CN106241827A - A kind of preparation method of Al Bi Ce La mixing and doping MCM 48 mesopore molecular sieve - Google Patents
A kind of preparation method of Al Bi Ce La mixing and doping MCM 48 mesopore molecular sieve Download PDFInfo
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Abstract
The present invention relates to organic dyestuff absorption degradation technical field, be specifically related to the preparation method of a kind of Al Bi Ce La mixing and doping MCM 48 mesopore molecular sieve.MCM 48 mesopore molecular sieve is dispersed in dehydrated alcohol, and mix homogeneously forms solution A, then weighs AlCl3、Ce(NO3)3.6H2O、LaCl3.nH2O and BiCl3Being dispersed in dehydrated alcohol, be slowly dropped in solution A after stirring so that two kinds of solution mixing, and be further continued for stirring, during this, hetero atom adsorbs on the surface of molecular sieve；The most dropwise instill the C solution being made up of dilute hydrochloric acid and dehydrated alcohol, then drip water, continue stirring after hydrolysis completely and guarantee TBOT hydrolysis completely, post processing.Al Bi Ce La mixing and doping MCM 48 mesopore molecular sieve of preparation maintains good absorption degradation, more can reach the effect to colored dyes decolouring very well.
Description
Technical field
The present invention relates to organic dyestuff absorption degradation technical field, be specifically related to a kind of Al-Bi-Ce-La mixing and doping
The preparation method of MCM-48 mesopore molecular sieve.
Background technology
MCM-48 is that a kind of uniform pore diameter is about 2.6nm, the most also has the three-dimensional spiral duct net that two sets are separate
The mesopore molecular sieve of network structure.Structure is Emission in Cubic, and adjustable extent is in the transmission of 2-l0nm, beneficially macromolecular substances.In choosing
The catalysis of selecting property, macromolecules adsorption separation, Industrial Wastewater Treatment, the aspect such as assembling of nanocluster have a extensive future.But pure silicon
MCM-48 mesopore molecular sieve for want of active center, such as acid activity site, active site etc., range is limited to, only
Can carrying can not specifically be catalyzed.Meanwhile, pure silicon MCM-48 acid content is low, and intensity is low, and has less ion-exchange capacity, lacks
Few catalytic oxidation ability；Mesoporous material skeleton connects with the connection of Si-O-Si key-like formula, and its surface is with Si-OH shape
Formula link, these are different with atom connected mode from the atom of micropore, it addition, mesoporous material is indefiniteness structure, and zeolite material
Material has certain crystallographic structure, and therefore be all not so good as micropore with water stability good for catalytic property, and temperature is set as high value, then
Mesoporous material hole wall and be susceptible to hydrolysis, cause Si-O-Si bond fission, structure collapses；In order to extend the mesoporous material of MCM-48
The range of application of material so that mesoporous material occurs to promote largely, scientist is to this primary study of leavening dough, right by attempting
The aperture of mesoporous material is adjusted, modify the skeleton of mesopore molecular sieve, that mesopore molecular sieve is carried out organic and inorganic is miscellaneous
The aspect researchs such as change, find to want the means strengthening mesoporous material performance to enrich.Such as: by some organic groups introduce duct it
In, make organic group (amino, mercaptan etc.) silanization by the technology of grafting so that these organic groups possess more new spy
Point；In duct, introduce metal ion, difference according to demand, convert introducing ion toward different aspects；Organic and inorganic is miscellaneous
Changing also to make the functional group of material can introduce in material so that material has more special performance；Can be with carried heteropoly acid, material
Material surface Bransted acidic site increases.
How to be modified, select which kind of hetero atom and methods to be modified, be problem to be solved.Example
As, directly prepare mesoporous material be doped into simultaneously rare-earth heteroatoms be change MCM-48 performance a kind of simple and effective side
Method.Heteroatomic introduction can improve the performance of pure silicon-based mesoporous molecular sieve from many aspects so that MCM-48 molecular sieve structure
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 seldom
Part activity is strong, and carries out grafting to change its poor performance with active function groups, and therefore people use other hetero atom
Replace pure Si atoms, make hetero atom obtain soda acid or redox center.The metallic atom that hetero atom is mainly introduced, metal from
The introduction in sub-active center is easily destroyed the long-range order of MCM-48, the hetero atom that people the most successfully introduce have Ce, Cr, V,
Al, Fe, Cu, Zr etc..And the material such as bimetallic (Cu-Zn, W-Mn, Ru-Pt), characterize display hetero atom quilt by a series of
Introducing such as active center, heteroatomic introducing makes the hole wall of MCM-48 and duct have a series of modification to change, and repaiies
The MCM-48 mesopore molecular sieve adornd is in photoelectrocatalysis, ion exchange, the removal of heavy metal ion, fixing, organic dirt of fuel
The aspects such as the degraded absorption of dye thing suffer from wide Research Significance.
The method that hetero atom is introduced mesopore molecular sieve has several sides such as doping in situ, grafting and (dipping) method of injection
Method.Doping method is directly to join in mixed liquor by the hetero atom handled well during preparing mesopore molecular sieve in situ,
In the solution, hetero atom predecessor can be with the hydrolytie polycondensation mistake of predecessor the most spontaneous generation silicon source, silicon source predecessor
Journey, then repeats crystallization steps, and the metal ion of final doping method in situ doping enters framework of molecular sieve.Infusion process and grafting
Similar process, both of which is that pure silicon mesopore molecular sieve carries out the process in later stage, and concrete grammar is the MCM-that will prepare
48 mix with heteroatomic precursor liquid under certain conditions, then stir certain time, until complete hydrolysis, centrifugal,
The operations such as washing, dry, high-temperature calcination, obtain modified MC M-48；And grafting difference is that be suitable for 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, prepares modified molecular screen through washing, drying and other steps the most again.The infusion process heteroatomic advantage of doping is metal
The content that ion mixes skeleton is higher than doping in situ, but the most several knot being highly vulnerable to breakage MCM-48 of too high tenor
Structure, so the doping method for different selecting response is different.
Summary of the invention
The purpose of the present invention is to propose to the preparation method of a kind of Al-Bi-Ce-La mixing and doping MCM-48 mesopore molecular sieve,
To overcome the drawbacks described above of prior art.
For realizing this purpose, present invention employs techniques below scheme:
The preparation method of a kind of Al-Bi-Ce-La mixing and doping MCM-48 mesopore molecular sieve, uses infusion process, weighs 0.4g
MCM-48 mesopore molecular sieve be dispersed in the beaker of the dehydrated alcohol filling 35mL, formed solution A, stirring 30min to solution
It is mixed thoroughly；Weigh the AlCl of 0.2g again3, the Ce (NO of 0.6g3)3.6H2The LaCl of O, 0.5g3.nH2O's and 0.64g
BiCl3It is dispersed in 15mL dehydrated alcohol, is slowly dropped to after stirring in solution A so that two kinds of solution mixing, and again
Continuing stirring 1h, during this, hetero atom adsorbs on the surface of molecular sieve；The most dropwise instill by the dilute hydrochloric acid of 5mL 0.5M
The C solution formed with the dehydrated alcohol of 10mL, is stirred for 2h, then dropping 10mL water, continues stirring 2h and guarantee after hydrolysis completely
TBOT hydrolysis is completely, centrifugal, is washed with deionized water, and 100 DEG C are dried, 500 DEG C of calcining 4h, and natural cooling obtains Al-after grinding
Bi-Ce-La mixing and doping MCM-48 mesopore molecular sieve.
As optimal technical scheme, the preparation method of described MCM-48 mesopore molecular sieve is:
1. it is, with CTAB single template, the homogeneous solution of preparation cation template
Weighing 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 particle is completely dissolved；
2. the pH of cation template solution, is regulated
According to volume ratio ammonia: dehydrated alcohol=13.2:66.7 prepares mixed solution, is added into cation template
Homogeneous solution continues stirring, until after two kinds of solution mix homogeneously, now the pH of solution reaches neutral or alkaline；
3., inorganic silicon source is added so that it is with organic formwork agent polycondensation
Being slowly added dropwise silester (TEOS) in solution after regulating pH, this process reaction time is 1-2h, and
It is always maintained at stirring, template and silicon source so could be allowed to react complete；
4., the most molten for reaction colloidal solution is shifted and crystallizes
Being moved in reactor by colloidal solution mixed solution, controlling temperature is 120 DEG C, allows solution crystallization in a kettle.
18h, obtains the MCM-48 not having removed template method after having crystallized；
5., the sample later stage processes
By sample clean, sucking filtration, dried at 550 DEG C of temperature lower calcination 6h, obtain MCM-48 mesopore molecular sieve.
Beneficial effects of the present invention shows:
The preparation method that the present invention selects is to improve on the basis of doping method in position, and doping method is in preparation in situ
Directly the hetero atom handled well is joined in mixed liquor during mesopore molecular sieve, in the solution, hetero atom predecessor
Crystallization steps can be then repeated with the hydrolytie polycondensation process of predecessor the most spontaneous generation silicon source, silicon source predecessor,
The metal ion of final doping method in situ doping enters framework of molecular sieve, and replaces Si and become Si-O-M from Si-O-Si (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, eventually pass and wash
Wash, be dried, the step such as calcining obtains the modified MCM-48 product crossed.In this, method is the most simple and convenient, and hetero atom is easy
Enter the skeleton of molecular sieve, and the molecular sieve functional diversities after modification, and when the active component energy entered that adulterates is long
Effectively preserve, and substantially increase the activity in some performance so that some action effect of molecular sieve is more preferable.Shortcoming
It is that, when hetero atom produces the biggest with the structural parameters of pure Si atoms when, heteroatomic doping can destroy original molecular sieve
Skeleton, synthesis condition is the harshest, and heteroatomic content may be relatively low.
Al-Bi-Ce-La mixing and doping MCM-48 mesopore molecular sieve prepared by the present invention maintains good absorption degradation
Property, more can reach the effect to colored dyes decolouring very well.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the target product of embodiment 2 preparation.
Fig. 2 is the XRD figure of the target product of embodiment 3 preparation.
Fig. 3 is the XRD figure of the target product of embodiment 4 preparation.
Fig. 4 is the XRD figure of the target product of embodiment 5 preparation.
Fig. 5 is the XRD figure of the target product of embodiment 1 preparation.
Fig. 6 is the SEM figure of four kinds of different multiplying of the target product of embodiment 2 preparation.
Fig. 7 is the SEM figure of four kinds of different multiplying of the target product of embodiment 3 preparation.
Fig. 8 is the SEM figure of four kinds of different multiplying of the target product of embodiment 4 preparation.
Fig. 9 is the SEM figure of four kinds of different multiplying of the target product of embodiment 5 preparation.
Figure 10 is the SEM figure of two kinds of different multiplying of the target product of embodiment 1 preparation.
Figure 11 is the N2 adsorption desorption curve figure of the target product of embodiment 1 preparation.
Figure 12 is the thermogravimetric curve figure of the target product of embodiment 2 preparation.
Figure 13 is the thermogravimetric curve figure of the target product of embodiment 3 preparation.
Figure 14 is the thermogravimetric curve figure of the target product of embodiment 4 preparation.
Figure 15 is the thermogravimetric curve figure of the target product of embodiment 5 preparation.
Figure 16 is the thermogravimetric curve figure of the target product of embodiment 1 preparation.
Figure 17 is the infrared spectrogram of target product prepared by embodiment 2-5.
Figure 18 is the infrared spectrogram of the target product of embodiment 1 preparation.
Figure 19 is the methylene blue solution absorption degradation curve of target product prepared by embodiment 1-5.
Detailed description of the invention
The one of the present invention is further described for Al-Bi-Ce-La mixing and doping below by way of specific embodiment
The preparation method of MCM-48 mesopore molecular sieve.
One, preparation embodiment
Embodiment 1
1, the preparation of MCM-48 mesopore molecular sieve:
1. it is, with CTAB single template, the homogeneous solution of preparation cation template
Weighing 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 particle is completely dissolved.
2. the pH of cation template solution, is regulated
According to volume ratio ammonia: dehydrated alcohol=13.2:66.7 prepares mixed solution, is added into cation template
Homogeneous solution continues stirring, until after two kinds of solution mix homogeneously, now the pH of solution reaches neutral or alkaline.
3., inorganic silicon source is added so that it is with organic formwork agent polycondensation
Being slowly added dropwise silester (TEOS) in solution after regulating pH, this process reaction time is 1-2h, and
It is always maintained at stirring, template and silicon source so could be allowed to react complete.
4., the most molten for reaction colloidal solution is shifted and crystallizes
Being moved in reactor by colloidal solution mixed solution, controlling temperature is 120 DEG C, allows solution crystallization in a kettle.
18h, obtains the MCM-48 not having removed template method after having crystallized.
5., the sample later stage processes
By sample clean, sucking filtration, dried at 550 DEG C of temperature lower calcination 6h, obtain MCM-48 mesopore molecular sieve.
2, the preparation of Al-Bi-Ce-La mixing and doping MCM-48 mesopore molecular sieve:
The MCM-48 mesopore molecular sieve weighing 0.4g is dispersed in the beaker of the dehydrated alcohol filling 35mL, forms solution A,
Stirring 30min is mixed thoroughly to solution.Weigh the AlCl of 0.2g again3, the Ce (NO of 0.6g3)3.6H2O, 0.5g's
LaCl3.nH2The BiCl of O and 0.64g3It is dispersed in 15mL dehydrated alcohol, is slowly dropped to after stirring in solution A so that
Two kinds of solution mixing, and be further continued for stirring 1h, during this, hetero atom adsorbs on the surface of molecular sieve.The most dropwise instill
The C solution being made up of the dilute hydrochloric acid of 5mL 0.5M and the dehydrated alcohol of 10mL, is stirred for 2h, and then dropping 10mL water, has hydrolyzed
Continue stirring 2h after complete and guarantee TBOT hydrolysis completely, centrifugal, it is washed with deionized water three times, 100 DEG C are dried, 500 DEG C of calcining 4h, from
So cooling, obtains Al-Bi-Ce-La mixing and doping MCM-48 mesopore molecular sieve after grinding.
Embodiment 2
The preparation of Al doping MCM-48 mesopore molecular sieve:
The MCM-48 mesopore molecular sieve weighing 0.4g is dispersed in the beaker of the dehydrated alcohol filling 35mL, forms solution A,
Stirring 30min is mixed thoroughly to solution；Weigh the AlCl of 0.7g again3It is dispersed in 15mL dehydrated alcohol, after stirring
Being slowly dropped in solution A so that two kinds of solution mixing, and be further continued for stirring 1h, during this, hetero atom absorption is dividing
The surface of son sieve；The most dropwise instill the C solution that the dehydrated alcohol of the dilute hydrochloric acid by 5mL 0.5M and 10mL forms, be stirred for
2h, then dropping 10mL water, continue stirring 2h and guarantee TBOT hydrolysis completely after hydrolysis completely, centrifugal, is washed with deionized water three times,
100 DEG C are dried, 500 DEG C of calcining 4h, and natural cooling obtains Al doping MCM-48 mesopore molecular sieve after grinding.
Embodiment 3
The preparation of Bi doping MCM-48 mesopore molecular sieve:
The MCM-48 mesopore molecular sieve weighing 0.4g is dispersed in the beaker of the dehydrated alcohol filling 35mL, forms solution A,
Stirring 30min is mixed thoroughly to solution；Weigh the BiCl of 2.55g again3It is dispersed in 15mL dehydrated alcohol, after stirring
Being slowly dropped in solution A so that two kinds of solution mixing, and be further continued for stirring 1h, during this, hetero atom absorption is dividing
The surface of son sieve；The most dropwise instill the C solution that the dehydrated alcohol of the dilute hydrochloric acid by 5mL 0.5M and 10mL forms, be stirred for
2h, then dropping 10mL water, continue stirring 2h and guarantee TBOT hydrolysis completely after hydrolysis completely, centrifugal, is washed with deionized water three times,
100 DEG C are dried, 500 DEG C of calcining 4h, and natural cooling obtains Bi doping MCM-48 mesopore molecular sieve after grinding.
Embodiment 4
The preparation of Ce doping MCM-48 mesopore molecular sieve:
The MCM-48 mesopore molecular sieve weighing 0.4g is dispersed in the beaker of the dehydrated alcohol filling 35mL, forms solution A,
Stirring 30min is mixed thoroughly to solution；Weigh the Ce (NO of 2.3g again3)3.6H2The LaCl of O, 0.5g3.nH2O's and 0.64g
BiCl3It is dispersed in 15mL dehydrated alcohol, is slowly dropped to after stirring in solution A so that two kinds of solution mixing, and again
Continuing stirring 1h, during this, hetero atom adsorbs on the surface of molecular sieve；The most dropwise instill by the dilute hydrochloric acid of 5mL 0.5M
The C solution formed with the dehydrated alcohol of 10mL, is stirred for 2h, then dropping 10mL water, continues stirring 2h and guarantee after hydrolysis completely
TBOT hydrolysis is completely, centrifugal, is washed with deionized water three times, and 100 DEG C are dried, 500 DEG C of calcining 4h, and natural cooling obtains after grinding
Ce adulterates MCM-48 mesopore molecular sieve.
Embodiment 5
The preparation of La doping MCM-48 mesopore molecular sieve:
The MCM-48 mesopore molecular sieve weighing 0.4g is dispersed in the beaker of the dehydrated alcohol filling 35mL, forms solution A,
Stirring 30min is mixed thoroughly to solution；Weigh the LaCl of 1.9g again3.nH2The BiCl of O and 0.64g3It is dispersed in 15mL anhydrous
In ethanol, it is slowly dropped to after stirring in solution A so that two kinds of solution mixing, and is further continued for stirring 1h, this process
Middle hetero atom adsorbs on the surface of molecular sieve；The dehydrated alcohol the most dropwise instilling the dilute hydrochloric acid by 5mL 0.5M and 10mL forms
C solution, be stirred for 2h, then dropping 10mL water, continue stirring 2h after hydrolysis completely and guarantee TBOT hydrolysis completely, centrifugal, use
Deionization is washed three times, and 100 DEG C are dried, 500 DEG C of calcining 4h, and natural cooling obtains La doping MCM-48 mesoporous molecular after grinding
Sieve.
Two, the sign of doped samples
1, X-ray diffraction (XRD) is analyzed
Fig. 1 is the XRD figure of the target product of embodiment 2 preparation.Because the angle of this experiment test is relatively big, so by figure
From the point of view of shape, can only see at 2 θ=one the most sharp-pointed but wide peak of 21-22 ° of appearance, this peak is that MCM-48 is under wide-angle
Characteristic peak, illustrate that heteroatomic doping maintains the pore passage structure that MCM-48 mesoporous material is original, and this peak be more
Sharply, being because orderly cubic structure degree of crystallinity big, Another reason is that after hetero atom mixes, the intensity at peak is overlapped mutually；
List of references understands, with standard MCM-48 at 2 θ=21-22 ° of peak gone out compared with, after adulterated al ion, peak becomes strong, illustrates
This ion has had a certain amount of being entrained in skeleton, result in the enhancing at peak；An Al is had time additionally about 2 θ=40 °2O3
Characteristic peak, and relatively strong, illustrate that more silicon ion is substituted by aluminium ion on skeleton.
Fig. 2 is the XRD figure of the target product of embodiment 3 preparation.Can analyze from figure in 2 θ=21-22 ° of appearance one
Individual more sharp-pointed but SiO that intensity is the highest2Characteristic peak, illustrate that the doping of bismuth ion also maintains the hole that mesoporous material is original
Road structure, degree of crystallinity is good not as the aluminum ions mesoporous material that adulterates, and this intensity is poor with standard MCM-48 feature steamed bread peak
Seldom, it is impossible to know bismuth ion and be the most successfully doped in skeleton.But after experimental analysis understands in 2 θ=25 °, occur
The crystal face peak of multiple bismuth oxide, illustrates that the bismuth ion amount successfully adulterated is less.
Fig. 3 is the XRD figure of the target product of embodiment 4 preparation.It can be seen that 2 θ=21-22 ° of characteristic peak is with many
The peak containing cerium oxide planting form is the strongest, illustrates that material modified degree of crystallinity is high, and cerium replaces silicon ion in a large number simultaneously, miscellaneous
Random strong peak is overlapped mutually after also illustrating to be probably incorporation hetero atom.But it is more by occurring after 2 θ > 30 ° knowable to analysis
SiO2Characteristic peak, illustrates that the undefined structure of hole wall keeps complete, does not destroy.
Fig. 4 is the XRD figure of the target product of embodiment 5 preparation.Stronger spreading out of intensity is occurred in that in 2 θ=11.95 °
Penetrate peak, in 2 θ=21.38 °, a wider diffraction maximum occurs, illustrate that sample crystallinity is the highest, and long-range order keeps good
Good, hetero atom is the most successfully doped in skeleton, improves the stability of modified molecular screen.
Fig. 5 is the XRD figure of the target product of embodiment 1 preparation.Can find out that several metal is common with rare earth element by figure
Mesoporous point of MCM-48 after doping vario-property still maintains good pore passage structure from sieve, but crystallization degree is not as single doping shape
Formula is good, has also detected that the oxide containing each metal ion species and Si oxide in figure, so explanation doping is respond well.
2, sem analysis
Fig. 6 is the SEM figure of four kinds of different multiplying of the target product of embodiment 2 preparation.Can be seen that adulterated al is modified
The shape of MCM-48 regular, without phenomenon of rupture, illustrate that the Al-MCM-48 of modification maintains good meso-hole structure.Its profile
SEM figure is similar to bar-shaped, illustrates that grain shape is uniform.And by (a) it can also be seen that, have one between granule and granule relatively
Big space, this is by studying the Al-MCM-48 adsorptivity discovery to methylene blue, and its absorption property is fine, thus it is speculated that these
Uniform space serves preferably effect；Find out that the doping of Al ion makes crystal grain reunion degree high secondly by (c), (d) figure,
It is uniformly dispersed, also can prove that with reference to its XRD figure, this is because during synthesis MCM-48 mesopore molecular sieve, dripping of silicon source
Acceleration is controlled preferably so that the amount reunited together in silicon source is moderate, so mesopore molecular sieve is of moderate size.Secondly molecular sieve phase
Interweaving mutually, uniform particle sizes is about about 0.5 μm, and grain diameter is moderate, and illustrative material maintains the aperture response of mesoporous material.
Fig. 7 is the SEM figure of four kinds of different multiplying of the target product of embodiment 3 preparation.It can be seen that the size of granule is not
Being visibly homogeneous, aperture, between 0.5-1 μm, illustrates that hole is relatively big, and hetero atom mixes may be on extension impact.Secondly by figure
A () (b) can find out that granule is rounded, have the tendency of reunion between partial particulate, be distributed with crystallization situation be all not so good as adulterated al it
After uniform.
Fig. 8 is the SEM figure of four kinds of different multiplying of the target product of embodiment 4 preparation.Can be seen that its granule is uniform, and
And occurring in that serious agglomeration, particle surface is rough, occurs that the reason of this situation is probably the dropping of silicon source too much, shape
The material become occurs the compound of the more siliceous and cerium of kind, it is also possible to be because in Sample Preparation Procedure not washing dry
Only, impurity occurs, but according to major part 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 figure of four kinds of different multiplying of the target product of embodiment 5 preparation.Can be seen that crystallization effect is not
Very well, but grain shape is the most uniform, rounded, has agglomeration between partial particulate, it may be possible to because silicon source dropping speed
Spend fast, formed and pile up.Granule pore size is similar with pure MCM-48, maintains MCM-48 original after doping hetero atom is described
Structure.
Figure 10 is the SEM figure of two kinds of different multiplying of the target product of embodiment 1 preparation.It can be seen that the profile of granule
Have a very large change, similar wooden dipper shape, in conjunction with the application of Al-Bi-Ce-La-MCM-48 it can be seen that this wooden dipper shape structure can
To be effectively adsorbed with organic dye, the reason author that in this, shape causes wants that being probably hetero atom enters in duct, destroys material
The hole wall structure of material.And particle diameter is about 0.8 μm, illustrate that hetero atom makes mesoporous material diauxic growth.Meanwhile, from figure
In it can also be seen that the degree of crystallinity of granule is high.
3, BET analyzes
Figure 11 is the N2 adsorption desorption curve figure of the target product of embodiment 1 preparation.Found out that adsorption isotherm belongs to by figure
IV kind, so the Al-Bi-Ce-La-MCM-48 of gained has preferable meso-hole structure, is found out first stage relative pressure by figure
Smaller area (P/P0=0.05-0.4) adsorption isothermal curve projection is upwards；Second stage is at relative pressure upper zone (P/P0=
0.4-0.98), isothermal curve increases rapidly, and reason is the coacervation that adsorbate in this process creates capillary tube, because of
For there being the coacervation of capillary tube, this stage is it can be seen that desorption curve is misaligned with adsorption curve, and desorption curve exists
The hysteresis produced above adsorption curve, the most clearly hysteresis loop, the generation producing hysteresis is
Because the size and shape in hole is different, the position P/P in the drawings of aperture cohesion0The ground of the beginning of=0.4 position, i.e. hysteresis loop
Side, the position that maximum pore condenses completely is at P/P0=098, i.e. the final position of hysteresis loop, coagulation liquid is filled full whole
The various piece of system, in figure, entirety finds out that low pressure hysteresis loop is less, illustrates that samples long-range order slightly reduces, and this can
Can be because crystallization time long cause crystallization dissolve.Phase III (P/P0=0.98-1) when all apertures of adsorbate complete to coagulate
After Ju, the outer surface generation adsorption phenomena of granule, although the area of outer surface is much smaller than inner surface, but the absorption of this section of process
Make isothermal curve at P/P0In=0.9-0.98 region on the rise, curve close to 1 place the most precipitous on
Rising, be because adsorbance and be increased dramatically, the reason causing this phenomenon is that macroporous absorption starts.Understood modified by analysis
MCM-48 specific surface area is 105.179m2/ g, aperture is 15.345nm, and specific surface area reduces, and aperture also reduces, and this is probably crystalline substance
Changing overlong time, cause dissolution of crystals, or dopant ion is more, ratio is bad, destroys the pore passage structure of sample, from
SEM it can also be seen that, the appearance of mixed and modified MCM-48 changes, and similar splitting recrystallizes again.
4, TG analyzes
Thermogravimetric analysis is that a kind of material mass of studying varies with temperature the analysis means of relation, and main operational principle is to work as thing
Matter its quality in thermal histories can change, and causes the reason of change to have many-side, such as: nature series of physical chemistry
Change, it can be common that the vaporization of material, distillation, the loss of water of crystallization, decomposition etc., it is simply that the abscissa of thermogravimetric curve represents temperature
Degree, corresponding vertical coordinate 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 the target product of embodiment 2 preparation.Find out Al-MCM-48 in TG figure initial point
Solve temperature be 25 DEG C, tend to balance after 550 DEG C, material do not continue to decompose, from DTA graph discovery at 45 DEG C time occur in that one
Sharp-pointed peak, this positional representation sample has exothermic reaction to occur in this temperature, can calculate Al-MCM-48 sample from TG figure
Product weight-loss ratio, i.e. Δ W%=W0%-WEnd%=99.01%-82.82%=16.9%；Visible undecomposed impurity remains
Amount is 83.1%, and undecomposed amount is bigger.Find out that Al-MCM-48 the most substantially goes out peak, T=when T=45 DEG C by DTA figure
215 DEG C the most weak go out peak, go out each time peak correspondence TG curve weight change.T=45 DEG C go out peak main cause be because of
For in sample moisture scatter and disappear.The topmost reason in peak produced when T=215 DEG C is 1. prepared organic-inorganic material
Machine template does not removes totally, molecular chain rupture will occur again, finally with CO at this temperature2、H2The small-molecule substances such as O will
Disperse.In 150-250 DEG C of interval, there is Hoffmann decomposition, C in CTAB16H33(CH2)3N+→C16H32+N(CH3)3+H+Hereafter,
C16H32Because boiling point is at 157 DEG C, burning-point 240 DEG C, therefore continues to rise according to temperature, C16H32Continue fracture to decompose, N (CH3)3
Burning-point 190 DEG C, therefore along with the increase of temperature, N (CH3)3The gases such as burned generation, at about 215 DEG C, organic formwork agent quilt
Decompose about 50%.2. and in the process between inorganic silicon source and aluminum source, also small part generation polycondensation forms Si-O-Al key, and
Surface be reaction Si-OH dehydrating polycondensation be Si-O-Si key.3. a small amount of aluminium hydroxide or other complex that produce in solution exist
This generates aluminium oxide less than 200 DEG C of dehydrations.
Figure 13 is the thermogravimetric curve figure of the target product of embodiment 3 preparation.Can be seen that sample 20 DEG C-590 DEG C decomposition,
Weight-loss ratio Δ W%=W0%-WEnd%=100%-88.55%=11.45%, finds out obvious two peaks, at T on DTA figure
When=50 DEG C occur a sharp-pointed peak, illustrate have exothermic reaction to occur at this temperature, reason be moisture at this temperature
A large amount of scattering and disappearing, template CTAB ruptures the molecule C16H32Portion fractures at this temperature, generates less molecule.At T=
160 DEG C there is a more weak peak, and reason is probably organic-inorganic material and the most once carried out hydrothermal treatment consists with ammonia
Cross, when 100-160 DEG C in structure the halogen ion of intermediate medium electric charge and ammonium ion with NH4The form of X removes.
Figure 14 is the thermogravimetric curve figure of the target product of embodiment 4 preparation.Can be seen that sample decomposition temperature interval is 25
DEG C-500 DEG C, DTG curve has twice peak the most sharp-pointed, and T=50 DEG C goes out peak reason and above two metal ion mixing reason
Identical, mainly moisture is lost, and the T=195 DEG C of reason going out peak is primarily threefold: 1. do not remove clean CTAB template
The fracture of agent；2. silicon source and cerium are derived from main dress polycondensation dehydration and form key, do not react polycondensation between silicon source completely；3. add
Cerium source (cerous nitrate) can form cerium hydroxide at 50 DEG C-200 DEG C in the basic conditions, forms cerium oxide after calcining.
Figure 15 is the thermogravimetric curve figure of the target product of embodiment 5 preparation.Can be seen that sample decomposition temperature interval is 25
DEG C-590 DEG C, DTG curve has twice peak the most sharp-pointed, and T=50 DEG C goes out peak reason and above two metal ion mixing reason
Identical, mainly moisture is lost, and the T=360 DEG C of reason going out peak is probably the fracture not removing CTAB template thoroughly, raw
The C become16H32Burning generates CO2、H2The little molecule such as O, and N (CH3)3Burning generates CO2、H2O、NO、NO2Several little molecules.
Figure 16 is the thermogravimetric curve figure of the target product of embodiment 1 preparation.Can be seen that sample decomposition temperature 25 DEG C-
Between 590 DEG C and similar with monometallic ion doping weight-loss ratio, within 20%, except for the difference that monometallic ion doping is only
Having twice and go out peak, and the doping of four kinds of combining forms makes the DTA curve of sample have three times to go out peak, this goes out the reason at peak more three times
Comprehensively, T=45 DEG C there is more sharp-pointed peak, because moisture scattered and disappeared in a large number in this stage；T=155 DEG C there is more weak peak, reason
Be the template removed the most completely just this stage fracture burning, with little molecular forms scatter and disappear；Small part unreacted silicon source and its
He is dehydrated in source metal generation polycondensation；Ammonia be used in an experiment processing organic-inorganic material, after the final impurity produced with
NH4The form of X removes；T=290 DEG C there is more weak peak, and main cause is not remove clean template to continue decomposition combustion；
The decomposeds such as Organic substance dehydrated alcohol；The easy complex of some metal ion generation during synthesis, but major part meeting
Exist with hydroxide form, regardless of existence form, the most at high temperature can become oxide by kinetics.
5, FT-IR analyzes
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 to go out peak on infrared spectrum more, and before the infrared spectrum after adulterating and non-undoped p
Similar, substantially can represent the functional group of complete sample and the information of chemical bond.At 3410cm-1There is a suction wider relatively by force in place
Receiving peak, this is typical by ≡ Si (OH) ,=Si (OH)2、-Si(OH)3Form absworption peak Deng silicone hydroxyl key chattering, illustrate
The silicone hydroxyl key on the surface of sample is a lot.And hydroxyl concentration is relatively big, just increasing intermolecular hydrogen bonding, absworption peak now just broadens
Can be widened, but the appearance of characteristic peak that the absworption peak of this position is skeleton is the most just illustrated that the interpolation of metal ion is preferable
Maintain MCM-48 original silicon framing structure.Two can be clearly apparent by-CH in sample infrared spectrogram simultaneously3Or-
CH2-the weak peak that causes of antisymmetric stretching vibration.At 3100cm-1Being one, wave number is at 2930cm-1It it is again one.?
2030cm-1There is a absworption peak the most weak in place, and reason is a small amount of=Si (OH)2At 1540cm-1And 1620cm-1Peak very
Sharply, and compare figure and find out that every kind of sample all goes out peak at this, this is because sample exists Bronsted (1540-
1630cm-1) sour and Lewis (1450-1620cm-1) acid, and can find out that the L acid that makes of the doping of a few metal ion species compares B-acid
Acid amount many, contrast the spectrogram after several ion doping, find that the L acid acidity amount of Bi-MCM-48 is maximum.And B-acid is acid
Amount is almost.At 1090cm-1There is strong and sharp-pointed peak in place, and the silicon-oxy tetrahedron Si-O-Si key antisymmetry of reason skeleton is stretched
Vibration can be vibrated, the sharp-pointed peak of formation, and in the case of wavelength is relatively big, silicon-oxy tetrahedron can occur symmetrical stretching to shake
Dynamic, form the 856cm in figure-1Peak, place；At 417cm-1The peak of left and right is to cause owing to the bending vibration of Si-O-Si absorbs, from
Figure can be seen that 856cm-1With 417cm-1The peak at place is different with doping metals varying strength, wherein La-MCM-48 maximum intensity,
Bi-MCM-48 is the most weak, and inspection information understands compared with pure MCM-48, and two absorption peak strength all have reducing tendency, it may be possible to because of
Mix in skeleton for metallic atom, instead of mono-silicon of Si-O-Si, form Si-O-R (R refers to Al, Bi, Ce, La) ion, thus
Result in intensity to reduce.At 1495cm-1、2854cm-1、2924cm-1There is no obvious c h bond shuttle belt Deng position, illustrate mould
Plate agent is eliminated the cleanest, has analyzed in thermogravimetric analysis.
Figure 18 is the infrared spectrogram of the target product of embodiment 1 preparation.It is seen that 856cm-1There is typical case in place
Peak, this be under bigger wavelength silicon-oxy tetrahedron symmetrical stretching vibration form seen from be no matter single doping or mixing and doping all
There will be this type of peak.At 1087cm-1There is strong and sharp-pointed peak in place, this is because silicon-oxy tetrahedron Si-O-Si key antisymmetry is stretched
Contracting vibration, illustrates that the doping of multiple rare earth element and metal ion maintains the framing structure of original MCM-48,1219cm-1Go out
An existing more weak peak is because what C-O key stretching vibration was formed, 1415cm-1Occur in stronger and sharp-pointed peak explanation sample
Containing Lewis (1450-1620cm-1) acid, and Lewis acid acidity amount is the biggest.
Three, absorption degradation experiment
Prepare 10 test tubes (2 test tubes of every kind of sample), be added with into 8ml methylene blue solution to every test tube counterpoise,
The PH of methylene blue solution is modulated to 7, and concentration is 6mg/L, weighs 5 kinds of samples after modification with electronic balance the most again,
Every kind of sample precisely claims 0.04g, and is added in ready methylene blue solution by sample, waits sample to submerge after in solution with can
See illumination irradiate test tube, this experimental selection is strong sunlight, static, each time interval is 15min, 30min,
Respectively to the sample in five test tubes when 45min, 1h, every kind of solution takes 4ml, proceeds in centrifuge tube by the sample of acquirement,
Regulation centrifuge, revolution is 4000r/min, and the time is 5min.Take the supernatant of the solution being centrifuged, be then transferred into visible point
In the photometric cuvette of light, the absorbance of the methylene blue surveyed all surveys (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.Can be seen by curve
Going out, the degradability of 5 kinds of samples is all fine, and percent of decolourization is the highest, and minimum percent of decolourization reaches about 82%, can reach 98% left
Right；Secondly totally can be seen that no matter modified MCM-48 is the doping of monometallic form or four kinds of metal co-dopeds, inhale
Attached degradation speed is the most quickly, the most degradable in 150min.Except for the difference that through the MCM-48 of different metal ion modification
Its absorption degradation effect is different, and shown in figure, Ce-MCM-48 percent of decolourization at the beginning is the highest, through the illumination of 150min
Rear decoloring rate remains unchanged the highest, illustrates that its effect is best, in how metal-doped Al-Bi-Ce-La-MCM-48 finds out the whole time
Percent of decolourization all compares between two parties.Above content analysis substantially can illustrate each not phase of the adsorbent effect after different metal doping
With.
It is pointed out that the present invention is not limited only to embodiment listed above, every can be direct from present invention
Derive or the enlightenment conceivable correlation technique of connection all should belong to the present invention and contain the scope of protection.
Claims (3)
1. a preparation method for Al-Bi-Ce-La mixing and doping MCM-48 mesopore molecular sieve, uses infusion process, and its feature exists
In, the MCM-48 mesopore molecular sieve weighing 0.4g is dispersed in the beaker of the dehydrated alcohol filling 35mL, forms solution A, stirring
30min is mixed thoroughly to solution；Weigh the AlCl of 0.2g again3, the Ce (NO of 0.6g3)3.6H2The LaCl of O, 0.5g3.nH2O
BiCl with 0.64g3It is dispersed in 15mL dehydrated alcohol, is slowly dropped to after stirring in solution A so that two kinds of solution mix
Closing, and be further continued for stirring 1h, during this, hetero atom adsorbs on the surface of molecular sieve；The most dropwise instill by 5mL 0.5M
Dilute hydrochloric acid and the C solution of dehydrated alcohol composition of 10mL, be stirred for 2h, then dropping 10mL water, continue to stir after hydrolysis completely
Mix 2h and guarantee TBOT hydrolysis completely, centrifugal, it is washed with deionized water, 100 DEG C are dried, and 500 DEG C of calcining 4h, natural cooling, after grinding
Obtain Al-Bi-Ce-La mixing and doping MCM-48 mesopore molecular sieve.
2. preparation method as claimed in claim 1, it is characterised in that the preparation method of described MCM-48 mesopore molecular sieve is:
1. it is, with CTAB single template, the homogeneous solution of preparation cation template
Weighing 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 particle is completely dissolved；
2. the pH of cation template solution, is regulated
According to volume ratio ammonia: dehydrated alcohol=13.2:66.7 prepares mixed solution, is added into the uniform of cation template
Solution continues stirring, until after two kinds of solution mix homogeneously, now the pH of solution reaches neutral or alkaline；
3., inorganic silicon source is added so that it is with organic formwork agent polycondensation
Being slowly added dropwise silester (TEOS) in solution after regulating pH, this process reaction time is 1-2h, and always
It is kept stirring for state, template and silicon source so could be allowed to react complete；
4., the most molten for reaction colloidal solution is shifted and crystallizes
Being moved in reactor by colloidal solution mixed solution, controlling temperature is 120 DEG C, allows solution crystallization 18h in a kettle., knot
Crystalline substance obtains the MCM-48 not having removed template method after completing；
5., the sample later stage processes
By sample clean, sucking filtration, dried at 550 DEG C of temperature lower calcination 6h, obtain MCM-48 mesopore molecular sieve.
3. the Al-Bi-Ce-La mixing and doping MCM-48 mesopore molecular sieve conduct that prepared by a method as claimed in claim 1 or 2
The application of absorption degradation organic dyestuff.
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| US5209838A (en) * | 1991-10-07 | 1993-05-11 | Aluminum Company Of America | Purification of an oil-containing liquid using a surface treated permeable inorganic membrane |
| US20070297975A1 (en) * | 2006-06-23 | 2007-12-27 | Janssen Marcel J | Metal loading of molecular sieves using organic carriers with limited water content |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5209838A (en) * | 1991-10-07 | 1993-05-11 | Aluminum Company Of America | Purification of an oil-containing liquid using a surface treated permeable inorganic membrane |
| US20070297975A1 (en) * | 2006-06-23 | 2007-12-27 | Janssen Marcel J | Metal loading of molecular sieves using organic carriers with limited water content |
| 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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| CN111097384A (en) * | 2019-12-16 | 2020-05-05 | 合肥学院 | C-Bi2O3-CuO-ZnO adsorption material and preparation method and application thereof |
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Effective date of registration: 20201203 Address after: Taihu County, Anhui city of Anqing Province Jin Xi Zhen 246400 Patentee after: Taihu County market supervision and Inspection Institute (Taihu County functional membrane Testing Institute) Address before: 230601 No. 99 Jinxiu Avenue, Hefei economic and Technological Development Zone, Anhui, China Patentee before: HEFEI University |