CN105833852B - A kind of MOFs composite adsorbing materials IMI@Cu-BTC and preparation method thereof - Google Patents
A kind of MOFs composite adsorbing materials IMI@Cu-BTC and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to sorbing material technical field, a kind of MOFs composite adsorbing materials IMI@Cu BTC and preparation method thereof are disclosed.The preparation method is that：ZnO is dissolved in deionized water and N, ZnO solution is obtained in N dimethylformamides；By Cu (NO3)2·3H2O, which is dissolved in deionized water, obtains Cu (NO3)2Solution；Trimesic acid (BTC) and imidazoles (IMI) are dissolved in ethyl alcohol and obtain organic ligand solution；Then by Cu (NO3)2Solution is added in ZnO solution, is added organic ligand solution and is stirred to react 5~10min, reaction product separating, washing, drying and vacuum activating, obtains product.The present invention reduces adsorption of the material to vapor due to the introducing of imidazoles (IMI), enhances its structural stability under humidity environment, while can keep to CO again2There is higher adsorption capacity.
Description
Technical field
The invention belongs to sorbing material technical fields, and in particular to a kind of MOFs composite adsorbing materials IMI@Cu-BTC and its
Preparation method.
Background technology
Greenhouse gases CO2A large amount of discharges caused by global warming to be that the mankind face so far the most serious
Global Environmental Problems.Therefore, to CO2Being captured and sealed up for safekeeping will be as reducing and controls CO2One of effective means of discharge.Closely
Nian Lai, a kind of emerging porous MOFs materials make it have in gas absorption separation field due to its superhigh specific surface area and Kong Rong
Boundless application prospect.Cu-BTC therein is (also referred to as：HKUST-1 it is) that one kind has gas under normal temperature and pressure conditions
There is one of the material of good adsorbent performance.(Paolo Aprea DC, the Nicola Gargiulo, Fabio such as Aprea
Iucolano,and Francesco Pepe.Modeling Carbon Dioxide Adsorption on Microporous
Substrates Comparison between Cu-BTC Metal-Organic Framework and 13X Zeolitic
Molecular Sieve [J] .J Chem Eng Data.2010,55) Cu-BTC is reported in 283K and 1bar to CO2's
Adsorption capacity is up to 7.0mmol/g, is best one of the MOF materials of 2 performance of CO absorption under low pressure generally acknowledged at present；Zeng
(Zeng Y,Zhu X,Yuan Y,Zhang X,Ju S.Molecular simulations for adsorption and
separation of thiophene and benzene in Cu-BTC and IRMOF-1metal–organic
frameworks[J].Separation and Purification Technology.2012,95:149-56.) have studied
Under the conditions of 298K and 8kPa, Cu-BTC is up to 5.39mmolg-1 to the adsorption capacity of benzene；(the Qing Min Wang such as Qing
DS,Martin BC,ulow*MLL,Shuguang Deng,FrankR.Fitch,Norberto O.Lemcoff,Jessica
Semanscin.Metallo-organic molecular sieve for gas separation and purification
[J].Microporous and Mesoporous Materials.2002,55:13) it is reported under the conditions of 295K and 1bar,
Cu-BTC is to the adsorbance of ethylene close to 6mmolg-1.Its absorption property be far above traditional activated carbon and molecular sieve with
And silica type sorbing material.However, in practical applications, water vapour is ubiquitous, since the water stability of Cu-BTC is poor,
Once with moisture, structure cave in quickly (DeCoste JB, Peterson GW, Schindler BJ, Killops KL,
Browe MA,Mahle JJ.The effect of water adsorption on the structure of the
carboxylate containing metal–organic frameworks Cu-BTC,Mg-MOF-74,and UiO-66
[J].Journal of Materials Chemistry A.2013,1(38):11922-32；Schoenecker PM,
Carson CG,Jasuja H,Flemming CJ,Walton KS.Effect of water adsorption on
retention of structure and surface area of metal–organic frameworks[J]
.Industrial&Engineering Chemistry Research.2012,51(18):6513-9；Küsgens P,Rose
M,Senkovska I, H,Henschel A,Siegle S,et al.Characterization of metal-
organic frameworks by water adsorption[J].Microporous and Mesoporous
Materials.2009,120(3):325-30), this deficiency greatly limits its practical application.Therefore, such as
What improves its steam stability, it has also become one of many researcher's key problems-solvings.For example, (the Decoste such as DeCoste
JB,Peterson GW,Smith MW,Stone CA,Willis CR.Enhanced Stability of Cu-BTC MOF
via Perfluorohexane Plasma-Enhanced Chemical Vapor Deposition[J].Journal of
the American Chemical Society.2012,134(3):1486-9；Decoste JB,Peterson
GW.Preparation of hydrophobic metal-organic frameworks via plasma enhanced
chemical vapor deposition of perfluoroalkanes for the removal of ammonia[J]
.JoVE(Journal of Visualized Experiments).2013(80):E51175-e) hydride modified by application
The surface of Cu-BTC materials makes it have hydrophobicity to achieve the effect that water is stablized, and result of study shows that contact angle increases from 60 °
One times, the material after modification has preferable hydrophobic performance；Li et al. (Li Y, Miao J, Sun X, Xiao J, Li Y, Wang
H,et al.Mechanochemical synthesis of Cu-BTC@GO with enhanced water stability
and toluene adsorption capacity[J].Chemical Engineering Journal.2016,298:191-
7) it has studied Mechanical Method and is prepared for a kind of composite material Cu-BTC@GO of Cu-BTC and graphite oxide GO, the water of this composite material
Stability is significantly enhanced, and after impregnating 10 hours in water, its BET specific surface area still has 1000m2/g。
(Mustafa D, Breynaert E, Bajpe SR, Martens JA, the Kirschhock CE.Stability such as Mustafa
improvement of Cu3(BTC)2metal–organic frameworks under steaming conditions by
encapsulation of a Keggin polyoxometalate[J].Chemical Communications.2011,47
(28):8037-9) multi-metal oxygen cluster (POMs) is added in Cu-BTC materials, although it is good that material can be made to have at 210 DEG C
Good water stability, but the pore structure of POMs meeting blocking materials is added, causing hole to hold reduces, and makes under the absorption property of material
Drop.
Invention content
In order to solve the disadvantage that the above prior art and shortcoming, the primary purpose of the present invention is that providing a kind of MOFs
The preparation method of composite adsorbing material IMI@Cu-BTC.
Another object of the present invention is to provide a kind of MOFs composite adsorbing materials being prepared by the above method
IMI@Cu-BTC。
The object of the invention is achieved through the following technical solutions：
A kind of preparation method of MOFs composite adsorbing materials IMI@Cu-BTC, including following preparation process：
(1) ZnO is dissolved in deionized water, n,N-Dimethylformamide (DMF) is added after ultrasonic disperse, obtains ZnO
Solution；By Cu (NO3)2·3H2O is dissolved in deionized water, obtains Cu (NO3)2Solution；By trimesic acid (BTC) and imidazoles
(IMI) it is dissolved in ethyl alcohol, obtains organic ligand solution；
(2) Cu (NO for obtaining step (1)3)2Solution is added in ZnO solution, is uniformly mixed, and is added organic
Ligand solution is stirred to react 5~10min and obtains the blue solution of the@of IMI containing reaction product Cu-BTC, by the organic filter membrane of solution
It is filtered, solid product through ethyl alcohol immersion, centrifugation and drying, obtains the IMI@Cu-BTC solid powders of blue successively；
(3) step (2) obtained solid powder is subjected to vacuum activating, obtains IMI@Cu-BTC sorbing materials.
ZnO described in step (1) and Cu (NO3)2·3H2The molar ratio of O is preferably (0.5~0.8):1.
Deionized water total amount described in step (1):DMF:The volume ratio of ethyl alcohol is preferably (1~1.1):(1~1.2):(1
~1.3).
In organic ligand solution described in step (1) molar ratio of trimesic acid (BTC) and imidazoles (IMI) be (2~
4):1。
Organic filter membrane that organic preferred average pore size of filter membrane described in step (2) is 0.45 μm.
Drying described in step (2) refers in 40~80 DEG C of dry 4~8h.
Vacuum activating described in step (3) refers to that 8~16h of vacuum activating is carried out at 120~200 DEG C.
A kind of MOFs composite adsorbing materials IMI@Cu-BTC, are prepared by the above method.
The present invention preparation method and obtained product has the following advantages that and advantageous effect：
(1) preparation method of the present invention is easy to operate, easy to implement, reproducible；The time of synthetic reaction is shorter, completes whole
A synthetic reaction only needs 5~10min, and traditional hydro-thermal method synthesis Cu-BTC needs 1-2 days time；
(2) compared with existing Cu-BTC sorbing materials, IMI@Cu-BTC sorbing materials prepared by the present invention, due to imidazoles
(IMI) introducing of functional group reduces adsorption of the material to vapor, and it is steady to enhance its structure under humidity environment
It is qualitative, while can keep to CO again2There is higher adsorption capacity.
Description of the drawings
The IMI@Cu-BTC samples that Fig. 1 is Cu- (BTC) and each embodiment is prepared are to N2Adsorption isotherm (77K)
Figure；
Fig. 2 is 2 gained IMI of Cu-BTC and embodiment1/3The XRD spectra of@Cu-BTC；
The IMI that Fig. 3 is Cu-BTC (left side) and prepared by embodiment 21/3The SEM of@Cu-BTC (right side) schemes；
The IMI that Fig. 4 is Cu-BTC and prepared by embodiment 21/3The FTIR of@Cu-BTC schemes；
Fig. 5 is IMI1/3The H of@Cu-BTC and Cu-BTC2O-TPD curve graphs；
Fig. 6 is 2 gained IMI of Cu-BTC (left side) and embodiment1/3@Cu-BTC (right side) place different number of days at RH=80%
Material XRD diagram；
Fig. 7 is 2 gained IMI of Cu-BTC (left side) and embodiment1/3It is RH=80% that@Cu-BTC (right side), which are exposed to relative humidity,
In air, after placing different number of days, then material sample is measured to CO2Adsorption isotherm map.
Specific implementation mode
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited
In this.
Embodiment 1
(1) ZnO (5.76mmol, n are weighed1) it is dissolved in deionized water (8ml, n2) in, DMF is added after ultrasonic 5min
(19ml, n3), obtain ZnO solution；Weigh Cu (NO3)2·3H2O (7.2mmol, n4) it is dissolved in deionized water (8ml, n5) in stir
10min is mixed, Cu (NO are obtained3)2Solution；By trimesic acid (BTC) (3.2mmol, n6) and imidazoles (IMI) (0.8mmol, n7)
It is dissolved in ethyl alcohol (16ml, n8) stirring 8min, obtain organic ligand solution；The usage ratio of wherein various substances is (n2+n5):
n3:n8=1:1.2:1；n1:n4=0.8.
(2) by Cu (NO3)2Solution is added in the solution of ZnO, stirs 10min at 35 DEG C, it is molten to add organic ligand
Liquid obtains the blue solution of the Cu-BTC of IMI containing reaction product after stirring and carrying out synthetic reaction 5min, by solution with 0.45 μm
Organic filter membrane be filtered, solid product carries out immersion 48h using 100ml ethyl alcohol, changes a solution per 12h, after centrifugation,
80 DEG C of dry 8h obtain blue powder.
(3) blue powder obtained by step (2) is placed in 120 DEG C of progress vacuum activating 16h, obtains IMI@Cu-BTC adsorption materials
Material, is denoted as：IMI1/4@Cu-BTC。
Embodiment 2
(1) ZnO (3.6mmol, n are weighed1) it is dissolved in deionized water (8ml, n2) in, DMF is added after ultrasonic 10min
(16ml, n3), obtain ZnO solution；Weigh Cu (NO3)2·3H2O (7.2mmol, n4) it is dissolved in deionized water (8ml, n5) in stir
5min is mixed, Cu (NO are obtained3)2Solution；By trimesic acid (BTC) (3mmol, n6) and imidazoles (IMI) (1mmol, n7) be dissolved in
Ethyl alcohol (16ml, n8) stirring 10min, obtain organic ligand solution；The usage ratio of wherein various substances is (n2+n5):n3:n8=
1:1:1；n1:n4=0.5.
(2) by Cu (NO3)2Solution is added in the solution of ZnO, stirs 10min at 35 DEG C, it is molten to add organic ligand
Liquid obtains the blue solution of the Cu-BTC of IMI containing reaction product after stirring and carrying out synthetic reaction 5min, by solution with 0.45 μm
Organic filter membrane be filtered, solid product carries out immersion 72h using 100ml ethyl alcohol, changes a solution per 12h, after centrifugation,
80 DEG C of dry 8h obtain blue powder.
(3) blue powder obtained by step (2) is placed in 150 DEG C of progress vacuum activating 10h, obtains IMI@Cu-BTC adsorption materials
Material, is denoted as：IMI1/3@Cu-BTC。
Embodiment 3
(1) ZnO (3.6mmol, n are weighed1) it is dissolved in deionized water (8ml, n2) in, after ultrasonic 5min be added DMF (16ml,
n3), obtain ZnO solution；Weigh Cu (NO3)2·3H2O (7.2mmol, n4) it is dissolved in deionized water (8ml, n5) in stir 5min,
Obtain Cu (NO3)2Solution；By trimesic acid (BTC) (2.7mmol, n6) and imidazoles (IMI) (1.35mmol, n7) it is dissolved in second
Alcohol (21ml, n8) stirring 10min, obtain organic ligand solution；The usage ratio of wherein various substances is (n2+n5):n3:n8=1:
1:1.3；n1:n4=0.5.
(2) by Cu (NO3)2Solution is added in the solution of ZnO, stirs 10min at 35 DEG C, it is molten to add organic ligand
Liquid obtains the blue solution of the Cu-BTC of IMI containing reaction product after stirring and carrying out synthetic reaction 10min, by solution with 0.45 μ
Organic filter membrane of m is filtered, and solid product carries out immersion 48h using 50ml ethyl alcohol, and a solution is changed per 12h, after centrifugation,
80 DEG C of dry 4h obtain blue powder.
(3) blue powder obtained by step (2) is placed in 200 DEG C of progress vacuum activating 16h, obtains IMI@Cu-BTC adsorption materials
Material, is denoted as：IMI1/2@Cu-BTC。
The characterization of IMI@Cu-BTC sorbing materials and performance measurement obtained by above example：
(1) IMI@Cu-BTC sorbing materials characterize
The IMI@Cu-BTC samples that Fig. 1 is Cu- (BTC) and each embodiment is prepared are to N2Adsorption isotherm (77K),
Table 1 is BET the and Langmuir specific surface areas of IMI@Cu-BTC samples prepared by each embodiment.It can be seen by result above
Go out, IMI1/3@Cu-BTC specific surface areas prepared by embodiment 2 are maximum, reached 1695m2/ g, but the excessive IMI that is added can be caused
The decline of specific surface area, such as embodiment 3.But it can be seen that IMI@Cu-BTC prepared by each embodiment have good porous knot
Structure.
The specific surface area of IMI@Cu-BTC prepared by 1 each embodiment of table
| Sample | BET specific surface area (m2/g) | Langmuir specific surface areas (m2/g) |
| Cu-BTC | 1796 | 1992 |
| IMI1/4@Cu-BTC | 1597 | 1781 |
| IMI1/3@Cu-BTC | 1695 | 1904 |
| IMI1/2@Cu-BTC | 1431 | 1627 |
Fig. 2 is 2 gained IMI of Cu-BTC and embodiment1/3The XRD spectrum of@Cu-BTC.It can be seen from the figure that Cu-BTC exists
2 θ=5.9 °, 9.5 °, the stronger characteristic peaks of positions appearance such as 11.6 °, these characteristic peaks and document (Li L, Liu XL, Geng
HY,Hu B,Song GW,Xu ZS.A MOF/graphite oxide hybrid(MOF:HKUST-1)material for
the adsorption of methylene blue from aqueous solution[J].Journal of
Materials Chemistry A.2013,1(35):The characteristic peak positions reported in 10292-9) are consistent, IMI@Cu-BTC
Characteristic peak it is similar to the characteristic peak of Cu-BTC, show that IMI@Cu-BTC's and Cu-BTC has similar crystal structure.
The IMI that Fig. 3 is Cu-BTC (left side) and prepared by embodiment 21/3The SEM of@Cu-BTC (right side) schemes, it can be seen that IMI1/3@
Cu-BTC crystal is irregular polyhedron, and Cu-BTC crystal is regular octahedron shape.
Fig. 4 shows Cu-BTC and IMI prepared by embodiment 21/3The FTIR of@Cu-BTC schemes, it can be seen that IMI1/3@Cu-
BTC and Cu-BTC has similar infrared spectrum.It is worth noting that, in 1660-1590cm-1There are imidazole ligands in range
(IMI) stretching vibration peak of C=C and C=N show that imidazoles (IMI) ligand is successfully modified.
(2)IMI1/3@Cu-BTC materials are to H2The TPD of O
Fig. 5 is IMI1/3The H of@Cu-BTC and Cu-BTC2O-TPD curve graphs.We can observe that in IMI1/3@Cu-
The H of BTC2On O-TPD curves, H2The desorption peaks temperature of O appears in 382K, and the H of Cu-BTC2H on O-TPD curves2The desorption peaks of O
Temperature shows H in 385K, the former peak temperature less than the latter2O molecules and IMI1/3The binding force of@Cu-BTC will be weaker than itself and Cu-
The binding force of BTC.Illustrate the adsorption that the doping of IMI weakens material to steam, this will be helpful to the water of reinforcing material
Vapour stability.
(3) Cu-BTC and IMI1/3The steam stability of@Cu-BTC materials
Fig. 6 is steam Stability Determination (the 2 gained IMI of Cu-BTC (left side) and embodiment based on XRD analysis1/3@Cu-BTC
(right side) places the XRD diagram of the material of different number of days at RH=80%).It can be seen from the figure that after Cu-BTC is placed 10 days
The characteristic peak of XRD spectra obviously weakens, and characteristic peak disappears substantially after placing 20 days, illustrates that Cu-BTC caves in completely.
IMI1/3After@Cu-BTC are placed 20 days at RH=80%, characteristic peak is held essentially constant, and shows that its crystal structure is not sent out
Changing.
Fig. 7 is to be based on CO2The steam Stability Determination of the sample of adsorbance detection.
In order to detect the steam stability of sample, sample that we prepare Cu-BTC samples (left side) and embodiment 2
IMI1/3It is after placing different number of days, then to measure material sample in RH=80% air that@Cu-BTC (right side), which are exposed to relative humidity,
To CO2Adsorption isotherm.It can be seen from figure 7 that Cu-BTC place 10 days after its CO2Large amount of adsorption amplitude declines, only
0.64mmol/g has dropped 86%, its CO after placing 20 days2Adsorbance is almost nil, illustrates the steam stability of Cu-BTC very
Difference.This is because contain the sites unsatuated metal Cu in Cu-BTC, when material and hydrone contact, one side hydrone can be with
Chemical bonding effect occurs for unsatuated metal site, destroys the crystal structure of material, another aspect hydrone can in Cu-BTC
Hydrophilic radical have an effect crystalline framework caused to be caved in (Levasseur B, Petit C, Bandosz TJ.Reactive
Adsorption of NO2on Copper-Based Metal-Organic Framework and Graphite Oxide/
Metal-Organic Framework Composites[J].ACS applied materials&interfaces.2010,2
(12):3606-13).And sample IMI prepared by embodiment1/3@Cu-BTC, after being placed 10 days under RH=80% environment, CO2
Adsorbance is 3.76mmol/g, only has dropped 14%, and after placing 20 days, and adsorbance still has 3.4mmol/g, table
The IMI@Cu-BTC materials of the bright present invention have very strong steam stability.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (7)
1. a kind of preparation method of MOFs composite adsorbing materials IMI@Cu-BTC, it is characterised in that including following preparation process：
(1) ZnO is dissolved in deionized water, n,N-Dimethylformamide is added after ultrasonic disperse, obtain ZnO solution；By Cu
(NO3)2·3H2O is dissolved in deionized water, obtains Cu (NO3)2Solution；Trimesic acid and imidazoles are dissolved in ethyl alcohol, obtained
To organic ligand solution；
(2) Cu (NO for obtaining step (1)3)2Solution is added in ZnO solution, is uniformly mixed, and organic ligand is added
Solution, is stirred to react 5~10min and obtains the blue solution of the@of IMI containing reaction product Cu-BTC, and solution is carried out with organic filter membrane
Filtering, solid product through ethyl alcohol immersion, centrifugation and drying, obtain the IMI@Cu-BTC solid powders of blue successively；
(3) step (2) obtained solid powder is subjected to vacuum activating, obtains IMI@Cu-BTC sorbing materials；
The molar ratio of trimesic acid and imidazoles is (2~4) in organic ligand solution described in step (1):1.
2. the preparation method of MOFs composite adsorbing materials IMI@Cu-BTC according to claim 1 a kind of, feature exist：Step
Suddenly ZnO described in (1) and Cu (NO3)2·3H2The molar ratio of O is (0.5~0.8):1.
3. the preparation method of MOFs composite adsorbing materials IMI@Cu-BTC according to claim 1 a kind of, feature exist：Step
Suddenly deionized water total amount described in (1):DMF:The volume ratio of ethyl alcohol is (1~1.1):(1~1.2):(1~1.3).
4. the preparation method of MOFs composite adsorbing materials IMI@Cu-BTC according to claim 1 a kind of, feature exist：Step
Suddenly organic filter membrane described in (2) refers to organic filter membrane that average pore size is 0.45 μm.
5. the preparation method of MOFs composite adsorbing materials IMI@Cu-BTC according to claim 1 a kind of, feature exist：Step
Suddenly the drying described in (2) refers in 40~80 DEG C of dry 4~8h.
6. the preparation method of MOFs composite adsorbing materials IMI@Cu-BTC according to claim 1 a kind of, feature exist：Step
Suddenly the vacuum activating described in (3) refers to that 8~16h of vacuum activating is carried out at 120~200 DEG C.
7. a kind of MOFs composite adsorbing materials IMI@Cu-BTC, it is characterised in that：Pass through claim 1~6 any one of them
Method is prepared.
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| CN109759137B (en) * | 2019-02-26 | 2021-09-28 | 东南大学 | Heterogeneous catalyst derived from metal organic material and synthetic method thereof |
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