CN103833002A - Coordination polymer and carbon nanotube composite material, preparation method and application in gas adsorption aspect - Google Patents
Coordination polymer and carbon nanotube composite material, preparation method and application in gas adsorption aspect Download PDFInfo
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Abstract
The invention claims a coordination polymer and carbon nanotube composite material, preparation method and application in gas adsorption, and belongs to the technical field of porous material. The composite material is prepared by adding carboxyl modified multi-wall carbon nanotube MWCNTs in JUC-32(Y) coordination polymer, wherein the JUC-32(Y) coordination polymer is subjected to heterocaryosis growth along the MWCNTs, and the JUC-32(Y) coordination polymer covers the surface of the MWCNTs, wherein the mass ratio of the MWCNTs to the JUC-32(Y) is 1: (200-1000). The composite material can be widely applied to the adsorption of gas (CO2 and CH4). In comparison with the pure JUC-32(Y) material, the adsorption efficiency and the adsorbing capacity of unit specific surface area are obviously improved, and the adsorption enthalpy for balancing the material and the acting force of the adsorption gas is further improved.
Description
Technical field
The invention belongs to porous material technical field, be specifically related to a kind of ligand polymer and carbon nano tube compound material, preparation method and the application of this material aspect gas adsorption.
Background technology
Metallic organic framework compound (MOF), is also become porous coordination polymer material (PCPs) by people, is to form coordinate bond by the metal ion as coordination center with the organic ligand that is connected them to form.This material has been classified as molecular screen material recently, but with respect to traditional molecular screen material, coordination polymer material is except having the pore distribution of homogeneous when, also there is lot of advantages, the most outstanding is exactly the designability of its structure, can build model by first topology design and obtain a structure of wanting, the part of selecting again suitable metal center and they being linked together, last under suitable synthesis condition, be generally solvent thermal, obtain thering is the material that starts project organization most.The duct modulability of coordination polymer material is larger simultaneously, and people can obtain a series of materials of duct size very on a large scale that have by the part of simple replacing different lengths.Owing to having a lot of avtive spots and organic ligand likely to contain a large amount of active groups on metal center, we can also be by rear synthetic method to the further modification of original material and adjustment, to meet the demand of application.Just because of above advantage, this type material can be applied in a lot of fields, comprises clean energy storage, catalytic material, gas or liquid separation, sensor, medicament slow release and the imaging of medical science mark etc.
Be accompanied by socioeconomic development, the greenhouse gases carbonic acid gas that people's daily life produces is more and more, this has just constantly aggravated the problem of the temperature rise in global range, and this problem has further caused again that the two poles of the earth Melting Glaciers :s, sea horizon rise, global climate is abnormal etc. affects the problem of the normal productive life of people.In order to solve this problem, except reducing the discharge of carbonic acid gas, select to replace the new cleaning fuel of fossil energy, also should set about processing the carbonic acid gas being discharged in atmosphere, through various countries researchist's analysis, the conclusion obtaining is to be the most effective scheme of one by its adsorption storage, and this just needs a kind of carbonic acid gas to be had to very strong adsorption, the material high to carbon dioxide capture amount.At present, permitted porous material, being comprised: carbon back class (gac, football alkene and carbon nanotube etc.), molecular sieve, metallic organic framework compound and porous polymer polymer materials are all studied for capture carbon dioxide.But the effect of single-material is always little desirable, within 2009, once reported matrix material (the S J.Yang of a kind of MOF-5 and carbon nanotube, J.Y.Choi, H.K.Chae, J.H.Cho, K.S.Nahm, C.R.Park, Preparation and Enhanced Hydrostability and Hydrogen Storage Capacity of CNT@MOF-5Hybrid Composite, Chem.Mater.2009, 21, 1893 – 1897), it is that the method by growth in situ has obtained a kind of hybrid material in the growth mother liquid that contains multi-walled carbon nano-tubes, this material not only has than the higher thermostability of original pure MOF-5 material, also there is the hydrogen adsorption amount that relative starting material are higher.We know that MOF class material is widely studied storage of hydrogen, but it is always little desirable to the absorption of carbonic acid gas, here we are just incorporated into the carbon nano-tube material that is easy to absorbing carbon dioxide in coordination polymer material, and hope can improve the absorption property of material monolithic to carbonic acid gas and methane.
Summary of the invention
The present invention relates to a kind of nanometer ligand polymer Y (BTC) (H
2o) and the matrix material of multi-walled carbon nano-tubes (MWCNTs) modified of carboxyl (COOH), preparation method and this material application aspect carbonic acid gas absorption.
Related nanometer ligand polymer Y (BTC) (H
2o), metal center can be replaced by other thuliums, we are its called after JUC-32(Y) (Li Zhongyue, Liu Kun, Zhang Yunxing, Zhu Guangshan, Qiu Shilun, the gas storage of series of rare earth metallic organic framework and photoluminescent property, " Chinese Journal of Inorganic Chemistry " 2012 28 scrolling code 710-714).This structure is to have chirality spacer P4
322 three-dimensional framework.Each structural unit comprises the Y of seven coordinations
3+, trimesic acid (BTC) part and a water molecules, along [001] direction by metal center with form the coiled strand of one dimension from the carboxyl of part trimesic acid, these coiled strands are interlinked and are formed three-dimensional skeleton structure by the phenyl ring of part along [100] and [010] both direction respectively, contain the duct of an one dimension in structure; Remove after the end group water molecules that points to duct, diameter is about 0.6 nanometer.This material has good thermostability and the adsorptive power to hydrogen and carbonic acid gas.
We are at nanometer JUC-32(Y) add the multi-walled carbon nano-tubes (MWCNTs) of carboxyl modified in ligand polymer synthetic, making JUC-32(Y) ligand polymer crystal grows along MWCNTs heteronuclear, JUC-32(Y) ligand polymer crystal is coated on MWCNTs surface, obtain a kind of at JUC-32(Y) the MWCNTs@JUC-32(Y of the MWCNTs that adulterates in ligand polymer crystal) matrix material, MWCNTs and JUC-32(Y) mass ratio is 1:200～1000.
MWCNTs@JUC-32(Y of the present invention), its preparation process is as follows:
The dispersion of A.MWCNTs
Under ultrasound condition, the multi-walled carbon nano-tubes (representing the multi-walled carbon nano-tubes of carboxyl modified in the present invention with MWCNTs) that carboxyl (COOH) is modified joins DMF(dimethyl formamide) in, and continue ultrasonicly, it is uniformly dispersed;
B.MWCNTs@JUC-32(Y) matrix material (abbreviation MW-Y-x, x=1～4) synthetic: measure the DMF solution that is dispersed with MWCNTs, adding DMF to make the concentration of MWCNTs is 0.02～0.1 mg/ml, add again deionized water, making the volume ratio of DMF and deionized water in reaction system is 5:1, prepare two parts of above-mentioned solution, be designated as a solution and b solution; In a solution, add acetic acid yttrium stirring and dissolving, add trimesic acid (BTC) stirring and dissolving in b solution, wherein the mass ratio of MWCNTs and BTC is 1:200～1000, and the mass ratio of acetic acid yttrium and BTC is 2:1; And under the condition stirring, b solution is dropwise added drop-wise in a solution, after being added dropwise to complete, obtain the greyish white emulsion to black, continue to stir to make to react completely, liquid that reacted solution is left away under centrifugal condition, and use DMF washed product, then in baking oven, dry; Finally at high temperature vacuumize and remove guest molecule (DMF and water molecules), thereby obtain MWCNTs@JUC-32(Y) matrix material.
Matrix material of the present invention can be widely used in gas (CO
2and CH
4) absorption.The adsorptive capacity of its adsorption efficiency, unit specific surface area is with respect to pure JUC-32(Y) material is significantly improved (2～3 times, be shown in Fig. 3 and 4), also had lifting (Fig. 5) for weighing the adsorption enthalpy of material and adsorbed gas amount of force
Dependence test condition and the method that the present invention relates to:
Transmission electron microscope: the transmission electron microscope photo of sample is in the JEOL3010 of NEC type transmission electron microscope (acceleration voltage 300kV) photographs.
What X-ray electron diffraction spectrogram: XRD test was used is the LabXXRD-6000 powder X ray diffractometer of Japanese Shimadzu SHIMAZU.Adopt Cu firing site, scanning 2theta scope is 4～40 °.
Physical gas absorption: in physical adsorption appearance Autosorb iQ2adsorptometer(Quantachrome Instruments, the industry of health tower) the upper H that adopts
2(99.995%), CO
2(99.995%), CH
4and N (99.95%)
2(99.995%) test of carrying out.Test before all samples first at 120 DEG C vacuum oil pump vacuumize more than 10 hours, the temperature of gas physical adsorption is 77K, 273K and 298K.
Brief description of the drawings
The x-ray diffraction spectra (a is the standard spectrogram of simulation, the sample that the corresponding embodiment 1 to 4 of b-e obtains) of Fig. 1: embodiment 1～4 sample;
Fig. 2: transmission electron microscope (TEM) photo of embodiment sample;
The 273K(a of Fig. 3: embodiment 1～4, comparative example 1～2 sample) and the 298K(b) adsorption/desorption isotherms of carbon dioxide;
The 273K(a of Fig. 4: embodiment 1～4, comparative example 1～2 sample) and the 298K(b) adsorption/desorption isotherms of lower methane;
The carbonic acid gas (a) of Fig. 5: embodiment 1～4, comparative example 1～2 sample and the adsorption enthalpy of methane (b).
In Fig. 1: the powder X ray diffraction spectrogram that adds MW-Y-1～4 hybrid material of the difference composition that the multi-walled carbon nano-tubes suspension liquid of different volumes obtains when synthetic, pure JUC-32 material X-ray spectrogram contrast with simulation, can find that each peak mates fine, proved in the scope of the carbon nanotube amount of attempting adding, still can obtain the pore passage structure of coordination polymer material.
Fig. 2 is the projection electromicroscopic photograph of composite sample, and a is the pure JUC-32(Y that there is no composite carbon nanometer tube), be nano particle (20～50 nanometer) that b is the photo that embodiment 1 obtains sample MW-Y-1.C and d's is the high resolving power transmission electron microscope photo of embodiment 1 and 3 samples, can in polycoordination matter sample, find the MWCNTs interstitial void of 0.33 nanometer, proves that carbon nanotube is doped to ligand polymer and has suffered.
Fig. 3 is the unit specific surface area adsorption/desorption isotherms of 273K and the 298K carbon dioxide of embodiment 1～4 sample.The unit specific surface area carbon dioxide adsorption of the material of physical mixed is not significantly improved as shown in the figure, but greatly improve with respect to starting material by the unit specific surface area absorption property that adds the matrix material that MWCNTs obtains in synthetic system, but data show that adsorption effect declines on the contrary along with the increase of carbon nanotube add-on.
Fig. 4 is the unit specific surface area adsorption/desorption isotherms of methane under the 273K of embodiment 1～4 sample and 298K.The unit specific surface area methane adsorptive capacity of the material of physical mixed is not significantly improved as shown in the figure, but greatly improve with respect to starting material by the unit specific surface absorption property that adds the matrix material that MWCNTs obtains in synthetic system, but data show that adsorption effect declines on the contrary along with the increase of carbon nanotube add-on.
Fig. 5 is for utilizing material isothermal adsorption curve of (273K and 298K) under two kinds of differing tempss, according to carat Bai Long equation, we can calculate the adsorption enthalpy of material to gas molecule, adsorption enthalpy is larger, testimonial material surface or duct reactive force inner and gas molecule is stronger, easier adsorption gas molecule.Assembled carbon nanotube in JUC-32 material after, its adsorption enthalpy is significantly improved, and overall trend be assembling more adsorption enthalpies larger, this result just proves to have improved material to CO adding of carbon nanotube
2and CH
4ability.
Embodiment
Embodiment 1:
A. on ten thousand/balance, accurately take 0.005 gram-COOH modify multi-walled carbon nano-tubes (MWCNTs), the another DMF that measures 50 milliliters in the glass beaker of 100 milliliters, under ultrasonic condition, MWCNTs is joined in DMF, and continue ultrasonic 30 minutes, it is uniformly dispersed.
B.MWCNTs@JUC-32(Y) matrix material synthetic
Measure respectively the dimethyl formamide dispersion liquid of the MWCNTs of 2 milliliters, and mend 10 milliliters with pure DMF, then add 2 ml deionized water, prepare two parts of above-mentioned solution (a and b).In a solution, add 0.2 gram of acetic acid yttrium stirring and dissolving, separately in b solution, add the BTC of 0.1 gram to stir.And under the condition stirring, b solution is dropwise added drop-wise in a solution, within 30 minutes, be added dropwise to complete, obtain greyish white emulsion, continue to stir after 16 hours and react completely, by the solution having reacted at 10000 revs/min of conditions liquid of leaving away, and use DMF to wash product 2 times, then at 80 DEG C, dry.Finally vacuumize 10 hours and remove guest molecule at 120 DEG C and obtain matrix material MW-Y-1, carry out afterwards the test of gas adsorption performance.MWCNTs and JUC-32(Y) mass ratio 1:1000, specific surface area is 146 meters squared per gram.
Embodiment 2:
The dispersing method of A.MWCNTS is identical with embodiment 1.
B.MWCNTs@JUC-32(Y) material synthetic:
Measure respectively 5 milliliters of DMF solution that configure above, and mend 10 milliliters with pure DMF, then add 2 ml deionized water, prepare two parts of above-mentioned solution (a and b).In a solution, add 0.2g acetic acid yttrium stirring and dissolving, separately in b solution, add the BTC of 0.1 gram to stir.And under the condition stirring, b solution is dropwise added drop-wise in a solution, within 30min minute, be added dropwise to complete, obtain dark linen emulsion, continue to stir after 16 hours and react completely, at 10000 revs/min of conditions liquid of leaving away, and use DMF to wash product 2 times the solution having reacted, finally at 80 DEG C, dry.And vacuumize 10 hours and remove guest molecule at 120 DEG C and obtain matrix material MW-Y-2, carry out afterwards the test of gas adsorption performance.MWCNTs and JUC-32(Y) mass ratio is 1:400, matrix material specific surface area is 182 meters squared per gram.
Embodiment 3:
The dispersing method of A.MWCNTS is identical with embodiment 1
B.MWCNTs@JUC-32(Y) material synthetic:
Measure respectively 8 milliliters of DMF solution that configure above, and mend 10 milliliters with pure DMF, then add 2 ml deionized water, prepare two parts of above-mentioned solution (a and b).In a solution, add 0.2 gram of acetic acid yttrium stirring and dissolving, separately in b solution, add the BTC of 0.1 gram to stir.And under the condition stirring, b solution is dropwise added drop-wise in a solution, within 30min minute, be added dropwise to complete, obtain the emulsion of grey black, continue to stir after 16 hours and react completely, at 10000 revs/min of conditions liquid of leaving away, and use DMF to wash product 2 times the solution having reacted, finally at 80 DEG C, dry.And vacuumize 10 hours and remove guest molecule at 120 DEG C and obtain matrix material MW-Y-3, carry out afterwards the test of gas adsorption performance.MWCNTs and JUC-32(Y) mass ratio is 1:250, matrix material specific surface area is 205 meters squared per gram.
Embodiment 4:
The dispersing method of A.MWCNTS is identical with embodiment 1
B.MWCNTs@JUC-32(Y) material synthetic:
Measure respectively 10 milliliters of DMF solution that configure above, then add 2 ml deionized water, prepare two parts of above-mentioned solution (a and b).In a solution, add 0.2 gram of acetic acid yttrium stirring and dissolving, separately in b, add the BTC of 0.1 gram to stir.And under the condition stirring, b solution is dropwise added drop-wise in a solution, within 30 minutes, be added dropwise to complete, obtain the emulsion of dark-grey black, continue to stir after 16 hours and react completely, at 10000 revs/min of conditions liquid of leaving away, and use DMF to wash product 2 times the solution having reacted, finally at 80 DEG C, dry.And vacuumize 10 hours and remove guest molecule at 120 DEG C and obtain matrix material MW-Y-4, carry out afterwards the test of gas adsorption performance.MWCNTs and JUC-32(Y) mass ratio is 1:200, matrix material specific surface area is 207 meters squared per gram.
Add the amount of the DMF that is mixed with MWCNTs by adjusting, regulate MWCNTs at JUC-32(Y) in incorporation, can find following problem from test result: the crystal x-ray diffraction spectra explanation doping has still kept the structure of JUC-32; Add after MWCNTs, the carbonic acid gas of matrix material and methane unit's specific surface area adsorptive capacity obviously improve, but along with add-on strengthen adsorption efficiency reduce on the contrary but still higher than pure JUC-32(Y).Final certification has obtained a kind of novel matrix material by the MWCNTs that adulterates in ligand polymer, the coordination polymer material that this material is relatively original, there is more efficient assimilation effect for carbonic acid gas with methane, there is certain application prospect in greenhouse gases processing and clean energy storage art.
Comparative example 1:
Pure JUC-32(Y) preparation: measure 10 milliliters of DMF and add 2 ml deionized water, prepare two parts of this solution (a and b).In a solution, add 0.2 gram of acetic acid yttrium stirring and dissolving, separately in b, add the BTC of 0.1 gram to stir.And under the condition stirring, b solution is dropwise added drop-wise in a solution, within 30 minutes, be added dropwise to complete, obtain linen emulsion, continue to stir after 16 hours and react completely, by the solution having reacted at 10000 revs/min of conditions liquid of leaving away, and use DMF to wash product 2 times, finally at 80 DEG C, dry.And vacuumize 10 hours and remove guest molecule at 120 DEG C obtain pure coordination polymer material JUC-32(Y), carry out afterwards the test of gas adsorption performance.Obtain corresponding structure with the complete compound proof of x-ray diffraction spectra contrast of simulation.
Comparative example 2:
Take the synthetic pure JUC-32(Y of 1 gram of comparative example 1) and MWCNTs ground and mixed in mortar of 0.005 gram even, obtain physical mixed sample (physical mixture).Use this physical mixed sample and composite sample to compare.Specific surface area, the specific surface area of the sample of physical mixed is that numerical value 419 meters squared per gram of 414 meters squared per gram and comparative example 1 are basic identical, this is because physical mechanical mixing carbon nanotube does not affect the growth of JUC-32 with regard to not destroying the structural integrity in duct, so the specific surface area of the sample of physical mixed and pure phase are basic identical yet.And in MWCNTs just joins system before metallic organic framework compound formation time, it can affect the nucleating growth of JUC-32, MOF material can utilize the carboxyl heterogeneous nucleation of carbon nano tube surface, and this will form a large amount of defects, thereby has reduced the specific surface area of material.Adsorptive capacity, physical mixed sample with the synthetic pure JUC-32 (Y) of comparative example 1 there is no a considerable change more yet, further proved us before doped and compounded have obvious performance to improve.
Claims (4)
1. a ligand polymer and carbon nano tube compound material MWCNTs JUC-32(Y), it is characterized in that: be at JUC-32(Y) add the multi-walled carbon nano-tubes MWCNTs of carboxyl modified to prepare in ligand polymer synthetic, JUC-32(Y) ligand polymer is grown along MWCNTs heteronuclear, and JUC-32(Y) ligand polymer is coated on MWCNTs surface, wherein MWCNTs and JUC-32(Y) mass ratio be 1:200～1000.
2. ligand polymer claimed in claim 1 and carbon nano tube compound material MWCNTs@JUC-32(Y) preparation method, its step is as follows:
A) under ultrasound condition, the multi-walled carbon nano-tubes MWCNTs that carboxyl-COOH is modified joins in dimethyl formamide DMF, ultrasonic it is uniformly dispersed;
B) measure the DMF solution that is dispersed with MWCNTs, adding DMF to make the concentration of MWCNTs is 0.02～0.1 mg/ml, then adds deionized water, and making the volume ratio of DMF and deionized water in reaction system is 5:1, prepare two parts of above-mentioned solution, be designated as a solution and b solution;
C) in a solution, add acetic acid yttrium stirring and dissolving, add trimesic acid BTC stirring and dissolving in b solution, wherein the mass ratio of MWCNTs and BTC is 1:200～1000, and the mass ratio of acetic acid yttrium and BTC is 2:1; And under the condition stirring, b solution is dropwise added drop-wise in a solution, after being added dropwise to complete, obtain the greyish white emulsion to black, continue to stir to make to react completely, liquid that reacted solution is left away under centrifugal condition, and use DMF washed product, then in baking oven, dry; Finally at high temperature vacuumize and remove guest molecule DMF and water, thereby obtain ligand polymer and carbon nano tube compound material MWCNTs@JUC-32(Y).
3. ligand polymer claimed in claim 1 and carbon nano tube compound material MWCNTs@JUC-32(Y) application aspect gas adsorption.
4. ligand polymer as claimed in claim 3 and carbon nano tube compound material MWCNTs@JUC-32(Y) application aspect gas adsorption, it is characterized in that: gas is CO
2or CH
4.
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Application publication date: 20140604 |