CN106111080A - A kind of Cu BTC@pulp fibre composite material and molding method for preparing thereof - Google Patents
A kind of Cu BTC@pulp fibre composite material and molding method for preparing thereof Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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Abstract
The invention discloses a kind of Cu BTC@pulp fibre composite material and molding method for preparing thereof.Described method is: is scattered in distilled water after log pulp based paper pretreatment, obtains log pulp solution；ZnO is dissolved in distilled water, adds DMF after supersound process and obtain ZnO solution, more successively by ZnO solution, Cu (NO3)2Solution and organic ligand solution add in log pulp solution, obtain Cu BTC@paper pulp fiber solution；Then Cu BTC@paper pulp fiber solution is filtered, dry, vacuum drying, obtain lamellar Cu BTC@pulp fibre composite material.The present invention by the Cu BTC material load of starting powder form on the natural pulp fiber that pliability is high, have easy of use, reclaim convenient advantage, there is well actual application potential.And the molding method for preparing process of the present invention is simply effective, manufacturability is strong, reproducible.
Description
Technical field
The invention belongs to porous material field shaping technique, be specifically related to a kind of Cu-BTC@pulp fibre composite material and
Its molding method for preparing.
Background technology
In recent years, metal-organic framework (Metal-Organic Frameworks, MOFs) is as emerging micro-of family
Hole/mesoporous material, owing to having the highest specific surface area, flourishing pore structure, good stability, duct is adjustable and can basis
Target call makees the advantages such as chemical modification so that MOFs material is at CO2Capture and harmful gas adsorbing separation aspect have wide
Application prospect.Wherein, Cu-BTC material be a kind of under normal temperature and pressure conditions to CO2, ethylene-ethane, benzene, dimethylbenzene and each
Plant alkane steam and all there is a kind of MOFs material of very high-adsorption-capacity, there is good application prospect.
One of subject matter faced at present is: the MOFs material that synthesis obtains, is all the crystalline material of powder, if directly
Scoop out use, it is easy to blown away by gas and be not easily recycled；If being seated in pillar, the pressure drop that can cause again post is very big, and this is greatly
Limit its application in the industry.Therefore Cu-BTC is applied to actual CO absorption2Process, it is necessary to its molding or fixing
Change.
At present the most in the world, some about the fixed-type report of MOFs material.Such as, Fernandez passes through two para-crystals
Kind of growth method fixes Cu-BTC on cordierite, for tetrahydronaphthalene catalysis (Ramos-Fernandez, E.V.,
M.Garcia-Domingos,J.Juan-et al.MOFs meet monoliths:Hierarchical
structuring metal organic framework catalysts[J].Applied Catalysis A:General,
2011.391(1-2):p.261-267).It addition, according to Balakrishnan, Cu-BTC can in grafting carboxyl functional group
Growth shaping (Sivakumar Balakrishnan, Alison J.Downard, Shane G.Telfer.Cu-on glass carbon plate
BTC-1 growth on glassy carbon[J].Mater.Chem.,2011,21,19207).Rose passes through electrostatic spinning
Method on polymer fiber, successfully fix Cu-BTC (Rose, M., B.M.Jolly,et al.MOF
Processing by Electrospinning for Functional Textiles[J].Advanced Engineering
Materials,2011.13(4):p.356-360).But, the molding technique for fixing of these MOFs materials or be shaping carrier
Valency is high rare, or is owing to carrier lacks the chemical group of the most fixing MOFs crystal thus causes forming method loaded down with trivial details, because of
And practicality is the highest.In place of solving the shortcoming and defect of above prior art, the present invention mainly develops a kind of easy to be real
Cu-BTC@pulp fibre composite material molding method for preparing.
Summary of the invention
It is an object of the invention to provide a kind of simple and practical Cu-BTC@pulp fibre composite material and be prepared by molding
Method.
The object of the invention is achieved through the following technical solutions:
The molding method for preparing of a kind of Cu-BTC@pulp fibre composite material, comprises the following steps:
(1) log pulp based paper being mixed with hydrogenperoxide steam generator, stirring makes log pulp based paper dispersed one-tenth paper pulp, heating
Carry out oxidation reaction, after having reacted, be cooled to room temperature, filter, washing, it is dried, obtains the log pulp based paper of pretreatment；
(2) the log pulp based paper of step (1) pretreatment stirring in distilled water mixing, it is molten that dissolving obtains log paper pulp
Liquid；
(3) ZnO is dissolved in distilled water, adds DMF (DMF) after supersound process, obtain ZnO molten
Liquid；By Cu (NO3)2·3H2O is dissolved in distilled water, obtains Cu (NO3)2Solution；By trimesic acid (H3BTC) it is dissolved in work
In industry ethanol, obtain organic ligand solution；
(4) the ZnO solution that step (3) obtains is joined the log pulp solution of step (2), obtains mixed solution, so
After by Cu (NO3)2Solution joins in mixed solution, is uniformly mixed, and adds organic ligand solution, and continues to stir
To Cu-BTC@paper pulp fiber solution；
(5) the Cu-BTC@paper pulp fiber solution of gained in step (4) is filtered, dry, purification, vacuum drying, obtain sheet
Shape Cu-BTC@pulp fibre composite material.
Further, the hydrogenperoxide steam generator described in step (1) refers to the hydrogen peroxide that molar concentration is 1～3mol/L
Solution；Described log pulp based paper is 1:(100～500 with the mass ratio of hydrogenperoxide steam generator).
Further, the reaction temperature of the oxidation reaction described in step (1) is preferably 50～100 DEG C, and more preferably 70
～100 DEG C, the response time is 6～12h；Described washing refers to use distilled water wash；Described dry refer at 40～60 DEG C
It is dried under temperature conditions.
Further, described in step (3), the time of supersound process is preferably 5～30min.
Further, the ZnO:Cu (NO described in step (3)3)2·3H2The mol ratio of O: trimesic acid is preferably
(0.8～1): (1～2)；(0.7～1)；The concentration of described industrial alcohol is 96% (V/V)；
Further, the distilled water total amount that step (2), (3) are added: DMF: the volume of industrial alcohol
Than being (1～1.1): (1～1.2): (1～1.3).
Further, the stirring described in step (1), (2), (3) refers to be stirred at room temperature 15～30min.
Further, described in step (4), drying refers to 30～50 DEG C of drying；Described purification refers in dehydrated alcohol
Soak 24～48 hours, within every 12 hours, change a dehydrated alcohol；Described vacuum drying refers to 150～200 DEG C of vacuum drying.
Further, the load factor of Cu-BTC of the lamellar Cu-BTC@pulp fibre composite material prepared be 60%～
72%.
A kind of Cu-BTC@pulp fibre composite material prepared by above-mentioned preparation method.
Compared with prior art, the invention have the advantages that and beneficial effect:
(1) present invention uses natural pulp fiber as the shaping carrier of Cu-BTC dusty material, and natural pulp fiber is soft
Toughness is high, easy to use, and natural pulp fiber is cheap and easy to get, and cost is relatively low；
(2) the Cu-BTC@pulp fibre composite material of the present invention is relative to the Cu-BTC material of starting powder form, has
Easy of use, reclaim convenient advantage, there is good actual application value；
(3) present invention is by carrying out oxidation pre-treatment to natural pulp fiber so that the paper pulp fiber after process has greatly
The hydroxyl of amount and carboxyl, enhance the matrix material adhesive ability to Cu-BTC dusty material；
(4) the molding method for preparing process of the present invention is simply effective, and manufacturability is strong, reproducible.
Accompanying drawing explanation
Fig. 1 is 2#Cu-BTC@PFs Yu Cu-BTC that obtain of embodiment 2 and the PXRD spectrogram of paper pulp fiber；
Fig. 2 a and Fig. 2 b is the SEM figure of the 2#Cu-BTC@PFs that embodiment 2 obtains；
Fig. 3 is the SEM figure of 2#Cu-BTC@PFs Yu Cu-BTC that embodiment 2 obtains；
Fig. 4 is the log paper pulp fiber of embodiment 3 FTIR figure before and after pretreatment；
Fig. 5 is that the constant temperature oscillator of the 3#Cu-BTC@PFs adjustable frequency that embodiment 3 obtains is under the conditions of 2Hz and 4Hz
Anti-seismic performance test result figure；
Fig. 6 is the CO absorption of the Cu-BTC@PFs that obtains of each embodiment and original Cu-BTC crystal powder2Performance test is tied
Fruit figure.
Detailed description of the invention
The invention will be further described with detailed description of the invention below in conjunction with the accompanying drawings, and the present invention is not limited to this.
Embodiment 1
(1) 100% log pulp based paper is mixed with the 10ml hydrogenperoxide steam generator that molar concentration is 1mol/l, log paper pulp
Paper is 1:100 with the mass ratio of hydrogenperoxide steam generator, and stirring 0.5h makes log pulp based paper dispersed one-tenth paper pulp, then is placed in 100
DEG C heating 6h, be cooled to room temperature, use G4Funnel filters, and is washed with distilled water to neutrality, and 40 DEG C are dried, obtain the former of pretreatment
Wood pulp paper；
(2) by 0.5g (m1) it is placed in distilled water (3ml, V through the log pulp based paper that step (1) is pretreated0Stirring 5 points in)
Clock, obtains log pulp solution；
(3) ZnO (5.76mmol, n are weighed1) it is dissolved in distilled water (8ml, V2In), after ultrasonic 5min add DMF (19ml,
V3), obtain ZnO solution；Weigh Cu (NO3)2·3H2O (7.2mmol, n4) it is dissolved in distilled water (5ml, V5Stirring 10min in),
Obtain Cu (NO3)2Solution；By trimesic acid (4mmol, n6) it is dissolved in ethanol (21ml, V7) stirring 8min, obtain organic joining
Liquid solution；The usage ratio of the most various materials is (V0+V2+V5):V3:V7=1:1.2:1.3；n1:n4:n6=1:1.25:0.7；
(4) the ZnO solution that step (3) obtains is joined the log pulp solution of step (1), obtains mixed solution, so
After by Cu (NO3)2Solution joins in mixed solution, stirs 15min mix homogeneously, adds organic ligand solution, and continue to stir
Mix 15min and obtain Cu-BTC@paper pulp fiber solution；
(5) by the Cu-BTC@paper pulp fiber solution of gained with the membrane filtration of 0.45 micron, in 30 DEG C of drying, anhydrous
Ethanol soaks 24 hours, within every 12 hours, changes a dehydrated alcohol, and be vacuum dried purification in 150 DEG C, finally give lamellar 1#
Cu-BTC@PFs composite；Weigh quality m of 1#Cu-BTC@PFs composite2=1.25g, obtains Cu-BTC in composite
Load factor be (m2-m1)/m2=60%.Can directly applying of obtained 1#Cu-BTC@pulp fibre composite material.
Embodiment 2
(1) 100% log pulp based paper is mixed with the 20ml hydrogenperoxide steam generator that molar concentration is 3mol/l, log paper pulp
Paper is 1:200 with the mass ratio of hydrogenperoxide steam generator, and stirring 15min makes log pulp based paper dispersed one-tenth paper pulp, then is placed in 70
DEG C heating 12h, be cooled to room temperature, use G4Funnel filters, and is washed with distilled water to neutrality, and 60 DEG C are dried, obtain pretreatment
Log pulp based paper；
(2) by 0.4g (m1) it is placed in distilled water (5ml, V through the log pulp based paper that step (1) is pretreated0Stirring 15 points in)
Clock, obtains log pulp solution；
(3) ZnO (3.6mmol, n are weighed1) it is dissolved in distilled water (8ml, V2In), after ultrasonic 30min add DMF (16ml,
V3), obtain ZnO solution；Weigh Cu (NO3)2·3H2O (8mmol, n4) it is dissolved in distilled water (3ml, V5Stirring 10min in),
To Cu (NO3)2Solution；By trimesic acid (4mmol, n6) it is dissolved in ethanol (16ml, V7) stirring 8min, obtain organic ligand
Solution；The usage ratio of the most various materials is (V0+V2+V5):V3:V7=1:1:1；n1:n4:n6=0.9:2:1；
(4) the ZnO solution that step (3) obtains is joined the log pulp solution of step (2), obtains mixed solution, so
After by Cu (NO3)2Solution joins in mixed solution, stirs 20min mix homogeneously, adds organic ligand solution, and continue to stir
Mix 20min and obtain Cu-BTC@paper pulp fiber solution；
(5) by the Cu-BTC@paper pulp fiber solution of gained with the membrane filtration of 0.45 micron, in 50 DEG C of drying, anhydrous
Ethanol soaks 36 hours, within every 12 hours, changes a dehydrated alcohol, and be vacuum dried purification in 180 DEG C, finally give lamellar 2#
Cu-BTC@PFs composite；Weigh quality m of 2#Cu-BTC@PFs composite2=1.19g, obtains Cu-BTC in composite
Load factor be (m2-m1)/m2=66%.Can directly applying of obtained 2#Cu-BTC@pulp fibre composite material.
Fig. 1 is 2#Cu-BTC@PFs Yu Cu-BTC that obtain of the present embodiment and the PXRD spectrogram of paper pulp fiber.Can from figure
To find out, the sample of the 2#Cu-BTC@PFs of preparation occurs in that the characteristic peak of Cu-BTC, and the material Cu-BTC really of synthesis is described,
Composite exists Cu-BTC crystal really, and crystal formation is not damaged by loading process.Simultaneously it can also be seen that 2#Cu-
BTC@PFs also remains the characteristic peak of paper pulp fiber, at 16 ° and 23 °.
Fig. 2 a and Fig. 2 b is the SEM figure of the 2#Cu-BTC@PFs that the present embodiment obtains, and Fig. 3 is the SEM figure of Cu-BTC.By scheming
3 it can be seen that Cu-BTC has the most regular octahedral crystal structure；By Fig. 2 a, Fig. 2 b it can be seen that in 2#Cu-BTC@PFs
Cu-BTC crystal is attached to fixed on paper pulp fiber equably.
Embodiment 3
(1) 100% log pulp based paper is mixed with the 50ml hydrogenperoxide steam generator that molar concentration is 1mol/l, log paper pulp
Paper is 1:500 with the mass ratio of hydrogenperoxide steam generator, and stirring 0.5h makes log pulp based paper dispersed one-tenth paper pulp, then is placed in 80 DEG C
Heating 8h, is cooled to room temperature, uses G4Funnel filters, and is washed with distilled water to neutrality, and 40 DEG C are dried, obtain the log of pretreatment
Pulp based paper；
Fig. 4 is the FTIR figure of the log paper pulp fiber before and after pretreatment, from figure, starches paper fiber before and after oxidation processes
There is the strongest hydroxyl peak (3200～3600cm-1), before process, fiber is only at 1650cm-1There is the carboxyl of minimum amplitude in place
Peak, and after oxidation processes, fiber is at 1650cm-1And 1750cm-1All occurring in that extremely strong carboxyl characteristic peak, this shows, after process
Fiber in carboxyl showed increased.This is because H2O2Solution has extremely strong Oxidation, at a certain temperature, its energy
By the methyl in paper pulp fiber (PF), the radical oxidation such as methylene forms oxy radical, such as hydroxyl, and the part of hydroxyl in fiber
Continue oxidation and can form carboxyl.These oxy radicals contribute to MOFs and adhere to molding on matrix material；
(2) by 0.3g (m1) it is placed in distilled water (8ml, V through the log pulp based paper that step (1) is pretreated0Stirring 30 points in)
Clock, obtains log pulp solution；
(3) ZnO (4.5mmol, n are weighed1) it is dissolved in distilled water (6ml, V2In), after ultrasonic 5min add DMF (20ml,
V3), obtain ZnO solution；Weigh Cu (NO3)2·3H2O (7.5mmol, n4) it is dissolved in distilled water (8ml, V5Stirring 10min in),
Obtain Cu (NO3)2Solution；By trimesic acid (4mmol, n6) it is dissolved in industrial alcohol (20ml, V7) stirring 8min, had
Machine ligand solution；The usage ratio of the most various materials is (V0+V2+V5):V3:V7=1.1:1:1；n1:n4:n6=0.9:1.5:
0.8；
(4) the ZnO solution that step (3) obtains is joined the log pulp solution of step (2), obtains mixed solution, so
After by Cu (NO3)2Solution joins in mixed solution, stirs 30min mix homogeneously, adds organic ligand solution, and continue to stir
Mix 30min and obtain Cu-BTC@paper pulp fiber solution；
(5) by the Cu-BTC@paper pulp fiber solution of gained with the membrane filtration of 0.45 micron, in 40 DEG C of drying, anhydrous
Ethanol soaks 48 hours, within every 12 hours, changes a dehydrated alcohol, and be vacuum dried purification in 200 DEG C, finally give lamellar 3#
Quality m of Cu-BTC@PFs composite weighed 3#Cu-BTC@PFs composite2=1.08g, obtains Cu-BTC in composite
Load factor be (m2-m1)/m2=72%.Can directly applying of obtained 3#Cu-BTC@pulp fibre composite material.
The 3#Cu-BTC@PFs of the present embodiment is carried out measuring mechanical property: with the constant temperature oscillator of adjustable frequency at 2Hz
With test 3#Cu-BTC PFs anti-seismic performance under conditions of 4Hz, often vibration weighs an inferior quality, result such as Fig. 5 institute for 20 minutes
Show.From figure 5 it can be seen that in continuous oscillation after 2 hours, either under the conditions of 2Hz or 4Hz, the quality of 3#Cu-BTC@PFs
Have almost no change, illustrate that 3#Cu-BTC@PFs has outstanding anti-seismic performance.
The Cu-BTC@PFs that embodiment 1～3 is obtained and the CO absorption of original Cu-BTC crystal powder2The performance test results
As shown in Figure 6.By Fig. 6 result it can be seen that along with the raising of Cu-BTC load capacity, composite Cu-BTC@PFs is to CO2Inhale
Attached amount is gradually increasing.When load capacity reaches 72%, the Cu-BTC@PFs CO when 1bar obtained2Adsorbance is about
3.56mmol/g, CO now2Adsorbance is about the 70% of the original Cu-BTC crystalline material adsorbance when 1bar, illustrate with
The increase of load capacity, Cu-BTC@PFs can reach the absorption property close to Cu-BTC, proves the mistake of composite molding further
The gas absorption performance of Cu-BTC itself is affected little by journey.
Cu-BTC@PFs that embodiment 1～3 obtains and BET and the Langmuir specific surface area of original Cu-BTC crystal powder
Test result is as shown in table 1:
Table 1 BET and Langmuir specific surface area test result
| BET(m2/g) | Langmuir(m2/g) | |
| 1#Cu-BTC@PFs | 722 | 1089 |
| 2#Cu-BTC@PFs | 866 | 1149 |
| 3#Cu-BTC@PFs | 984 | 1421 |
| Cu-BTC | 1411 | 1991 |
As seen from the results in Table 1, along with the raising of Cu-BTC load capacity, the BET specific surface area of Cu-BTC@PFs and
Langmuir specific surface area rises rapidly.The BET specific surface area of 3#Cu-BTC@PFs reaches 984m2/ g, and it is sufficiently close to theory
BET specific surface area (1411m2/ g × 72%=1015m2/ g), it may be said that not crystal to Cu-BTC during bright molding
Structure produces big destruction, and Cu-BTC@PFs still has good loose structure.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-described embodiment
Limit, the change made under other any spirit without departing from the present invention and principle, modify, substitute, combine, simplify,
All should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (10)
1. the molding method for preparing of a Cu-BTC pulp fibre composite material, it is characterised in that comprise the following steps:
(1) log pulp based paper being mixed with hydrogenperoxide steam generator, stirring makes log pulp based paper dispersed one-tenth paper pulp, and heating is carried out
Oxidation reaction, is cooled to room temperature after having reacted, filter, and washing is dried, obtains the log pulp based paper of pretreatment；
(2) the log pulp based paper of step (1) pretreatment is stirred in distilled water, dissolve and obtain log pulp solution；
(3) ZnO is dissolved in distilled water, adds DMF after supersound process, obtain ZnO solution；By Cu
(NO3)2•3H2O is dissolved in distilled water, obtains Cu (NO3)2Solution；Trimesic acid is dissolved in industrial alcohol, is had
Machine ligand solution；
(4) the ZnO solution that step (3) obtains is joined the log pulp solution of step (2), obtains mixed solution, then will
Cu(NO3)2Solution joins in mixed solution, is uniformly mixed, and adds organic ligand solution, and continues stirring and obtain Cu-
BTC@paper pulp fiber solution；
(5) the Cu-BTC@paper pulp fiber solution of gained in step (4) is filtered, dry, purification, vacuum drying, obtain lamellar
Cu-BTC@pulp fibre composite material.
A kind of molding method for preparing of Cu-BTC@pulp fibre composite material, it is characterised in that
In step (1), described hydrogenperoxide steam generator refers to the hydrogenperoxide steam generator that molar concentration is 1 ~ 3 mol/L；Described log paper
Slurry paper is 1:(100 ~ 500 with the mass ratio of hydrogenperoxide steam generator).
A kind of molding method for preparing of Cu-BTC@pulp fibre composite material, it is characterised in that
In step (1), described oxidation reaction reacts 6 ~ 12 h at a temperature of 70 ~ 100 DEG C；Described washing refers to use distilled water wash；
Described being dried refers to be dried under 40 ~ 60 DEG C of temperature conditionss.
A kind of molding method for preparing of Cu-BTC@pulp fibre composite material, it is characterised in that
The time of the supersound process described in step (3) is 5 ~ 30min.
A kind of molding method for preparing of Cu-BTC@pulp fibre composite material, it is characterised in that
In step (3), described ZnO:Cu (NO3)2•3H2The mol ratio of O: trimesic acid is (0.8 ~ 1): (1 ~ 2): (0.7 ~ 1)；Institute
The concentration of the industrial alcohol stated is 96%(V/V).
A kind of molding method for preparing of Cu-BTC@pulp fibre composite material, it is characterised in that
In step (3), the distilled water total amount that step (2), (3) are added: DMF: the volume ratio of industrial alcohol for (1 ~
1.1): (1 ~ 1.2): (1 ~ 1.3).
A kind of molding method for preparing of Cu-BTC@pulp fibre composite material, it is characterised in that
Stirring described in step (1), (2), (3) refers to be stirred at room temperature 15 ~ 30min.
A kind of molding method for preparing of Cu-BTC@pulp fibre composite material, it is characterised in that
The temperature dried described in step (4) is 30 ~ 50 DEG C；Described purification refers to soak 24 ~ 48 hours in dehydrated alcohol, every 12 little
Time change a dehydrated alcohol；Described vacuum drying temperature is 150 ~ 200 DEG C.
A kind of molding method for preparing of Cu-BTC@pulp fibre composite material, it is characterised in that
The load factor of the Cu-BTC of the lamellar Cu-BTC@pulp fibre composite material prepared is 60% ~ 72%.
10. a kind of Cu-BTC@pulp fibre composite material prepared by preparation method described in any one of claim 1 ~ 8.
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| CN114870817A (en) * | 2022-05-06 | 2022-08-09 | 南通大学 | Preparation method for improving water stability of Cu-BTC and application thereof |
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