CN110054151A - A kind of hydrophobic DUT-4 and preparation method thereof - Google Patents
A kind of hydrophobic DUT-4 and preparation method thereof Download PDFInfo
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- CN110054151A CN110054151A CN201910468823.XA CN201910468823A CN110054151A CN 110054151 A CN110054151 A CN 110054151A CN 201910468823 A CN201910468823 A CN 201910468823A CN 110054151 A CN110054151 A CN 110054151A
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- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
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- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
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Abstract
The present invention provides a kind of hydrophobic DUT-4 and preparation method thereof, belong to technical field of material.The hydrophobic DUT-4 is by including that the raw material of following components is prepared: DUT-4 powder, organosilicon and organic solvent；Organosilicon includes DOW CORNING 1-2577；The mass ratio of DUT-4 powder and organosilicon is 500:20~100.The present invention carries out hydrophobically modified to DUT-4 using DOW CORNING 1-2577, forms one layer of organic silicon hydrophobic layer on the surface DUT-4；Silicone layer can be effectively protected DUT-4 not by the attack of hydrone, avoid DUT-4 that hydrolysis occurs and destroy, substantially increase water stability.Meanwhile controlling the mass ratio of DUT-4 powder and organosilicon for 500:20~100, it avoids the organosilicon blocking duct DUT-4, reduce DUT-4 specific surface area, ensure that DUT-4 hydrogen storage property；Also make DUT-4 that there is excellent hydrophobicity.
Description
Technical field
The present invention relates to technical field of material more particularly to a kind of hydrophobic DUT-4 and preparation method thereof.
Background technique
Metal organic frame (MOFs) is a kind of novel porous materials being made of organic linker and inorganic node.Due to
The diversity and adjustability of its component and structure, MOFs is stored in gas and separation, energy are converted and storage, catalysis, chemistry biography
Sense, the sacrifice template for synthesizing porous structure etc. have obtained extensive research.In numerous applications, hydrogen storage is received
It is special to pay attention to.The member of some MOFs shows specific activity charcoal and the higher storing hydrogen ability of molecular sieve.But they are meeting
To after steam, it will usually which structural collapse causes to lose gas storage capacity.Therefore, the preparation, transport and use of these materials need
No moisture condition is wanted, which has limited their applications in hydrogen storage field.
In order to make MOFs have good hydrogen storage property and recyclable property, the water stability for improving water-sensitive MOFs becomes
One of most important Task in the field MOFs.As far as we know, there are two types of the water stabilities that main method can be used for improving MOF
Or protected from water molecules attack.One is the MOFs that direct synthetic water is stable, can be by introducing open metallic site
It is realized with non-polar functional group is introduced in organic ligand.For example, introducing hydrophobicity phenyl can be improved the moisture-resistant of IFMC-29
Gas performance.However, this method is only effective to certain specific MOFs.Another method is modified after being related to synthesis, including will be hydrophobic
Property guest molecule (for example, carbon nanotube, fluorinated molecule and polyoxometallate) is encapsulated into the internal holes and channel of MOF, with
And outer surface functionalization of MOF etc..A modified method to have a great attraction of outer surface is applied on water sensitivity MOF crystal
Upper hydrophobic polymer, to prepare nucleocapsid MOFs@polymer composites, stability of the material in aqueous environment is than original
MOFs is more preferable.For example, by physical absorption by the hydrophobic P123 polymer deposits of a thin layer in the outer surface of MOFs.Polymers function
The water stability for changing MOFs is better than original MOFs.It is too small and can not provide however, the contact angle of coating MOFs is only 22~27 °
Lasting protection.
In general, the modified water stability that can be improved MOFs in surface.However, there are some limitations, examples for the above method
Such as, complicated preparation process, heating or the hydrophobic polymer using valuableness, or obtained MOFs hydrophobicity need further to be mentioned
It is high.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of hydrophobic DUT-4 and preparation method thereof.It is provided by the invention to dredge
Water DUT-4 all has excellent water stability in acid, neutral and alkaline aqueous solution.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
It the present invention provides a kind of hydrophobic DUT-4, is prepared by the raw material for including following components: DUT-4 powder, organic
Silicon and organic solvent；The organosilicon includes DOW CORNING 1-2577；The mass ratio of the DUT-4 powder and organosilicon is 500:20
~100.
Preferably, the mass ratio of the DUT-4 powder and organosilicon is 500:30~80.
Preferably, the mass ratio of the DUT-4 powder and organosilicon is 500:40~60.
Preferably, the partial size of the DUT-4 powder is 1~100nm.
Preferably, the DUT-4 powder is prepared by the preparation method included the following steps:
By 2,6- naphthalenedicarboxylic acid, Al (NO3)3·9H2O and DMF mixing, obtains mixture；
The mixture is heated to reaction 18h at 120 DEG C, by heating reaction solution centrifugation, gained precipitating is washed with DMF
It 3 times, is dried in 80 DEG C, obtains DUT-4 powder.
Preferably, the organic solvent includes heptane.
Preferably, the amount ratio of the organic solvent and organosilicon is 10mL:20~100mg.
The present invention also provides the preparation methods of the hydrophobic DUT-4 described in above-mentioned technical proposal, comprising the following steps:
Organosilicon, DUT-4 powder and organic solvent are mixed, suspension is obtained；
The suspension is subjected to curing reaction, obtains hydrophobic DUT-4.
Preferably, described be blended under conditions of ultrasound carries out, and the power of the ultrasound is 1~500W, and the time is 1~
30min。
Preferably, the temperature of the curing reaction be room temperature, the time be 0.1~for 24 hours.
It the present invention provides a kind of hydrophobic DUT-4, is prepared by the raw material for including following components: DUT-4 powder, organic
Silicon and organic solvent；The organosilicon includes DOW CORNING 1-2577；The mass ratio of the DUT-4 powder and organosilicon is 500:20
~100.The present invention carries out hydrophobically modified to DUT-4 using DOW CORNING 1-2577, forms one layer of organic silicon hydrophobic on the surface DUT-4
Layer；Organic silicon hydrophobic layer can be effectively protected DUT-4 not by the attack of hydrone, avoid DUT-4 that hydrolysis occurs and destroy, mention significantly
High water stability.Meanwhile controlling the mass ratio of DUT-4 powder and organosilicon for 500:20~100, avoid organosilicon blocking
The duct DUT-4 reduces DUT-4 specific surface area, ensure that the hydrogen storage property of DUT-4；Meanwhile also making DUT-4 that there is excellent dredge
It is aqueous.Hydrophobic DUT-4 provided by the invention in same aqueous solution, remain DUT-4 crystal structure, pattern, surface area and
Hydrogen-absorbing ability expands application range of the DUT-4 under aqueous environment.Embodiment statistics indicate that: it is provided by the invention hydrophobic
DUT-4 all has excellent hydrophobic stability in acid, alkalinity and neutral aqueous solution.
The present invention also provides the preparation method of hydrophobic DUT-4 described in above-mentioned technical proposal, preparation method letter of the invention
Easy operation, cost of material are low.
Detailed description of the invention
Fig. 1 is the XRD diagram of the 1 hydrophobic DUT-4 powder of gained of DUT-4 powder and embodiment without hydrophobic treatment；
Fig. 2 is the N of the 1 hydrophobic DUT-4 powder of gained of DUT-4 powder and embodiment without hydrophobic treatment2Absorption and desorption
Figure；
Fig. 3 is the SEM figure of the 1 hydrophobic DUT-4 powder of gained of DUT-4 powder and embodiment without hydrophobic treatment, wherein (a)
Scheme for the SEM of the DUT-4 powder without hydrophobic treatment, (b) schemes for the SEM of hydrophobic DUT-4 powder；
Fig. 4 is that the wetability of the 1 hydrophobic DUT-4 powder of gained of DUT-4 powder and embodiment without hydrophobic treatment tests effect
Fruit figure, wherein (a) is the wetability test effect figure of the DUT-4 powder without hydrophobic treatment, it is (b) hydrophobic DUT-4 powder
Wetability test effect figure；
Fig. 5 is the XPS figure of the 1 hydrophobic DUT-4 powder of gained of embodiment, wherein (a) is the wide range figure of XPS, (b) for XPS's
High-resolution spectrogram；
Fig. 6 is TEM micro-structure diagram, wherein (a) is that there are organosilicon comfort liners on hydrophobic DUT-4 powder surface, it (b) is thin
The TEM shape appearance figure of water DUT-4 powder, (c), (d), (e) and (f) be respectively Al element, carbon, oxygen element and element silicon member
Vegetarian noodles scanning figure；
Fig. 7 is the stability test effect picture in water of the DUT-4 powder without hydrophobic treatment；Wherein (a) is without hydrophobic
The DUT-4 powder of processing is exposed to the XRD diagram after acid solution；(b) alkalinity is exposed to for the DUT-4 powder without hydrophobic treatment
XRD diagram after solution (c) is exposed to the XRD diagram after neutral solution for the DUT-4 powder without hydrophobic treatment；
Fig. 8 is hydrophobic DUT-4 powder stability test effect picture in water；Wherein (a) is that hydrophobic DUT-4 powder is exposed to
XRD diagram after acid solution；(b) it is exposed to the XRD diagram after alkaline solution for hydrophobic DUT-4 powder, (c) is hydrophobic DUT-4 powder
End is exposed to the XRD diagram after neutral solution；
Fig. 9 is after the DUT-4 powder without hydrophobic treatment exposes 6 days in acid solution, alkaline solution and neutral solution
SEM figure；Wherein, (a) is the SEM figure after the DUT-4 powder without hydrophobic treatment exposes in an acidic solution；(b) for without
SEM figure of the DUT-4 powder of hydrophobic treatment in neutral solution after exposure；(c) the DUT-4 powder without hydrophobic treatment is in alkalinity
SEM figure in solution after exposure；
Figure 10 is SEM figure of the hydrophobic DUT-4 powder in acid solution, alkaline solution and neutral solution after exposure 6 days；Its
In, (a) is the SEM figure after hydrophobic DUT-4 powder exposes in an acidic solution；It (b) is hydrophobic DUT-4 powder in neutral solution
SEM figure after exposure；(c) SEM figure of the hydrophobic DUT-4 powder in alkaline solution after exposure；
Figure 11 is after the DUT-4 powder without hydrophobic treatment exposes 6 days in acid solution, alkaline solution and neutral solution
N2Adsorption desorption curve and graph of pore diameter distribution；Wherein (a) is that the DUT-4 powder without hydrophobic treatment is molten in acid solution, alkalinity
N in liquid and neutral solution after exposure 6 days2Adsorption desorption curve, (b) for the DUT-4 powder without hydrophobic treatment acid solution,
Graph of pore diameter distribution in alkaline solution and neutral solution after exposure 6 days；
Figure 12 is N of the hydrophobic DUT-4 powder in acid solution, alkaline solution and neutral solution after exposure 6 days2Adsorption desorption
Curve and graph of pore diameter distribution；Wherein (a) is hydrophobic DUT-4 powder exposure 6 days in acid solution, alkaline solution and neutral solution
N afterwards2Adsorption desorption curve, after (b) being exposed 6 days in acid solution, alkaline solution and neutral solution for hydrophobic DUT-4 powder
Graph of pore diameter distribution；
Figure 13 is DUT-4 powder without hydrophobic treatment and hydrophobic DUT-4 powder in acid solution, alkaline solution and neutrality
H in solution after exposure 6 days2Adsorption isothermal curve；Wherein, (a) be the DUT-4 powder without hydrophobic treatment acid solution,
H in alkaline solution and neutral solution after exposure 6 days2Adsorption isothermal curve is (b) hydrophobic DUT-4 powder in acid solution, alkali
Property solution and neutral solution in exposure 6 days after H2Adsorption isothermal curve；
Figure 14 is XRD spectrum of the 2 hydrophobic DUT-4 powder of gained of embodiment after neutral solution exposure 6 days；
Figure 15 is XRD spectrum of the 3 hydrophobic DUT-4 powder of gained of embodiment after neutral solution exposure 6 days；
Figure 16 is XRD spectrum of the 4 hydrophobic DUT-4 powder of gained of embodiment after neutral solution exposure 6 days；
Figure 17 is XRD spectrum of the 1 hydrophobic DUT-4 powder of gained of comparative example after acid solution exposure 6 days；
Figure 18 is the N of the 2 hydrophobic DUT-4 powder of gained of comparative example2Absorption and desorption figure.
Specific embodiment
It the present invention provides a kind of hydrophobic DUT-4, is prepared by the raw material for including following components: DUT-4 powder, organic
Silicon and organic solvent；The organosilicon includes DOW CORNING 1-2577；The mass ratio of the DUT-4 powder and organosilicon is 500:20
~100.
The raw material for preparing hydrophobic DUT-4 includes DUT-4 powder, and the partial size of the DUT-4 powder is preferably 1~100nm.?
In the present invention, the DUT-4 powder is preferably prepared by method comprising the following steps:
By 2,6- naphthalenedicarboxylic acid, Al (NO3)3·9H2O and DMF mixing, obtains mixture；
The mixture is heated to reaction 18h at 120 DEG C, by heating reaction solution centrifugation, gained precipitating is washed with DMF
It 3 times, is dried in 80 DEG C, obtains DUT-4 powder.
In the present invention, the 2,6-naphthalenedicarboxylic acid, Al (NO3)3·9H2The amount ratio of O and DMF is 0.26g:0.52g:
30mL.In the present invention, the 2,6-naphthalenedicarboxylic acid, Al (NO3)3·9H2The order by merging of O and DMF is preferred are as follows: by 2,6- naphthalene
Dioctyl phthalate is dissolved in DMF, and Al (NO is then added3)3·9H2O magnetic stirs 5min, obtains mixture.
In the present invention, the preparation method used time of the DUT-4 is short, and the preparation method compared to conventional DUT-4 powder will
The heating reaction time shortens 6h, has saved the energy, and DUT-4 powder has equally been prepared.
The raw material for preparing hydrophobic DUT-4 includes organosilicon, and the organosilicon includes healthy and free from worry 1-2577.In the present invention, institute
The mass ratio for stating DUT-4 powder and organosilicon is 500:20~100, preferably 500:30~80, further preferably 500:40
~60.The present invention both ensure that organosilicon pair by controlling the mass ratio of DUT-4 powder and organosilicon for 500:20~100
The hydrophobically modified effect of DUT-4 powder, while avoiding organosilicon blocking DUT- powder duct, reducing DUT-4 specific surface area, it protects
The hydrogen storage property of DUT-4 powder is demonstrate,proved.
The raw material for preparing hydrophobic DUT-4 includes organic solvent；The organic solvent preferably includes heptane.The present invention is to described
The dosage of organic solvent is not specifically limited, as long as dispersion organosilicon and DUT-4 powder can be dissolved；In the present invention,
The amount ratio of the organic solvent and organosilicon is preferably 10mL:20~100mg.
The present invention carries out hydrophobically modified to DUT-4 powder using organosilicon DOW CORNING 1-2577, and DOW CORNING 1-2577 exists
After DUT-4 powder surface cure, more uniform hydrophobic coating is formed；The coating can effectively repel hydrone, prevent moisture
Son is contacted with DUT-4, is prevented DUT-4 from hydrolysis occurs and is destroyed, keeps porous structure complete, do not collapse, finally improve DUT-4
Water stabilizing.
The present invention also provides the preparation methods of hydrophobic DUT-4 described in above-mentioned technical proposal, comprising the following steps:
Organosilicon, DUT-4 powder and organic solvent are mixed, suspension is obtained；
The suspension is subjected to curing reaction, obtains hydrophobic DUT-4.
The present invention mixes organosilicon, DUT-4 powder and organic solvent, obtains suspension.
In the present invention, the mixing preferably carries out under conditions of ultrasound, and the power of the ultrasound is preferably 1~
500W, further preferably 100~450W；The time of the ultrasound is preferably 1~30min, further preferably 5~25min.
In the present invention, the addition sequence when organosilicon, DUT-4 powder and organic solvent mix preferably will be organic
Silicon is dissolved in organic solvent, and the mixing of DUT-4 powder is then added.
Ultrasound condition is sufficiently mixed organosilicon with DUT-4 powder when the present invention is mixed by control, is formed uniform outstanding
Supernatant liquid, uniform suspension are that subsequent organosilicon uniformly be ready by modified DUT-4 powder.
After obtaining suspension, the suspension is carried out curing reaction by the present invention, obtains hydrophobic DUT-4.
The present invention is not specifically limited the condition of the curing reaction, as long as making organic solvent volatilize and consolidating organosilicon
Change is attached to DUT-4 powder surface.In a specific embodiment of the present invention, the temperature of the curing reaction is preferably room
Temperature；The time of the curing reaction is preferably 0.1h~for 24 hours, further preferably 12h；The curing reaction is preferably in vacuum item
It is carried out under part.In the present invention, i.e. curable at room temperature since DOW CORNING 1-2577 is one-component, so not needing to add
Heat, it is very easy to use.Certainly, curing reaction of the invention can also be carried out in the case where temperature is slightly higher, such as 40~80
DEG C, since organic solvent is more volatile at a temperature of relatively high, so even DOW CORNING can also be made shorter under normal pressure
Completion of cure in time.
The preparation method of hydrophobic DUT-4 provided by the invention carries out hydrophobic treatment using DOW CORNING 1-2577；Due to road health
Peaceful 1-2577 is one-component, i.e. curable at room temperature, and forms one layer of organosilicon membrane on DUT-4 powder surface；This method
Low raw-material cost simple to operation, and using.
Hydrophobic DUT-4 provided by the invention and preparation method thereof is described in detail below with reference to embodiment, still
They cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
The preparation of DUT-4 powder:
2,6-naphthalenedicarboxylic acid (0.26g, 1.2mmol) is dissolved in 30mL DMF, Al (NO is then added3)3·9H2O
(0.52g, 1.4mmol) magnetic stirs 5min, obtains mixture；The mixture is transferred into 100mL polytetrafluoroethyllining lining
After in autoclave, heating reaction 18h, obtains DUT-4 powder at 120 DEG C.
The preparation of hydrophobic DUT-4:
DOW CORNING 1-2577 (40mg) is dissolved in 10mL heptane, DUT-4 powder (500mg, partial size 1 are subsequently added into
~100nm), and it is ultrasonically treated 30min (ultrasonic power 100W), obtain suspension；By the suspension under room temperature in vacuo
Curing reaction 12h obtains hydrophobic DUT-4.
Performance test:
Fig. 1 is the XRD diagram of hydrophobic DUT-4 powder obtained by DUT-4 powder and the present embodiment without hydrophobic treatment.From Fig. 1
It can be seen that having synthesized the DUT-4 of pure phase；After hydrophobic treatment, the XRD spectrum of DUT-4 powder is held essentially constant, and is illustrated hydrophobic
The modified crystal structure for not influencing DUT-4 powder.Meanwhile not finding diffraction maximum related with organosilicon, this is because content
It is low.
Fig. 2 is the N of hydrophobic DUT-4 powder obtained by DUT-4 powder and the present embodiment without hydrophobic treatment2Absorption and desorption
Figure.As can be seen from Figure 2: DUT-4 powder and hydrophobic DUT-4 powder obtain the reversible thermoisopleth of I type, show DUT-4 powder
The permanent microporosity of last and hydrophobic DUT-4 powder；The BET surface area of DUT-4 powder is measured as 1183.8m2·g-1, hydrophobic DUT-
The BET surface area of 4 powder is measured as 1125.4m2·g-1, only lose 4.8%.
Fig. 3 is the SEM figure of hydrophobic DUT-4 powder obtained by DUT-4 powder and the present embodiment without hydrophobic treatment, wherein
(a) scheme for the SEM of the DUT-4 powder without hydrophobic treatment, (b) scheme for the SEM of hydrophobic DUT-4 powder.As can be seen from Figure 3:
DUT-4 powder and hydrophobic DUT-4 powder are all sheets.
Fig. 4 is that the wetability of hydrophobic DUT-4 powder obtained by DUT-4 powder and the present embodiment without hydrophobic treatment tests effect
Fruit figure, wherein (a) is the wetability test effect figure of the DUT-4 powder without hydrophobic treatment, it is (b) hydrophobic DUT-4 powder
Wetability test effect figure.As can be seen from Figure 4: DUT-4 powder be it is hydrophilic, water droplet is easy to spread above, water contact
Angle is 13 ± 2 °；Hydrophobic DUT-4 powder be it is hydrophobic, water contact angle reaches 148 ± 3 °, and spherical water droplets can be stopped freely
And indiffusion.
Fig. 5 is the XPS figure of hydrophobic DUT-4 powder obtained by the present embodiment, wherein (a) is the wide range figure of XPS, (b) for XPS's
High-resolution spectrogram.The wide range figure of XPS shows the characteristic peak of aluminium, oxygen, silicon and carbon；In XPS high-resolution spectrogram, in conjunction with can be
The peak of 102.3eV corresponds to the core level of Si 2P, it was confirmed that the presence of organosilicon.
Fig. 6 is TEM micro-structure diagram, from fig. 6, it can be seen that there are silicone layers on DUT-4 powder；Al, C, O and Si member
Element is uniformly distributed；Aluminium and element silicon are respectively derived from DUT-4 and cured organosilicon (DOW CORNING 1-2577).
Water stability test: it is carried out in acid (pH value 1), neutral and alkaline (pH value 14) aqueous solution respectively
Water stability testing.About 200mg DUT-4 powder or hydrophobic DUT-4 powder are directly placed into above-mentioned three kinds of solution (10mL)
Then one kind is sealed in centrifuge tube；Heating carries out water stability test in 50 DEG C of baking ovens, after a period of time, from
The heart collects powder, carries out performance detection after dry.
Fig. 7 is the stability test effect picture in water of the DUT-4 powder without hydrophobic treatment；Wherein (a) is without hydrophobic
The DUT-4 powder of processing is exposed to the XRD diagram after acid solution；(b) alkalinity is exposed to for the DUT-4 powder without hydrophobic treatment
XRD diagram after solution (c) is exposed to the XRD diagram after neutral solution for the DUT-4 powder without hydrophobic treatment.It can from (a)
Out: when the DUT-4 powder without hydrophobic treatment is exposed in 50 DEG C of acidic aqueous solutions, only new diffraction maximum occur after 1 day；?
After 6 days water stability testings, all diffraction maximums relevant to DUT-4 powder are all completely disappeared；This is undoubtedly illustrated without dredging
The DUT-4 powder of water process is very sensitive to acidic aqueous solution, and experienced structure transformation.The water carried out in alkaline aqueous solution
Stability test has obtained similar result (see figure (b)).From (c) it can be seen that in neutral aqueous solution, without hydrophobic treatment
The crystal structure of DUT-4 powder keep substantially 3 days, but be no more than 6 days.
Fig. 8 is hydrophobic DUT-4 powder stability test effect picture in water；Wherein (a) is that hydrophobic DUT-4 powder is exposed to
XRD diagram after acid solution；(b) it is exposed to the XRD diagram after alkaline solution for hydrophobic DUT-4 powder, (c) is hydrophobic DUT-4 powder
End is exposed to the XRD diagram after neutral solution.As can be seen from Figure 8: comparing DUT-4 powder, hydrophobic DUT-4 powder water stability exists
It is improved to a certain extent.From (a) it can be seen that after being exposed to acidic aqueous solution, hydrophobic DUT-4 powder is able to maintain that crystalline substance
Body structure 1 day；However, occurring a new broad peak after 3d at 2 θ=9.67 °, show that crystalline transformation takes place in it；It is hydrophobic
DUT-4 powder can keep respectively at least 6 days complete knots in neutral solution (see figure (c)) and alkaline solution (see figure (b))
Brilliant degree.These results indicate that the hydrophobic layer of hydrophobic DUT-4 powder has stronger water resistance, the water for improving DUT-4 is stablized
Property.
Fig. 9 is after the DUT-4 powder without hydrophobic treatment exposes 6 days in acid solution, alkaline solution and neutral solution
SEM figure；Wherein, (a) is the SEM figure after the DUT-4 powder without hydrophobic treatment exposes in an acidic solution；(b) for without
SEM figure of the DUT-4 powder of hydrophobic treatment in neutral solution after exposure；(c) the DUT-4 powder without hydrophobic treatment is in alkalinity
SEM figure in solution after exposure.As can be seen from Figure 9: after being impregnated 6 days in three kinds of aqueous solutions, the DUT-4 without hydrophobic treatment
The sheet-like particle of powder completely disappears, and subsphaeroidal nano particle occurs.
Figure 10 is SEM figure of the hydrophobic DUT-4 powder in acid solution, alkaline solution and neutral solution after exposure 6 days；Its
In, (a) is the SEM figure after hydrophobic DUT-4 powder exposes in an acidic solution；It (b) is hydrophobic DUT-4 powder in neutral solution
SEM figure after exposure；(c) SEM figure of the hydrophobic DUT-4 powder in alkaline solution after exposure.As can be seen from Figure 10: hydrophobic
DUT-4 powder keeps lamellar morphology, and water stability is strong.
Figure 11 is after the DUT-4 powder without hydrophobic treatment exposes 6 days in acid solution, alkaline solution and neutral solution
N2Adsorption desorption curve and graph of pore diameter distribution；Wherein (a) is that the DUT-4 powder without hydrophobic treatment is molten in acid solution, alkalinity
Adsorption desorption curve in liquid and neutral solution after exposure 6 days is (b) the DUT-4 powder without hydrophobic treatment in acid solution, alkali
Property solution and neutral solution in exposure 6 days after graph of pore diameter distribution.From in (a) it can be seen that the N of DUT-4 powder2Adsorption desorption is aobvious
It is shown as II type thermoisopleth, respectively in acid, neutral and alkaline aqueous solution after exposure, specific surface area is respectively 192.7,224.5
And 206.8m2·g-1, with original DUT-4 powder (1183.8m2·g-1) compare and sharply reduce about 80%.From (b) it can be seen that
Aperture is in macropore range.
Figure 12 is N of the hydrophobic DUT-4 powder in acid solution, alkaline solution and neutral solution after exposure 6 days2Adsorption desorption
Curve and graph of pore diameter distribution；Wherein (a) is hydrophobic DUT-4 powder exposure 6 days in acid solution, alkaline solution and neutral solution
N afterwards2Adsorption desorption curve, after (b) being exposed 6 days in acid solution, alkaline solution and neutral solution for hydrophobic DUT-4 powder
Graph of pore diameter distribution.From (a) it can be seen that the N of hydrophobic DUT-4 powder2Adsorption desorption show as I type thermoisopleth.Respectively it is acid,
In neutral and alkaline aqueous solution after exposure, specific surface area is measured respectively as 903.6,983.8 and 935.4m2·g-1, it is able to maintain that
About 80% initial specific surface；This is attributed to complete porous structure.
Figure 13 is DUT-4 powder without hydrophobic treatment and hydrophobic DUT-4 powder in acid solution, alkaline solution and neutrality
H in solution after exposure 6 days2Adsorption isothermal curve；Wherein, (a) be the DUT-4 powder without hydrophobic treatment acid solution,
H in alkaline solution and neutral solution after exposure 6 days2Adsorption isothermal curve is (b) hydrophobic DUT-4 powder in acid solution, alkali
Property solution and neutral solution in exposure 6 days after H2Adsorption isothermal curve.As can be seen from Figure 13: the H of hydrophobic DUT-4 powder2It inhales
Attached amount respectively reaches 115.7,138.6 and 127.9cm3·g-1.And the H of the DUT-4 powder without hydrophobic treatment2Adsorbance is only capable of
Reach 29.7,39.1 and 32.7cm3·g-1。
Embodiment 2
The preparation of hydrophobic DUT-4:
DOW CORNING 1-2577 (20mg) is dissolved in 10mL heptane, DUT-4 powder (500mg, partial size 1 are subsequently added into
~100nm), and it is ultrasonically treated 30min (ultrasonic power 100W), obtain suspension；By the suspension under room temperature in vacuo
Curing reaction 12h obtains hydrophobic DUT-4；
The preparation method is the same as that of Example 1 for the DUT-4 powder.
Figure 14 is XRD spectrum of the 2 hydrophobic DUT-4 powder of gained of embodiment after neutral solution exposure 6 days, and diffraction maximum is kept
Intact, crystallinity is still good.This shows that the hydrophobic layer of hydrophobic DUT-4 powder has stronger water resistance, improves DUT-4
Water stability.
Embodiment 3
The preparation of hydrophobic DUT-4:
DOW CORNING 1-2577 (30mg) is dissolved in 10mL heptane, DUT-4 powder (500mg, partial size 1 are subsequently added into
~100nm), and it is ultrasonically treated 10min (ultrasonic power 150W), obtain suspension；By the suspension under room temperature in vacuo
Curing reaction 12h obtains hydrophobic DUT-4；
The preparation method is the same as that of Example 1 for the DUT-4 powder.
Figure 15 is XRD spectrum of the 3 hydrophobic DUT-4 powder of gained of embodiment after neutral solution exposure 6 days, and diffraction maximum is kept
Intact, crystallinity is still good.This shows that the hydrophobic layer of hydrophobic DUT-4 powder has stronger water resistance, improves DUT-4
Water stability.
Embodiment 4
The preparation of hydrophobic DUT-4:
DOW CORNING 1-2577 (50mg) is dissolved in 10mL heptane, DUT-4 powder (500mg, partial size 1 are subsequently added into
~100nm), and it is ultrasonically treated 20min (ultrasonic power 200W), obtain suspension；By the suspension under room temperature in vacuo
Curing reaction 12h obtains hydrophobic DUT-4；
The preparation method is the same as that of Example 1 for the DUT-4 powder.
Figure 16 is XRD spectrum of the 4 hydrophobic DUT-4 powder of gained of embodiment after neutral solution exposure 6 days, and diffraction maximum is kept
Intact, crystallinity is still good.This shows that the hydrophobic layer of hydrophobic DUT-4 powder has stronger water resistance, improves DUT-4
Water stability.
Comparative example 1
The preparation of hydrophobic DUT-4:
DOW CORNING 1-2577 (10mg) is dissolved in 10mL heptane, DUT-4 powder (500mg, partial size 1 are subsequently added into
~100nm), and it is ultrasonically treated 30min (ultrasonic power 120W), obtain suspension；By the suspension under room temperature in vacuo
Curing reaction 12h obtains hydrophobic DUT-4；
The preparation method is the same as that of Example 1 for the DUT-4 powder.
Figure 17 is XRD spectrum of the 1 hydrophobic DUT-4 powder of gained of comparative example after acid solution exposure 6 days, and diffraction maximum occurs
There is new diffraction maximum in significant change, and the diffraction maximum of original DUT-4 is vanished from sight substantially.This shows that DOW CORNING 1-2577 has
Machine silicone content cannot provide permanently effective protective effect when less, the water stability of DUT-4 does not effectively improve.
Comparative example 2
The preparation of hydrophobic DUT-4:
DOW CORNING 1-2577 (120mg) is dissolved in 10mL heptane, DUT-4 powder (500mg, partial size 1 are subsequently added into
~100nm), and it is ultrasonically treated 30min (ultrasonic power 120W), obtain suspension；By the suspension under room temperature in vacuo
Curing reaction 12h obtains hydrophobic DUT-4；
The preparation method is the same as that of Example 1 for the DUT-4 powder.
Figure 18 is the N of the 2 hydrophobic DUT-4 powder of gained of comparative example2Absorption and desorption figure.As seen from the figure, N2Adsorption desorption curve is not
I type is presented again, the specific surface of hydrophobic DUT-4 powder is only 265.7m2g-1, substantially reduced than initial specific surface.This explanation, road
Healthy and free from worry 1-2577 organosilicon dosage will lead to the duct of blocking DUT-4 too much, reduces specific surface area, is unfavorable for hydrogen storage.Organosilicon
Content is the key parameter for needing to control.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of hydrophobic DUT-4, which is characterized in that be prepared by the raw material for including following component: DUT-4 powder, organosilicon
And organic solvent；The organosilicon includes DOW CORNING 1-2577；The mass ratio of the DUT-4 powder and organosilicon be 500:20~
100。
2. hydrophobic DUT-4 according to claim 1, which is characterized in that the mass ratio of the DUT-4 powder and organosilicon is
500:30~80.
3. hydrophobic DUT-4 according to claim 1 or 2, which is characterized in that the quality of the DUT-4 powder and organosilicon
Than for 500:40~60.
4. hydrophobic DUT-4 according to claim 1, which is characterized in that the partial size of the DUT-4 powder is 1~100nm.
5. hydrophobic DUT-4 according to claim 1 or 4, which is characterized in that the DUT-4 powder is by including the following steps
Method be prepared:
By 2,6- naphthalenedicarboxylic acid, Al (NO3)3·9H2O and DMF mixing, obtains mixture；
The mixture is heated to reaction 18h at 120 DEG C, by heating reaction solution centrifugation, gained precipitating is washed 3 times with DMF,
It is dried in 80 DEG C, obtains DUT-4 powder.
6. hydrophobic DUT-4 according to claim 1, which is characterized in that the organic solvent includes heptane.
7. hydrophobic DUT-4 according to claim 6, which is characterized in that the amount ratio of the organic solvent and organosilicon is
10mL:20~100mg.
8. the preparation method of the described in any item hydrophobic DUT-4 of claim 1~7, comprising the following steps:
Organosilicon, DUT-4 powder and organic solvent are mixed, suspension is obtained；
The suspension is subjected to curing reaction, obtains hydrophobic DUT-4.
9. preparation method according to claim 8, which is characterized in that described be blended under conditions of ultrasound carries out, described
The power of ultrasound is 1~500W, and the time is 1~30min.
10. preparation method according to claim 8, which is characterized in that the temperature of the curing reaction is room temperature, and the time is
0.1~for 24 hours.
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