioned over 80 DEG C of baking ovens in dry 5h；
3) by step 2) the middle metal organic framework compound Co-BTC powders for obtaining, under an argon atmosphere, with 2 DEG C of min-1 Heat up at a slow speed and 430 DEG C and be incubated 8h, you can obtain the micron film structural material (product) of CNT assembling.
With obtained by the present embodiment CNT assemble micron film structural material, as shown in figure 16, presoma have compared with It is uniform pattern and crystallinity high；The micron film structure and morphology of the bright CNT assembling of SEM charts is uniform.
Embodiment 5：
1) the six water nickel nitrates of 1mmol are weighed, 1mmol trimesic acids and 1.5g polyvinylpyrrolidones are dissolved in 30mL Mixed solution (water：Ethanol：N,N-dimethylformamide=1：1：1) in, it is sufficiently stirred for, is then transferred into 50mL reactors 10h is incubated at 150 DEG C.Metal organic framework compound Ni-BTC powders are obtained for three times with methanol solution centrifuge washing；
2) to step 1) obtain powder be positioned over 80 DEG C of baking ovens in dry 5h；
3) by step 2) the middle metal organic framework compound Ni-BTC powders for obtaining, under an argon atmosphere, with 2 DEG C of min-1 Heat up at a slow speed and 430 DEG C and be incubated 8h, you can obtain the hollow microsphere structural material (product) of CNT assembling.
With the hollow microsphere structural material that the CNT obtained by the present embodiment is assembled, as shown in figure 17, presoma has More uniform pattern and crystallinity high；The hollow microsphere structure and morphology of the bright CNT assembling of SEM charts is uniform.
Embodiment 6：
1) 2mmol trimesic acids are weighed and is dissolved in 200mL 1:1 ethanol and water mixed solution, by 1M NaOH solutions by It is added dropwise to, the PH of solution is close to 7；Then, 2mmol cobalt nitrate hexahydrates are dissolved in the aqueous solution of 50mL, and are added dropwise to Former solution, stirs 12h.Metal organic framework compound Co-MOF powders are obtained for three times with methanol solution centrifuge washing；
2) to step 1) obtain powder be positioned over 80 DEG C of baking ovens in dry 5h；
3) by step 2) the middle metal organic framework compound Co-MOF powders for obtaining, under an argon atmosphere, with 2 DEG C of min-1 Heat up at a slow speed and 430 DEG C and be incubated 8h, you can obtain the nanorod structure material (product) of CNT assembling.
With obtained by the present embodiment CNT assemble nanorod structure material, as shown in figure 18, presoma have compared with It is uniform pattern and crystallinity high；The nanorod structure pattern of the bright CNT assembling of SEM charts is uniform.

Claims (10)

1. the method for the nano structural material of the CNT assembling for being prepared based on metal organic framework compound low temperature pyrogenation, bag Include following steps：
S1 weighs appropriate slaine and organic ligand respectively, and is completely dissolved in solvent, forms homogeneous transparent solution, passes through Liquid phase synthesis, make metal ion and organic ligand in solvent that complexation reaction to occur, and form metal organic framework compound, pass through Washing, obtains metal organic framework compound powder；
S2 dries 5~10h during 80~100 DEG C of baking ovens are positioned over to the powder that step S1 is obtained；
The metal organic framework compound powder that S3 will be obtained in step S2, under an inert atmosphere, with 1~2 DEG C of min-1Rise at a slow speed 420~450 DEG C of temperature is simultaneously incubated 8~10h, you can obtain the nano structural material of CNT assembling.
2. the nanometer that the CNT based on the preparation of metal organic framework compound low temperature pyrogenation as described in claim 1 is assembled The method of structural material, it is characterised in that the nano structural material of the CNT assembling for being obtained is also by atmosphere 280 DEG C~320 DEG C insulation 3~5h heat treatment.
3. the nanometer that the CNT based on the preparation of metal organic framework compound low temperature pyrogenation as described in claim 1 is assembled The method of structural material, it is characterised in that described slaine is any one or they in the inorganic salts of cobalt, nickel and iron Mixing.
4. the nanometer that the CNT based on the preparation of metal organic framework compound low temperature pyrogenation as described in claim 1 is assembled The method of structural material, it is characterised in that described slaine is cobalt nitrate, any one or it in nickel nitrate and ferric nitrate Mixing.
5. the nanometer that the CNT based on the preparation of metal organic framework compound low temperature pyrogenation as described in claim 1 is assembled The method of structural material, it is characterised in that described organic ligand is terephthalic acid (TPA), 2-methylimidazole or trimesic acid.
6. the nanometer that the CNT based on the preparation of metal organic framework compound low temperature pyrogenation as described in claim 1 is assembled The method of structural material, it is characterised in that described slaine is 1 with the mol ratio of organic ligand:1~1:4.
7. it is a kind of based on metal organic framework compound low temperature pyrogenation prepare CNT assembling nano structural material, its by The end coated metal or metal oxide nanoparticles of the CNT of CNT or N doping simultaneously assemble, described The length of CNT is 200~500nm, and internal diameter is 3~5nm, and external diameter is 10~20nm.
8. the nano structural material that the CNT as described in claim 7 is assembled, it is characterised in that described CNT group The nano structural material of dress is hollow dodecahedron structure, microballoon, micron film or nanometer rods.
9. the nano structural material of the CNT assembling described in claim 7 is used as electro catalytic activity material.
10. the nano structural material of the CNT assembling described in claim 7 is used as lithium ion battery anode active material.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101428791A (en) * 2008-12-16 2009-05-13 南京大学 Method for producing multi-wall nano-carbon tube
CN103816905A (en) * 2014-03-21 2014-05-28 南开大学 Preparation method of carbon nano-tube loaded nano-cobalt catalyst
CN104953135A (en) * 2015-04-30 2015-09-30 北京化工大学 N-doped carbon nano tube loaded cobalt-based electro-catalytic material and preparation method thereof
CN106169381A (en) * 2016-07-26 2016-11-30 北京工业大学 A kind of synthetic method constructing the azotized carbon nano pipe with electrochemical capacitance performance based on ZIF 67

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101428791A (en) * 2008-12-16 2009-05-13 南京大学 Method for producing multi-wall nano-carbon tube
CN103816905A (en) * 2014-03-21 2014-05-28 南开大学 Preparation method of carbon nano-tube loaded nano-cobalt catalyst
CN104953135A (en) * 2015-04-30 2015-09-30 北京化工大学 N-doped carbon nano tube loaded cobalt-based electro-catalytic material and preparation method thereof
CN106169381A (en) * 2016-07-26 2016-11-30 北京工业大学 A kind of synthetic method constructing the azotized carbon nano pipe with electrochemical capacitance performance based on ZIF 67

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
BAO YU XIA ET AL.: "A metal–organic framework-derived bifunctional oxygen electrocatalyst", 《NANO ENERGY》 *

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