CN106241827B - A kind of preparation method of the mesopore molecular sieves of Al Bi Ce La mixing and dopings MCM 48 - Google Patents
A kind of preparation method of the mesopore molecular sieves of Al Bi Ce La mixing and dopings MCM 48 Download PDFInfo
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Abstract
The present invention relates to organic dyestuff absorption degradation technical field, is specifically related to a kind of preparation method of the mesopore molecular sieves of Al Bi Ce La mixing and dopings MCM 48.The mesopore molecular sieves of MCM 48 are dispersed in absolute ethyl alcohol, well mixed to form solution A, then weigh AlCl3、Ce(NO3)3.6H2O、LaCl3.nH2O and BiCl3It is dispersed in absolute ethyl alcohol, is slowly dropped to after stirring in solution A so that two kinds of solution mixing, and be further continued for stirring, hetero atom absorption is on the surface of molecular sieve during this；Then the C solution being made up of watery hydrochloric acid and absolute ethyl alcohol is instilled dropwise, and water is then added dropwise, continues to stir after hydrolysis completely, post processing.The mesopore molecular sieves of Al Bi Ce La mixing and dopings MCM 48 of preparation maintain good absorption degradation, can more reach the effect decolourized to colored dyes very well.
Description
Technical field
The present invention relates to organic dyestuff absorption degradation technical field, is specifically related to a kind of Al-Bi-Ce-La mixing and dopings
The preparation method of MCM-48 mesopore molecular sieves.
Background technology
MCM-48 is that a kind of uniform pore diameter is about 2.6nm, while also has two sets of separate three-dimensional spiral duct nets
The mesopore molecular sieve of network structure.Structure is in Emission in Cubic, and adjustable extent is advantageous to the transmission of macromolecular substances in 2-l0nm.Selecting
The catalysis of selecting property, macromolecules adsorption separation, the assembling etc. of Industrial Wastewater Treatment, nanocluster have a extensive future.But pure silicon
MCM-48 mesopore molecular sieves are due to a lack of activated centre, such as acid activity site, active site etc., use range are limited to, only
Can carry specifically to be catalyzed.Meanwhile pure silicon MCM-48 acid contents are low, low intensity, and have less ion-exchange capacity, lack
Few catalytic oxidation ability；The connection of mesoporous material skeleton is with the connection of Si-O-Si key-shapeds formula, and its surface is with Si-OH shapes
Formula link, this is different with atom connected mode from the atom of micropore, in addition, mesoporous material is indefiniteness structure, and zeolite material
Material has a certain crystallographic structure, therefore to be all not so good as micropore good for catalytic property and water stability, and temperature is set as high value, then
Mesoporous material hole wall and its easily hydrolyze, cause Si-O-Si keys to be broken, structure collapses；In order to extend the mesoporous materials of MCM-48
The application of material so that mesoporous material occurs largely to be lifted, and scientist passes through trial pair to this fermentation primary study
The aperture of mesoporous material is adjusted, the skeleton of mesopore molecular sieve is modified, that mesopore molecular sieve is carried out into organic and inorganic is miscellaneous
Change etc. research, the means for finding to want enhancing mesoporous material performance are enriched.Such as：By some organic groups introduce duct it
In, pass through technology organic group (amino, mercaptan etc.) silanization of grafting so that these organic groups possess more new special
Point；Metal ion is introduced in duct, difference according to demand, ion will be introduced and converted toward different aspects；Organic and inorganic is miscellaneous
Change also can enable the functional group of material be introduced into material so that material possesses more special performances；Can be with carried heteropoly acid, material
Expect the increase of surface Bransted acidic sites.
How to be modified, select which kind of hetero atom and methods to be modified, be problem to be solved.Example
Such as, directly preparing mesoporous material while be doped into a kind of simple and effective side that rare-earth heteroatoms are change MCM-48 performances
Method.Heteroatomic introduction can improve the performance of pure silicon-based mesoporous molecular sieve from many aspects so that MCM-48 molecular sieve structures
It is not easy to cave in, and improves its catalytic performance and ion exchangeable.The surface silicon of the mesopore molecular sieve of pure silicon base is only seldom
A part of activity is strong, and carries out grafting with active function groups to change its poor performance, therefore people use other hetero atoms
Instead of pure Si atoms, hetero atom is set to obtain soda acid or redox center.Hetero atom be mainly introduce metallic atom, metal from
The introduction in sub- activated centre is easily destroyed MCM-48 long-range order, people succeeded introduction hetero atom have Ce, Cr, V,
Al, Fe, Cu, Zr etc..And the material such as bimetallic (Cu-Zn, W-Mn, Ru-Pt), hetero atom quilt is shown by a series of characterize
Such as activated centre, heteroatomic introduce is introduced to cause MCM-48 hole wall and duct to have a series of modification to change, repair
The MCM-48 mesopore molecular sieves adornd are in photoelectrocatalysis, ion exchange, the removal of heavy metal ion, the fixation of fuel, organic dirt
Degraded absorption of dye thing etc. suffers from wide Research Significance.
The method that hetero atom introduces mesopore molecular sieve there are into several sides such as doping, grafting and injection (dipping) method in situ
Method.Doping method in situ is that directly the hetero atom handled well is being added in mixed liquor during preparing mesopore molecular sieve,
In the solution, hetero atom predecessor can be with the hydrolytie polycondensation mistake of silicon source predecessor spontaneous generation silicon source predecessor in the basic conditions
Journey, then repeatedly crystallization steps, the metal ion of final doping method doping in situ enter framework of molecular sieve.Infusion process and grafting
Process is similar, and both of which is that the processing in later stage is carried out to pure silicon mesopore molecular sieve, and specific method is the MCM- that will be prepared
48 are mixed with heteroatomic precursor liquid under certain conditions, then stir certain time, until complete hydrolysis, centrifugation,
The processes such as washing, drying, high-temperature calcination, obtain modified MC M-48；And grafting difference is that be applicable system is non-aqueous
System, in building-up process, grafting needs first to configure the predecessor non-aqueous solution of metal heteroatom, can be alcoholic solution or
Organic solution, modified molecular screen then is made by washing, drying and other steps again.It is metal that infusion process, which adulterates heteroatomic advantage,
The content of ion incorporation skeleton is higher than original position doping, but too high tenor also several knots for being highly vulnerable to breakage MCM-48
Structure, so different for the doping method of different selecting responses.
The content of the invention
The purpose of the present invention is to propose to a kind of preparation method of Al-Bi-Ce-La mixing and dopings MCM-48 mesopore molecular sieves,
To overcome the drawbacks described above of prior art.
In order to achieve this, present invention employs following technical scheme：
A kind of preparation method of Al-Bi-Ce-La mixing and dopings MCM-48 mesopore molecular sieves, using infusion process, weighs 0.4g
MCM-48 mesopore molecular sieves be dispersed in the beaker for the absolute ethyl alcohol for filling 35mL, form solution A, 30min is to solution for stirring
It is mixed thoroughly；0.2g AlCl is weighed again3, 0.6g Ce (NO3)3.6H2O, 0.5g LaCl3.nH2O's and 0.64g
BiCl3It is dispersed in 15mL absolute ethyl alcohols, is slowly dropped to after stirring in solution A so that two kinds of solution mixing, and again
Continue to stir 1h, hetero atom absorption is on the surface of molecular sieve during this；Then instill dropwise by 5mL 0.5M watery hydrochloric acid
The C solution formed with 10mL absolute ethyl alcohol, is stirred for 2h, and 10mL water is then added dropwise, and continues to stir 2h after hydrolysis completely, from
The heart, it is washed with deionized water, 100 DEG C of dryings, 500 DEG C of calcining 4h, natural cooling, Al-Bi-Ce-La mixing and dopings is obtained after grinding
MCM-48 mesopore molecular sieves.
As optimal technical scheme, the preparation method of the MCM-48 mesopore molecular sieves is：
1., using CTAB as single template, prepare cation template homogeneous solution
Weigh appropriate cation template and be dissolved in deionized water, both weight ratios are 2.2：42.3, use magnetic agitation
Device stirs always, until CTAB solid particles are completely dissolved；
2., regulation cation template solution pH
According to volume ratio ammoniacal liquor：Absolute ethyl alcohol=13.2：66.7 prepare mixed solution, are added into cation template
Continue to stir in homogeneous solution, after two kinds of solution are well mixed, now the pH of solution reaches neutral or alkalescence；
3., add inorganic silicon source, make itself and organic formwork agent polycondensation
Silester (TEOS) is slowly added dropwise to regulating in the solution after pH, this process reaction time is 1-2h, and
Stirring is always maintained at, could so allow template to react complete with silicon source；
4., the complete molten colloidal solution of reaction shifted and crystallized
Colloidal solution mixed solution is moved into reactor, control temperature as 120 DEG C, allows solution crystallization in a kettle
18h, the MCM-48 of no removed template method is obtained after the completion of crystallization；
5., sample post-processing
, in 550 DEG C of temperature lower calcination 6h, MCM-48 mesopore molecular sieves will be obtained after sample clean, suction filtration, drying.
Beneficial effects of the present invention are shown：
The preparation method that the present invention selects is to be improved in the original location on the basis of doping method, and doping method in situ is to prepare
Directly the hetero atom handled well is added in mixed liquor during mesopore molecular sieve, in the solution, hetero atom predecessor
Can with the hydrolytie polycondensation process of silicon source predecessor spontaneous generation silicon source predecessor in the basic conditions, then repeatedly crystallization steps,
The metal ion of final doping method doping in situ enters framework of molecular sieve, and replaces Si and from Si-O-Si be changed into Si-O-M (M is
Metallic element), now there is silicon atom also to have hetero atom in the skeleton of molecular sieve, form a kind of mixed matrix, finally by washing
The MCM-48 products that step was modified such as wash, dry, calcining.Method very simple is convenient in this, and hetero atom is easy
Into the skeleton of molecular sieve, and the molecular sieve functional diversities after being modified, and when the active component for adulterating entrance can be long
Effectively preserve, and substantially increase the activity in some performances so that some action effects of molecular sieve are more preferable.Shortcoming
It is that when the production of the structural parameters of hetero atom and pure Si atoms is not very big, heteroatomic doping can destroy original molecular sieve
Skeleton, synthesis condition is more harsh, and heteroatomic content may be relatively low.
Al-Bi-Ce-La mixing and doping MCM-48 mesopore molecular sieves prepared by the present invention maintain good absorption degradation
Property, it can more reach the effect decolourized to colored dyes very well.
Brief description of the drawings
Fig. 1 is the XRD of target product prepared by embodiment 2.
Fig. 2 is the XRD of target product prepared by embodiment 3.
Fig. 3 is the XRD of target product prepared by embodiment 4.
Fig. 4 is the XRD of target product prepared by embodiment 5.
Fig. 5 is the XRD of target product prepared by embodiment 1.
Fig. 6 is the SEM figures of four kinds of different multiplyings of target product prepared by embodiment 2.
Fig. 7 is the SEM figures of four kinds of different multiplyings of target product prepared by embodiment 3.
Fig. 8 is the SEM figures of four kinds of different multiplyings of target product prepared by embodiment 4.
Fig. 9 is the SEM figures of four kinds of different multiplyings of target product prepared by embodiment 5.
Figure 10 is the SEM figures of two kinds of different multiplyings of target product prepared by embodiment 1.
Figure 11 is the N2 adsorption desorption curve figure of target product prepared by embodiment 1.
Figure 12 is the thermogravimetric curve figure of target product prepared by embodiment 2.
Figure 13 is the thermogravimetric curve figure of target product prepared by embodiment 3.
Figure 14 is the thermogravimetric curve figure of target product prepared by embodiment 4.
Figure 15 is the thermogravimetric curve figure of target product prepared by embodiment 5.
Figure 16 is the thermogravimetric curve figure of target product prepared by embodiment 1.
Figure 17 is the infrared spectrogram of target product prepared by embodiment 2-5.
Figure 18 is the infrared spectrogram of target product prepared by embodiment 1.
Figure 19 is the methylene blue solution absorption degradation curve of target product prepared by embodiment 1-5.
Embodiment
One kind that the present invention is further described below by way of specific embodiment is used for Al-Bi-Ce-La mixing and dopings
The preparation method of MCM-48 mesopore molecular sieves.
First, embodiment is prepared
Embodiment 1
1st, the preparation of MCM-48 mesopore molecular sieves：
1., using CTAB as single template, prepare cation template homogeneous solution
Weigh appropriate cation template and be dissolved in deionized water, both weight ratios are 2.2：42.3, use magnetic agitation
Device stirs always, until CTAB solid particles are completely dissolved.
2., regulation cation template solution pH
According to volume ratio ammoniacal liquor：Absolute ethyl alcohol=13.2：66.7 prepare mixed solution, are added into cation template
Continue to stir in homogeneous solution, after two kinds of solution are well mixed, now the pH of solution reaches neutral or alkalescence.
3., add inorganic silicon source, make itself and organic formwork agent polycondensation
Silester (TEOS) is slowly added dropwise to regulating in the solution after pH, this process reaction time is 1-2h, and
Stirring is always maintained at, could so allow template to react complete with silicon source.
4., the complete molten colloidal solution of reaction shifted and crystallized
Colloidal solution mixed solution is moved into reactor, control temperature as 120 DEG C, allows solution crystallization in a kettle
18h, the MCM-48 of no removed template method is obtained after the completion of crystallization.
5., sample post-processing
, in 550 DEG C of temperature lower calcination 6h, MCM-48 mesopore molecular sieves will be obtained after sample clean, suction filtration, drying.
2nd, the preparation of Al-Bi-Ce-La mixing and dopings MCM-48 mesopore molecular sieves：
The MCM-48 mesopore molecular sieves for weighing 0.4g are dispersed in the beaker for the absolute ethyl alcohol for filling 35mL, form solution A,
Stirring 30min is mixed thoroughly to solution.0.2g AlCl is weighed again3, 0.6g Ce (NO3)3.6H2O, 0.5g
LaCl3.nH2O and 0.64g BiCl3It is dispersed in 15mL absolute ethyl alcohols, is slowly dropped to after stirring in solution A so that
Two kinds of solution mixing, and be further continued for stirring 1h, hetero atom absorption is on the surface of molecular sieve during this.Then instill dropwise
The C solution being made up of 5mL 0.5M watery hydrochloric acid and 10mL absolute ethyl alcohol, is stirred for 2h, and 10mL water is then added dropwise, has hydrolyzed
Continue to stir 2h after complete, centrifugation, be washed with deionized water three times, 100 DEG C of dryings, 500 DEG C of calcining 4h, natural cooling, after grinding
To Al-Bi-Ce-La mixing and doping MCM-48 mesopore molecular sieves.
Embodiment 2
Al adulterates the preparation of MCM-48 mesopore molecular sieves：
The MCM-48 mesopore molecular sieves for weighing 0.4g are dispersed in the beaker for the absolute ethyl alcohol for filling 35mL, form solution A,
Stirring 30min is mixed thoroughly to solution；0.7g AlCl is weighed again3It is dispersed in 15mL absolute ethyl alcohols, after stirring
It is slowly dropped in solution A so that two kinds of solution mixing, and be further continued for stirring 1h, hetero atom, which adsorbs, during this is dividing
The surface of son sieve；Then the C solution being made up of 5mL 0.5M watery hydrochloric acid and 10mL absolute ethyl alcohol is instilled dropwise, is stirred for
2h, 10mL water is then added dropwise, continues to stir 2h after hydrolysis completely, centrifugation, be washed with deionized water three times, 100 DEG C of dryings, 500 DEG C
4h is calcined, natural cooling, Al doping MCM-48 mesopore molecular sieves are obtained after grinding.
Embodiment 3
Bi adulterates the preparation of MCM-48 mesopore molecular sieves：
The MCM-48 mesopore molecular sieves for weighing 0.4g are dispersed in the beaker for the absolute ethyl alcohol for filling 35mL, form solution A,
Stirring 30min is mixed thoroughly to solution；2.55g BiCl is weighed again3It is dispersed in 15mL absolute ethyl alcohols, after stirring
It is slowly dropped in solution A so that two kinds of solution mixing, and be further continued for stirring 1h, hetero atom, which adsorbs, during this is dividing
The surface of son sieve；Then the C solution being made up of 5mL 0.5M watery hydrochloric acid and 10mL absolute ethyl alcohol is instilled dropwise, is stirred for
2h, 10mL water is then added dropwise, continues to stir 2h after hydrolysis completely, centrifugation, be washed with deionized water three times, 100 DEG C of dryings, 500 DEG C
4h is calcined, natural cooling, Bi doping MCM-48 mesopore molecular sieves are obtained after grinding.
Embodiment 4
Ce adulterates the preparation of MCM-48 mesopore molecular sieves：
The MCM-48 mesopore molecular sieves for weighing 0.4g are dispersed in the beaker for the absolute ethyl alcohol for filling 35mL, form solution A,
Stirring 30min is mixed thoroughly to solution；2.3g Ce (NO are weighed again3)3.6H2O, 0.5g LaCl3.nH2O's and 0.64g
BiCl3It is dispersed in 15mL absolute ethyl alcohols, is slowly dropped to after stirring in solution A so that two kinds of solution mixing, and again
Continue to stir 1h, hetero atom absorption is on the surface of molecular sieve during this；Then instill dropwise by 5mL 0.5M watery hydrochloric acid
The C solution formed with 10mL absolute ethyl alcohol, is stirred for 2h, and 10mL water is then added dropwise, and continues to stir 2h after hydrolysis completely, from
The heart, it is washed with deionized water three times, 100 DEG C of dryings, 500 DEG C of calcining 4h, natural cooling, it is mesoporous that Ce doping MCM-48 is obtained after grinding
Molecular sieve.
Embodiment 5
La adulterates the preparation of MCM-48 mesopore molecular sieves：
The MCM-48 mesopore molecular sieves for weighing 0.4g are dispersed in the beaker for the absolute ethyl alcohol for filling 35mL, form solution A,
Stirring 30min is mixed thoroughly to solution；1.9g LaCl is weighed again3.nH2O and 0.64g BiCl3It is anhydrous to be dispersed in 15mL
In ethanol, it is slowly dropped to after stirring in solution A so that two kinds of solution mixing, and be further continued for stirring 1h, this process
Middle hetero atom absorption is on the surface of molecular sieve；Then instill and be made up of 5mL 0.5M watery hydrochloric acid and 10mL absolute ethyl alcohol dropwise
C solution, be stirred for 2h, then be added dropwise 10mL water, hydrolysis completely after continue stir 2h, centrifugation, be washed with deionized water three times,
100 DEG C of dryings, 500 DEG C of calcining 4h, natural cooling, La doping MCM-48 mesopore molecular sieves are obtained after grinding.
2nd, the sign of doped samples
1st, X-ray diffraction (XRD) is analyzed
Fig. 1 is the XRD of target product prepared by embodiment 2.Because the angle of this experiment test is larger, pass through figure
From the point of view of shape, it can only see at 2 θ=one more sharp but wide peak of 21-22 ° of appearance, this peak is MCM-48 under wide-angle
Characteristic peak, illustrate that heteroatomic doping maintains the original pore passage structure of MCM-48 mesoporous materials, and this peak is more
Sharply, it is because orderly cubic structure crystallinity is big, Another reason is that the intensity at peak is overlapped mutually after hetero atom mixes；
Bibliography is understood, compared with standard MCM-48 is at 2 θ=21-22 ° of peak gone out, after adulterating aluminium ion, peak becomes strong, illustrates
This ion has had a certain amount of enhancing for being entrained in skeleton, result in peak；There is an Al at 2 θ=40 ° or so in addition2O3
Characteristic peak, it is and relatively strong, illustrate that existing more silicon ion is substituted by aluminium ion on skeleton.
Fig. 2 is the XRD of target product prepared by embodiment 3.It can be analyzed from figure in 2 θ=21-22 ° of appearance one
Individual more sharp but not high intensity SiO2Characteristic peak, illustrate that the doping of bismuth ion also maintains the original hole of mesoporous material
Road structure, crystallinity is good not as adulterating aluminum ions mesoporous material, and this intensity and standard MCM-48 feature steamed bun peaks are poor
Seldom, it is impossible to know whether bismuth ion is successfully doped into skeleton.But after experimental analysis understands in 2 θ=25 °, occur
The crystal face peaks of multiple bismuth oxides, illustrate that the bismuth ion amount successfully adulterated is less.
Fig. 3 is the XRD of target product prepared by embodiment 4.It can be seen that 2 θ=21-22 ° of characteristic peak with it is more
The peak containing cerium oxide of kind form is all relatively strong, illustrates that material modified crystallinity is high, while cerium largely substitutes silicon ion, miscellaneous
Random strong peak also illustrates to be probably to be overlapped mutually after mixing hetero atom.But understood by analysis in 2 θ>Occur after 30 ° more
SiO2Characteristic peak, illustrate that the undefined structure of hole wall keeps complete, do not destroy.
Fig. 4 is the XRD of target product prepared by embodiment 5.Occur that an intensity is stronger to spread out in 2 θ=11.95 °
Peak is penetrated, a wider diffraction maximum occurs in 2 θ=21.38 °, illustrates that sample crystallinity is very high, and long-range order keeps good
Good, hetero atom is also successfully doped into skeleton, improves the stability of modified molecular screen.
Fig. 5 is the XRD of target product prepared by embodiment 1.It can find out that several metals and rare earth element are common by figure
Mesoporous point of MCM-48 after doping vario-property still maintains good pore passage structure from sieve, but crystallization degree is not so good as single doping shape
Formula is good, and oxide and Si oxide containing each metal ion species have been also detected that in figure, so explanation doping works well.
2nd, sem analysis
Fig. 6 is the SEM figures of four kinds of different multiplyings of target product prepared by embodiment 2.It can be seen that adulterated al is modified
MCM-48 shape it is regular, no phenomenon of rupture, illustrate that modified Al-MCM-48 maintains good meso-hole structure.Its profile
It is similar bar-shaped in SEM figures, illustrate that grain shape is uniform.And can also be found out by (a), have between particle and particle one compared with
Big space, this finds that its absorption property is fine by studying Al-MCM-48 to the adsorptivity of methylene blue, thus it is speculated that these
Uniform space serves preferable effect；Find out that the doping of Al ions make it that crystal grain reunion degree is high secondly by (c), (d) figure,
It is uniformly dispersed, also can prove that with reference to its XRD, because during MCM-48 mesopore molecular sieves are synthesized, the drop of silicon source
Acceleration is controlled preferable so that the amount that silicon source is reunited together is moderate, so mesopore molecular sieve is of moderate size.Secondly molecular sieve phase
Mutually interweave, uniform particle sizes are about 0.5 μm or so, and grain diameter is moderate, illustrate that material maintains the aperture response of mesoporous material.
Fig. 7 is the SEM figures of four kinds of different multiplyings of target product prepared by embodiment 3.As can be seen that the size of particle is not
It is visibly homogeneous, aperture illustrates that hole is larger between 0.5-1 μm, and hetero atom incorporation may influence on extension.Secondly by figure
(a) (b) can find out that particle is rounded, there is reunion between partial particulate, distribution and crystallization situation all not as adulterated al it
Afterwards uniform.
Fig. 8 is the SEM figures of four kinds of different multiplyings of target product prepared by embodiment 4.It can be seen that its particle is uniform, and
And there is serious agglomeration, particle surface is rough, and it is probably that excessive, shape is added dropwise in silicon source the reason for such case occur
Into material in there is the compound of the more siliceous and cerium of species, it is also possible to be because Sample Preparation Procedure in do not wash it is dry
Only, there is impurity, but according to most of figure from the point of view of, particle diameter has increased, and this also illustrates that cerium atom successfully adulterates.
Fig. 9 is the SEM figures of four kinds of different multiplyings of target product prepared by embodiment 5.It can be seen that crystallization effect is not
Very well, but grain shape is still very uniform, rounded, there is agglomeration between partial particulate, it may be possible to because speed is added dropwise in silicon source
Spend fast, formation accumulation.Particle pore size and pure MCM-48 are similar, illustrate to adulterate after hetero atom that to maintain MCM-48 original
Structure.
Figure 10 is the SEM figures of two kinds of different multiplyings of target product prepared by embodiment 1.As can be seen that the profile of particle
Have a very large change, similar wooden dipper shape, with reference to Al-Bi-Ce-La-MCM-48 application can be seen that this wooden dipper shape structure can
Effectively to adsorb organic dyestuff, author thinks the reason for shape causes in this be probably that hetero atom enters in duct, destroys material
The hole wall structure of material.And particle diameter illustrates that hetero atom causes mesoporous material diauxic growth at 0.8 μm or so.Meanwhile from figure
In can also find out that the crystallinity of particle is high.
3rd, BET is analyzed
Figure 11 is the N2 adsorption desorption curve figure of target product prepared by embodiment 1.Find out that adsorption isotherm belongs to by figure
IV kinds, so the Al-Bi-Ce-La-MCM-48 of gained has preferable meso-hole structure, first stage relative pressure is found out by figure
Smaller area (P/P0=0.05-0.4) adsorption isothermal curve projection is upwards；Second stage is in relative pressure upper zone (P/P0=
0.4-0.98), isothermal curve increases rapidly, and reason is the coacervation that adsorbate generates capillary in this process, because
To there is the coacervation of capillary, it is misaligned with adsorption curve that this stage can see desorption curve, and desorption curve exists
Caused hysteresis above adsorption curve, clearly hysteresis loop as we can see from the figure, producing the generation of hysteresis is
Because the size and shape in hole is different, aperture cohesion position in figure P/P0The ground of the beginning of=0.4 position, i.e. hysteresis loop
Side, the position that maximum pore condenses completely is in P/P0=098, the i.e. final position of hysteresis loop, coagulation liquid filling are full whole
The various pieces of system, integrally find out that low pressure hysteresis loop is smaller in figure, illustrate that samples long-range order slightly reduces, this can
Can cause crystallization to be dissolved because crystallization time is long.Phase III (P/P0=0.98-1) when all apertures of adsorbate complete to coagulate
After poly-, adsorption phenomena occurs for the outer surface of particle, although the area of outer surface is much smaller than inner surface, the absorption of this section of process
So that isothermal curve is in P/P0On the rise in=0.9-0.98 regions, curve is on significantly precipitous close to 1 place
Rise, be because the reason for adsorbance increased dramatically, cause this phenomenon is that macroporous absorption starts.Understood by analysis modified
MCM-48 specific surface areas are 105.179m2/ g, aperture 15.345nm, specific surface area reduce, and aperture also reduces, and this is probably brilliant
Change overlong time, cause dissolution of crystals, or Doped ions are more, ratio is bad, destroys the pore passage structure of sample, from
SEM it can also be seen that, mixed and modified MCM-48 appearance changes, and similar split recrystallizes again.
4th, TG is analyzed
Thermogravimetric analysis is a kind of analysis means studied material mass and vary with temperature relation, and main operational principle is to work as thing
Matter has many-side the reason for its quality can change, cause change in thermal histories, such as:Nature a series of physical chemistry
Change, it can be common that the vaporization of material, distillation, the loss of the crystallization water, decompositions etc., the abscissa for being exactly thermogravimetric curve represent warm
Degree, corresponding ordinate is mass change, and by understanding curve, we can analyze weight, material and the generation that material loses
The information such as the temperature of change.
Figure 12 is the thermogravimetric curve figure of target product prepared by embodiment 2.Al-MCM-48 starting point is found out in TG figures
Solve temperature be 25 DEG C, tended to balance after 550 DEG C, material does not continue to decompose, from DTA graph discoveries at 45 DEG C when occur one
Sharp peak, this positional representation sample have exothermic reaction in this temperature, and Al-MCM-48 samples can be calculated from TG figures
The weight-loss ratio of product, i.e. Δ W%=W0%-WEnd%=99.01%-82.82%=16.9%；It can be seen that undecomposed impurity is remaining
Measure as 83.1%, undecomposed amount is larger.Al-MCM-48 once obvious appearances at T=45 DEG C, T=are found out by DTA figures
215 DEG C of once weaker appearances, each time appearance correspond to the weight change of TG curves.T=45 DEG C of appearance main cause be because
For in sample moisture scatter and disappear.The most important reason in peak caused by T=215 DEG C is 1. prepared organic-inorganic material
Machine template does not remove totally, molecular chain rupture will occur again at this temperature, finally with CO2、H2The small-molecule substances such as O will
Disperse.In 150-250 DEG C of section, Hoffmann decomposition, C occur for CTAB16H33(CH2)3N+→C16H32+N(CH3)3+H+Hereafter,
C16H32Because boiling point is at 157 DEG C, 240 DEG C of burning-point, therefore continues to rise according to temperature, C16H32Continue fracture to decompose, N (CH3)3
190 DEG C of burning-point, therefore with the increase of temperature, N (CH3)3The gases such as burned generation, at 215 DEG C or so, organic formwork agent quilt
Decompose 50% or so.2. and in the process, also polycondensation formation Si-O-Al keys occur for small part between inorganic silicon source and silicon source, and
Surface is that the Si-OH dehydrating polycondensations of reaction are Si-O-Si keys.3. caused a small amount of aluminium hydroxide or other complex compounds exist in solution
This less than 200 DEG C dehydrations generate aluminum oxide.
Figure 13 is the thermogravimetric curve figure of target product prepared by embodiment 3.It can be seen that sample decomposes at 20 DEG C -590 DEG C,
Weight-loss ratio Δ W%=W0%-WEnd%=100%-88.55%=11.45%, obvious two peaks are found out on DTA figures, in T
At=50 DEG C occur a sharp peak, illustrate there is exothermic reaction at this temperature, reason be moisture at this temperature
It is a large amount of to scatter and disappear, the molecule C that template CTAB is broken out16H32Portion fractures at this temperature, the smaller molecule of generation.In T=
160 DEG C of appearance, one weaker peak, reason is probably that organic-inorganic material once carried out hydro-thermal process with ammoniacal liquor before being calcined
Cross, at 100-160 DEG C in structure the halogen ion of intermediate medium electric charge and ammonium ion with NH4X form removes.
Figure 14 is the thermogravimetric curve figure of target product prepared by embodiment 4.It can be seen that sample decomposition temperature section is 25
DEG C -500 DEG C, DTG curves have obvious sharp peak twice, T=50 DEG C of appearance reason and above two metal ion mixing reason
Identical, mainly moisture scatters and disappears, and is primarily threefold the reason for T=195 DEG C of appearance:1. clean CTAB templates are not removed
The fracture of agent；2. silicon source is derived from main dress polycondensation with cerium and is dehydrated to form key, polycondensation between complete silicon source is not reacted；3. add
Cerium source (cerous nitrate) can form cerium hydroxide at 50 DEG C -200 DEG C in the basic conditions, and cerium oxide is formed after calcining.
Figure 15 is the thermogravimetric curve figure of target product prepared by embodiment 5.It can be seen that sample decomposition temperature section is 25
DEG C -590 DEG C, DTG curves have obvious sharp peak twice, T=50 DEG C of appearance reason and above two metal ion mixing reason
Identical, mainly moisture scatters and disappears, and is probably the fracture for not removing thoroughly CTAB templates the reason for T=360 DEG C of appearance, raw
Into C16H32Burning generation CO2、H2The small molecules such as O, and N (CH3)3Burning generation CO2、H2O、NO、NO2Several small molecules.
Figure 16 is the thermogravimetric curve figure of target product prepared by embodiment 1.It can be seen that sample decomposition temperature 25 DEG C-
Between 590 DEG C, and it is similar with monometallic ion doping weight-loss ratio, within 20%, the difference is that monometallic ion doping is only
Have an appearance twice, and four kinds of combining forms are adulterated and cause the DTA curve of sample to have appearance three times, this three times appearance the reason for more
Comprehensive, T=45 DEG C there is more sharp peak, because moisture largely scatters and disappears in this stage；T=155 DEG C there is weaker peak, reason
It is that the template not removed completely is just broken burning in this stage, is scattered and disappeared in the form of small molecule；The unreacted silicon source of small part and its
Polycondensation dehydration occurs for his source metal；Ammoniacal liquor handles organic-inorganic material with being used in an experiment, it is final caused by after impurity with
NH4X form removes；T=290 DEG C there is weaker peak, and main cause is not remove clean template to continue decomposition combustion；
The decomposeds such as organic matter absolute ethyl alcohol；Some metal ions produce easy complex compound, but most of meeting during synthesis
Exist with hydroxide form, regardless of existence form, finally at high temperature can kinetics into oxide.
5th, FT-IR is analyzed
Figure 17 is the infrared spectrogram of target product prepared by embodiment 2-5.Adulterated as can be seen from Figure (Al, Bi,
Ce, La) etc. after metal ion sample appearance on infrared spectrum it is more, and the infrared spectrum after adulterating with not undoped with before
It is similar, it can represent the functional group of complete sample and the information of chemical bond substantially.In 3410cm-1There is one relatively strong wider suction in place
Peak is received, this is typically by ≡ Si (OH) ,=Si (OH)2、-Si(OH)3Absworption peak is formed Deng silicone hydroxyl key chattering, is illustrated
The silicone hydroxyl key on the surface of sample is a lot.And hydroxyl concentration is larger, intermolecular hydrogen bonding is just increased, absworption peak now broadens just
It can be widened, but the absworption peak of this position is that the appearance of the characteristic peak of skeleton also just illustrates that the addition of metal ion is preferable
Maintain the original silicon skeleton structures of MCM-48.Two can be clearly apparent by-CH in sample infrared spectrogram simultaneously3Or-
CH2- antisymmetric stretching vibration caused by weak peak.In 3100cm-1It it is one, wave number is in 2930cm-1It is one again.
2030cm-1There is a very weak absworption peak in place, and reason is a small amount of=Si (OH)2In 1540cm-1And 1620cm-1Peak very
Sharply, and compare figure and find out every kind of sample in this appearance, because Bronsted (1540- in sample be present
1630cm-1) sour and Lewis (1450-1620cm-1) acid, and can find out the doping of several metal ion species cause L acid than B acid
Acid amount it is more, contrast the spectrogram after several ion dopings, find the Bi-MCM-48 acid amount maximum of L acid.And B acid is acid
Amount is similar.In 1090cm-1There is strong and sharp peak in place, and the silicon-oxy tetrahedron Si-O-Si key antisymmetry of reason skeleton is stretched
Vibration can be vibrated, the sharp peak of formation, and in the case where wavelength is larger, silicon-oxy tetrahedron can occur symmetrical stretch and shake
856cm that is dynamic, being formed in figure-1Locate peak；In 417cm-1Caused by the peak of left and right is due to Si-O-Si flexural vibrations absorption, from
Figure is it can be seen that 856cm-1With 417cm-1The peak at place is different with doping metals varying strength, wherein La-MCM-48 maximum intensities,
Bi-MCM-48 is most weak, and inspection information understands that compared with pure MCM-48 two absorption peak strengths have reducing tendency, it may be possible to because
Mixed for metallic atom in skeleton, instead of mono- silicon of Si-O-Si, form Si-O-R (R refers to Al, Bi, Ce, La) ion, so as to
It result in intensity decreases.In 1495cm-1、2854cm-1、2924cm-1There is no obvious c h bond vibration band Deng position, illustrate mould
Plate agent is eliminated very clean, has been analyzed in thermogravimetric analysis.
Figure 18 is the infrared spectrogram of target product prepared by embodiment 1.It is seen that 856cm-1There is typical case in place
Peak, this is that silicon-oxy tetrahedron symmetrical stretching vibration forms visible either single doping or mixing and doping all under larger wavelength
Such peak occurs.In 1087cm-1There is strong and sharp peak in place, because silicon-oxy tetrahedron Si-O-Si key antisymmetry is stretched
Contracting vibration, illustrates that the doping of a variety of rare earth elements and metal ion maintains original MCM-48 skeleton structure, 1219cm-1Go out
An existing weaker peak is because of the stretching vibration of C-O keys is formed, 1415cm-1There is stronger and sharp peak to illustrate in sample
Contain Lewis (1450-1620cm-1) acid, and the acid amount of Lewis acid is very big.
3rd, absorption degradation is tested
Prepare 10 test tubes (2 test tubes of every kind of sample), be added with to every test tube counterpoise into 8ml methylene blue solutions,
The PH of methylene blue solution has been adjusted to 7, concentration 6mg/L, then weighs 5 kinds of samples after being modified with electronic balance again,
Every kind of sample precisely claims 0.04g, and sample is added in ready methylene blue solution, and waiting sample to be used after submerging in solution can
See illumination irradiate test tube, this experimental selection is strong sunshine, static, each time interval be 15min, 30min,
4ml is taken to the sample in five test tubes, every kind of solution respectively when 45min, 1h, the sample of acquirement is transferred in centrifuge tube,
Adjust centrifuge, revolution 4000r/min, time 5min.The supernatant of the solution centrifuged is taken, is then transferred into visible point
In the photometric cuvette of light, the absorbance for the methylene blue surveyed is surveyed (664nm) according to maximum absorption wavelength, record
Data.And according to formula DC=[(A0-A)/A0] × 100% calculates percent of decolourization.
Figure 19 is the methylene blue solution absorption degradation curve of target product prepared by embodiment 1-5.It can be seen by curve
Go out, the degradability of 5 kinds of samples is all fine, and percent of decolourization is very high, and minimum percent of decolourization reaches 82% or so, and it is left to can reach 98%
It is right；Secondly it is overall to can be seen that modified the MCM-48 either doping of monometallic form or four kinds of metal co-dopeds, inhale
Attached degradation speed is all quickly, almost degradable in 150min.The difference is that the MCM-48 being modified by different metal ions
Its absorption degradation effect is different, and shown in figure, percent of decolourization is with regard to highest at the beginning by Ce-MCM-48, by 150min illumination
Rear decoloring rate remains unchanged highest, illustrates that its effect is best, how metal-doped Al-Bi-Ce-La-MCM-48 was found out in the whole time
Percent of decolourization is all relatively more placed in the middle.Above content analysis can substantially illustrate each not phase of adsorbent adsorption effect after different metal doping
Together.
It is pointed out that the present invention is not limited only to embodiment listed above, it is every can be direct from present invention
Export or enlightenment, which join conceivable correlation technique, all should belong to the scope that the present invention covers protection.
Claims (3)
1. a kind of preparation method of Al-Bi-Ce-La mixing and dopings MCM-48 mesopore molecular sieves, using infusion process, its feature exists
In the MCM-48 mesopore molecular sieves for weighing 0.4g are dispersed in the beaker for the absolute ethyl alcohol for filling 35mL, form solution A, stirring
30min is mixed thoroughly to solution；0.2g AlCl is weighed again3, 0.6g Ce (NO3)3.6H2O, 0.5g LaCl3.nH2O
With 0.64g BiCl3It is dispersed in 15mL absolute ethyl alcohols, is slowly dropped to after stirring in solution A so that two kinds of solution mixes
Close, and be further continued for stirring 1h, hetero atom absorption is on the surface of molecular sieve during this；Then instill dropwise by 5mL 0.5M
Watery hydrochloric acid and 10mL absolute ethyl alcohol composition C solution, be stirred for 2h, then be added dropwise 10mL water, hydrolysis completely after continue to stir
2h is mixed, centrifuges, is washed with deionized water, 100 DEG C of dryings, 500 DEG C of calcining 4h, natural cooling, Al-Bi-Ce-La is obtained after grinding and mixes
Close doping MCM-48 mesopore molecular sieves.
2. preparation method as claimed in claim 1, it is characterised in that the preparation method of the MCM-48 mesopore molecular sieves is：
1., using CTAB as single template, prepare cation template homogeneous solution
Weigh appropriate cation template and be dissolved in deionized water, both weight ratios are 2.2：42.3, with magnetic stirring apparatus one
Straight stirring, until CTAB solid particles are completely dissolved；
2., regulation cation template solution pH
According to volume ratio ammoniacal liquor：Absolute ethyl alcohol=13.2：66.7 prepare mixed solution, are added into the uniform of cation template
Continue to stir in solution, after two kinds of solution are well mixed, now the pH of solution reaches neutral or alkalescence；
3., add inorganic silicon source, make itself and organic formwork agent polycondensation
Silester (TEOS) is slowly added dropwise to regulating in the solution after pH, this process reaction time is 1-2h, and always
State is kept stirring for, could so allow template to react complete with silicon source；
4., the complete molten colloidal solution of reaction shifted and crystallized
Colloidal solution mixed solution is moved into reactor, it is 120 DEG C control temperature, allows solution crystallization 18h in a kettle, is tied
The MCM-48 of no removed template method is obtained after the completion of crystalline substance；
5., sample post-processing
, in 550 DEG C of temperature lower calcination 6h, MCM-48 mesopore molecular sieves will be obtained after sample clean, suction filtration, drying.
A kind of 3. Al-Bi-Ce-La mixing and doping MCM-48 mesopore molecular sieve conducts that as claimed in claim 1 or 2 prepared by method
The application of absorption degradation organic dyestuff.
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| CN101199939A (en) * | 2007-12-21 | 2008-06-18 | 中国科学院山西煤炭化学研究所 | Catalyst of methanol and formaldehyde from methane oxidation synthesis and preparation and application thereof |
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| CN101199939A (en) * | 2007-12-21 | 2008-06-18 | 中国科学院山西煤炭化学研究所 | Catalyst of methanol and formaldehyde from methane oxidation synthesis and preparation and application thereof |
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