CN109368653A - A kind of pair of mesoporous Co-TUD-1 molecular sieve and preparation method thereof - Google Patents
A kind of pair of mesoporous Co-TUD-1 molecular sieve and preparation method thereof Download PDFInfo
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- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/005—Silicates, i.e. so-called metallosilicalites or metallozeosilites
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
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- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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Abstract
The present invention discloses a kind of pair of mesoporous Co-TUD-1 molecular sieve and preparation method thereof, wherein double mesoporous Co-TUD-1 molecular sieves have double meso-hole structures: small mesoporous and mesoporous greatly, small mesoporous aperture is in 7 ~ 8nm, and big mesoporous aperture is in 12 ~ 13nm.Double mesoporous Co-TUD-1 molecular sieve silicon hole diameter narrowly distributing, large specific surface area of the present invention, the Co of high degree of dispersion on carrier2+And its double mesoporous design features make Co-TUD-1 molecular sieve become a kind of nano catalytic material having great potential.
Description
Technical field
The present invention relates to the technical fields of support type oxidation catalyst, more particularly to a kind of double mesoporous Co-TUD-1 molecular sieves
And preparation method thereof.
Background technique
Double-mesoporous material is a kind of novel porous materials to grow up on the basis of mesopore molecular sieve in recent years.It is this
There are the meso-hole structures of two kinds of different pore sizes for material, and the big mesoporous molecule that can permit larger size enters, as mass transfer
Channel, have lesser diffusional resistance；The place of small mesoporous absorption point and reaction as substance, has preferably shape-selective urge
Change ability.This feature of double-mesoporous material makes it in petrochemical industry, fine chemistry industry, the life of pharmaceuticals industry and extraordinary polymeric material
Produce etc. has huge development potentiality.At present people for the research of double-mesoporous material also in the stage that is initial, groping,
Although people have been prepared under given conditions by adjusting or the parameter of the traditional mesoporous material preparation system of change with double
The material of pore size distribution feature, but the spatial distribution of two kinds of mesoporous pore structures and hole how is efficiently controlled, and how to be modified
To expand its application field or problem to be solved.In addition to this, double-mesoporous material synthesis is generally high using a large amount of prices
Expensive surfactant is template, substantially increases cost, preparation condition is also relatively harsh, these factors are largely made
About prospect of the double mesopore molecular sieve in practical application.
TUD-1 molecular sieve is a kind of representative one of Novel Mesoporous molecular sieve, because it is with synthesis condition temperature
With it is at low cost the advantages that, make it heterogeneous catalysis field have potential application prospect.TUD-1 framework of molecular sieve is by Si and O group
At there is inertia to most of reactions, therefore transition metal need to be introduced in its duct as active component.M-TUD-1(M is
Single metal or various metals) most common method be hydrothermal synthesis (DHT) method of precursor is directly added into rubber polymer, but this
The shortcomings that method is that the relatively multiple active components introduced can destroy the structure of molecular sieve, and reduce the dispersion degree of active component.Using
Active component can also be carried in TUD-1 molecular sieve by infusion process, but this method cannot ensure that active component is uniformly loaded
Into the duct of molecular sieve.Although existing Co-TUD-1 is list in addition, existing document reporting to Co-TUD-1
Mesoporous material, structure is single, this makes the property of Co-TUD-1 and the research of catalytic performance have certain limitation.
Therefore, the existing technology needs to be improved and developed.
Summary of the invention
In view of above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of double mesoporous Co-TUD-1 molecular sieves and
Preparation method, it is intended to which it is single to solve existing Co-TUD-1 material structure, the property of Co-TUD-1 and its research of catalytic performance
With the sex-limited problem of certain limitation.
Technical scheme is as follows:
A kind of double mesoporous Co-TUD-1 molecular sieves, wherein double mesoporous Co-TUD-1 molecular sieves have double meso-hole structures: Xiao Jie
Hole and big mesoporous, small mesoporous aperture is in 7 ~ 8nm, and big mesoporous aperture is in 12 ~ 13nm.
Described double mesoporous Co-TUD-1 molecular sieves, wherein double mesoporous Co-TUD-1 molecular sieves by carrier TUD-1 and
The active component Co composition being carried on the carrier TUD-1, the mass content of Co are 0.5 ~ 1%.
Double mesoporous Co-TUD-1 molecular sieves, wherein there are the skeletons of TUD-1 in the form of four-coordination by Co
In.
A kind of preparation method of such as above-mentioned double mesoporous Co-TUD-1 molecular sieves, wherein include:
Step A, trivalent cobalt amine complex is dissolved in deionized water, TEOS is added dropwise under stiring, TEA is then added, stirs
TEAOH is added after mixing 1h；
Step B, it is aged, dry crude product；
Step C, crude product is subjected to crystallization, be filtered, washed, finally roasted to obtain the final product.
The preparation method of double mesoporous Co-TUD-1 molecular sieves, wherein in the step A, the trivalent cobalt amine is matched
Conjunction object is [Co (NH3)6]Cl3Or Co (en)3Cl3。
The preparation method of double mesoporous Co-TUD-1 molecular sieves, wherein in the step A, TEOS, trivalent cobalt amine are matched
Closing object, deionized water, the molar ratio of TEA, TEAOH is 1:0.004 ~ 0.01:4.13:0.97 ~ 0.99:0.85.
The preparation method of double mesoporous Co-TUD-1 molecular sieves, wherein in the step B, the condition of the ageing
Are as follows: room temperature, 24 ~ 48h.
The preparation method of double mesoporous Co-TUD-1 molecular sieves, wherein in the step B, the condition of the drying
Are as follows: 100 ~ 150 DEG C, 24 ~ 48h.
The preparation method of double mesoporous Co-TUD-1 molecular sieves, wherein in the step C, the condition of the crystallization
Are as follows: 145 ~ 155 DEG C, 6 ~ 10h.
The preparation method of double mesoporous Co-TUD-1 molecular sieves, wherein in the step C, the condition of the roasting
Are as follows: 500 ~ 600 DEG C, 3 ~ 5h.
The utility model has the advantages that the present invention provides a kind of double mesoporous Co-TUD-1 molecular sieves and preparation method thereof, it is described double mesoporous
Co-TUD-1 molecular sieve silicon hole diameter narrowly distributing, large specific surface area, the Co of high degree of dispersion on carrier2+And its double mesoporous design features
Co-TUD-1 molecular sieve is set to become a kind of nano catalytic material having great potential.
Detailed description of the invention
Fig. 1 is the small angle XRD comparison diagram of the Co-TUD-1 of difference Co content made from the embodiment of the present invention and comparative example.
Fig. 2 is the wide-angle XRD comparison diagram of the Co-TUD-1 of difference Co content made from the embodiment of the present invention and comparative example.
The nitrogen adsorption desorption that Fig. 3 is present invention Co-TUD-1 of difference Co content made from embodiment and comparative example is bent
Line.
Fig. 4 is the graph of pore diameter distribution of the Co-TUD-1 of difference Co content made from the embodiment of the present invention and comparative example.
Fig. 5 is the ultraviolet-ray visible absorbing light of the Co-TUD-1 of difference Co content made from the embodiment of the present invention and comparative example
Spectrogram.
Fig. 6 is the laser Raman spectroscopy figure of the Co-TUD-1 of difference Co content made from the embodiment of the present invention and comparative example.
Specific embodiment
The present invention provides a kind of pair of mesoporous Co-TUD-1 molecular sieve and preparation method thereof, to make the purpose of the present invention, technology
Scheme and effect are clearer, clear, and the present invention is described in more detail below.It should be appreciated that described herein specific
Embodiment is only used to explain the present invention, is not intended to limit the present invention.
The embodiment of the present invention provides a kind of double mesoporous Co-TUD-1 molecular sieves, wherein double mesoporous Co-TUD-1 molecules
Sifter device has double meso-hole structures: small mesoporous and big mesoporous, small mesoporous aperture is in 7 ~ 8nm, and big mesoporous aperture is in 12 ~ 13nm.
In the present embodiment, the double mesoporous Co-TUD-1 molecular sieve silicon hole diameter narrowly distributings, large specific surface area, height on carrier
The Co of dispersion2+And its double mesoporous design features make Co-TUD-1 molecular sieve become a kind of nano-catalytic material having great potential
Material.
In a preferred embodiment, double mesoporous Co-TUD-1 molecular sieves by carrier TUD-1 and are carried on institute
The active component Co composition on carrier TUD-1 is stated, the mass content of Co is 0.5 ~ 1%.
In a preferred embodiment, there are in the skeleton of TUD-1 in the form of four-coordination by Co.This makes Co-
TUD-1 molecular sieve can be suitable for a variety of liquid phases and gas phase reaction as catalyst.
The embodiment of the invention provides a kind of preparation methods of double mesoporous Co-TUD-1 molecular sieves, wherein includes:
Step A, trivalent cobalt amine complex is dissolved in deionized water, TEOS is added dropwise under stiring, TEA is then added, stirs
TEAOH is added after mixing 1h；
Step B, it is aged, dry crude product；
Step C, crude product is subjected to crystallization, be filtered, washed, finally roasted to obtain the final product.
The present invention is without a large amount of expensive surfactants, for the first time using trivalent cobalt amine complex as additive,
It carries out preparing double mesoporous Co-TUD-1 molecular sieves using common triethanolamine, it is at low cost；Preparation method is simple, and can pass through tune
The additional amount of whole trivalent cobalt amine complex controls the ratio of two kinds of meso-hole structures in the material.
In a preferred embodiment, the trivalent cobalt amine complex can be [Co (NH3)6]Cl3Or Co (en)3Cl3.Trivalent cobalt amine complex [Co (NH3)6]Cl3、Co(en)3Cl3It is hexa-coordinate trivalent cobalt complex, exclusive space
Configuration and having a size of preparation there is the Co-TUD-1 molecular sieve of double meso-hole structures to provide possibility.More electedly, the trivalent cobalt
Amine complex is Co (en)3Cl3.Specifically, Co (en)3Cl3Preparation step are as follows: ethylenediamine and dilute salt are added in the reactor
CoCl is then added in acid into reactor2∙6H2The aqueous solution of O；Oxygen is passed through into above-mentioned reaction solution until reaction solution is in orange
Color；Evaporation, concentration, are added concentrated hydrochloric acid and dehydrated alcohol into the reaction solution after concentration while hot；Cooling, filtering, drying are to get orange
Yellow solid Co (en)3Cl3；Wherein, the concentration of dilute hydrochloric acid is 6mol/L, CoCl2∙6H2O, the molar ratio of ethylenediamine, dilute hydrochloric acid
For 1:3 ~ 4:1 ~ 1.2.
In a preferred embodiment, TEOS, trivalent cobalt amine complex, deionized water, the molar ratio of TEA, TEAOH
For 1:0.004 ~ 0.01:4.13:0.97 ~ 0.99:0.85.In this molar ratio range, Co-TUD-1 molecular sieve obtained has
Double meso-hole structure features；And the additive amount by adjusting trivalent cobalt amine complex can control the ratio of two kinds of meso-hole structures in the material
Example.
In a preferred embodiment, the condition of the ageing can be with are as follows: room temperature, 24 ~ 48h.It is highly preferred that described
The time of ageing is for 24 hours.
In a preferred embodiment, the condition of the drying can be with are as follows: and 100 ~ 150 DEG C, 24 ~ 48h.More preferably
Ground, the condition of the drying are as follows: 100 DEG C, for 24 hours.
In a preferred embodiment, the condition of the crystallization can be with are as follows: and 145 ~ 155 DEG C, 6 ~ 10h.It is highly preferred that
The condition of the crystallization are as follows: 150 DEG C, 6h.
In a preferred embodiment, the condition of the roasting can be with are as follows: and 500 ~ 600 DEG C, 3 ~ 5h.It is highly preferred that
The condition of the roasting are as follows: 500 DEG C, 4h.It roasts under the above conditions, the water and organic matter in product can be removed completely.
Below by embodiment, the present invention is described in detail.
Co(en)3Cl3Preparation
12.0 mL ethylenediamines and 8.5 mL hydrochloric acid (6 mol/L) are added in round-bottomed flask；12.0 g CoCl are weighed again2∙
6H2O is allowed to be dissolved in 38.5 mL water；Above-mentioned two solution is mixed to and is passed through oxygen until solution is in orange；It then will be anti-
Liquid evaporation, concentration are answered, the dense HCl of 7.5 mL and 15.0 ml dehydrated alcohols is added in the reaction system while hot；It sinks after cooling, filtering
It is in orange-yellow for forming sediment, dry to get cobalt amine complex three (ethylenediamine) cobalt chloride (III), is abbreviated as Co (en)3Cl3。
Embodiment 1
0.078g Co(en)3Cl3It is dissolved into 3.57g deionized water, 10.0g ethyl orthosilicate is added dropwise in whipping process
7.05g triethanolamine (Triethanolamine, TEA) then is added, room in (Tetraethyl orthosilicate, TEOS)
6.05g tetraethyl ammonium hydroxide (Tetraethylammonium hydroxide, TEAOH) is added after temperature stirring 1h；Room temperature
For 24 hours, subsequent 100 DEG C of dryings for 24 hours, obtain crude product for lower ageing；Crude product is transferred to again in autoclave (liner is polytetrafluoroethylene (PTFE))
150 DEG C of crystallization 6h are filtered after crystallization on vacuum pump, and are washed with deionized 3-5 times, finally put obtained solid
Enter 500 DEG C of roasting 4h in high temperature furnace；Co content is 0.5wt% in Co-TUD-1 obtained, therefore will be made from the embodiment
Co-TUD-1 is named as Co-0.5.
Embodiment 2
Difference from Example 1 is, Co (en)3Cl3Additional amount be 0.155 g, the additional amount of TEA is 6.95 g,
Remaining preparation condition is the same as embodiment 1；Co content is 1.0wt% in Co-TUD-1 obtained, therefore by Co- made from the embodiment
TUD-1 is named as Co-1.
Comparative example 1
Difference from Example 1 is, Co (en)3Cl3Additional amount be 0.039 g, the additional amount of TEA is 7.10g, remaining
Preparation condition with embodiment 1；Co content is 0.25wt% in Co-TUD-1 obtained, therefore by Co-TUD- made from the comparative example
1 is named as Co-0.25.
Comparative example 2
Difference from Example 1 is, Co (en)3Cl3Additional amount be 0.31 g, the additional amount of TEA is 6.74 g, remaining
Preparation condition with embodiment 1；Co content is 2.0wt% in Co-TUD-1 obtained, therefore by Co-TUD-1 made from the embodiment
It is named as Co-2.
X-ray diffraction is carried out to Co-0.25, Co-0.5, Co-1, Co-2 made from above-described embodiment 1-2 and comparative example 1-2
(XRD) test, the small angle XRD comparison diagram that measures as shown in Figure 1, Co-0.25, Co-0.5, Co-1, Co-2 near 2 θ=0.6 °
There is a very strong diffraction maximum, this illustrates that material has orderly meso-hole structure, with the increase of Co content, diffraction maximum
Position is gradually mobile to small angular direction, this raising of explanation with trivalent cobalt amine complex additional amount, the average hole of mesoporous material
Diameter is also gradually increased；The wide-angle XRD comparison diagram measured is not as shown in Fig. 2, Co-0.25, Co-0.5 and Co-1 occur cobalt
Object diffraction maximum is closed, this illustrates not having in sample Co-0.25, Co-0.5 and Co-1 the cobalt oxide of bulky grain crystallization to generate.
It is de- that nitrogen suction is carried out to Co-0.25, Co-0.5, Co-1, Co-2 made from above-described embodiment 1-2 and comparative example 1-2
Attached test, test results are shown in figure 3, it is known that Co-0.25 is only in P/P0Occur the prominent of one section of adsorbance between=0.5-0.8
Become, for Co-2 only in P/P0=0.85 nearby there is N2Adsorbance mutation；And Co-0.5 and Co-1 are in addition in P/P0 = 0.5-
Outside the mutation for occurring one section of adsorbance between 0.8, in higher relative pressure range (P/P0=0.8-0.9) it also shows that separately
The mutation of one section of adsorbance.Above-mentioned analytic explanation Co-0.25, Co-2 have single meso-hole structure, the mesoporous hole that the two has
Volume is different；Co-0.5, Co-1 have double meso-hole structures.
The aperture of Co-0.25, Co-0.5, Co-1, Co-2 made from above-described embodiment 1-2 and comparative example 1-2 are surveyed
Examination, the pore-size distribution for measuring 4 kinds of samples are as shown in Figure 4, it is known that as the cobalt content in Co-TUD-1 increases, the variation feelings in aperture
Condition are as follows: Co-0.25 is single mesoporous (7.1 nm)；Co-0.5 is double mesoporous (7.2nm (more), 12.3nm(is few))；Co-1 is double is situated between
Hole (7.2 nm (few), 12.6nm(is more))；Co-2 is single mesoporous (13.0nm).I.e. as the cobalt content in Co-TUD-1 increases,
There are orderly double meso-hole structures in Co-TUD-1, and the duct of large aperture in the material shared by ratio contain with complex
The increase of amount and gradually increase, pore volume also gradually increases.This is absolutely proved: Co (en)3Cl3Additive amount have to preparation
The Co-TUD-1 of double meso-hole structures is played a crucial role, by controlling Co (en)3Cl3Additional amount not only can be with Co-
TUD-1 pore structure type, and can control in single mesoporous Co-TUD-1 big in the size in aperture and double mesoporous Co-TUD-1
Small mesoporous shared ratio.In addition, the architectural characteristic value for measuring Co-0.25, Co-0.5, Co-1, Co-2 is as shown in table 1, table 1 into
One step confirms above-mentioned conclusion.
The architectural characteristic of table 1 Co-0.25, Co-0.5, Co-1, Co-2
Ultraviolet-ray visible absorbing is carried out to Co-0.25, Co-0.5, Co-1, Co-2 made from above-described embodiment 1-2 and comparative example 1-2
Spectrum and laser Raman spectroscopy test, the uv-visible absorption spectra measured is as shown in Figure 5, it is known that Co-0.25, Co-0.5 and
Co-1 all shows three absorption peaks near 520,580 and 655nm, is attributed to the Co of four-coordination2+, this demonstrate that in Co-
0.25, in Co-0.5 and Co-1 sample cobalt element with skeleton substitution ion (Co2+) form exist；The laser Raman spectroscopy measured
As shown in Figure 6, it is known that Co-0.25, Co-0.5 and Co-1 are in 400~1200cm-1Any Co is not shown in range3O4It is brilliant
The Raman peaks of body.To the XRD, uv-visible absorption spectra and laser Raman spectroscopy of Co-0.25, Co-0.5, Co-1, Co-2
Comprehensive analysis it is found that in Co-0.25, Co-0.5 and Co-1 sample high degree of dispersion Co2+SiO is entered in the form of four-coordination2
In inorganic skeleton.
In conclusion the present invention provides a kind of pair of mesoporous Co-TUD-1 molecular sieve and preparation method thereof.Double mesoporous Co-
TUD-1 molecular sieve silicon hole diameter narrowly distributing, large specific surface area, the Co of high degree of dispersion on carrier2+And its double mesoporous design features make
Co-TUD-1 molecular sieve becomes a kind of nano catalytic material having great potential；The preparation method is simple, without big
Expensive surfactant is measured, it is at low cost, it can control two kinds of mesoporous knots by adjusting the additional amount of trivalent cobalt amine complex
The ratio of structure in the material, the preparation method provide new approach to develop industrial oxidation catalyst.
It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can
With improvement or transformation based on the above description, all these modifications and variations all should belong to the guarantor of appended claims of the present invention
Protect range.
Claims (10)
1. a kind of double mesoporous Co-TUD-1 molecular sieves, which is characterized in that double mesoporous Co-TUD-1 molecular sieves have double mesoporous
Structure: small mesoporous and big mesoporous, small mesoporous aperture is in 7 ~ 8nm, and big mesoporous aperture is in 12 ~ 13nm.
2. double mesoporous Co-TUD-1 molecular sieves according to claim 1, which is characterized in that described double mesoporous Co-TUD-1 points
Son sieve is made of carrier TUD-1 and the active component Co being carried on the carrier TUD-1, and the mass content of Co is 0.5 ~ 1%.
3. double mesoporous Co-TUD-1 molecular sieves according to claim 2, which is characterized in that wherein, Co is with the shape of four-coordination
There are in the skeleton of TUD-1 for formula.
4. a kind of preparation method of double mesoporous Co-TUD-1 molecular sieves a method according to any one of claims 1-3, which is characterized in that packet
It includes:
Step A, trivalent cobalt amine complex is dissolved in deionized water, TEOS is added dropwise under stiring, TEA is then added, stirs
TEAOH is added after mixing 1h；
Step B, it is aged, dry crude product；
Step C, crude product is subjected to crystallization, be filtered, washed, finally roasted to obtain the final product.
5. the preparation method of double mesoporous Co-TUD-1 molecular sieves according to claim 4, which is characterized in that the step A
In, the trivalent cobalt amine complex is [Co (NH3)6]Cl3Or Co (en)3Cl3。
6. the preparation method of double mesoporous Co-TUD-1 molecular sieves according to claim 4, which is characterized in that the step A
In, TEOS, trivalent cobalt amine complex, deionized water, the molar ratio of TEA, TEAOH be 1:0.004 ~ 0.01:4.13:0.97 ~
0.99:0.85.
7. the preparation method of double mesoporous Co-TUD-1 molecular sieves according to claim 4, which is characterized in that the step B
In, the condition of the ageing are as follows: room temperature, 24 ~ 48h.
8. the preparation method of double mesoporous Co-TUD-1 molecular sieves according to claim 4, which is characterized in that the step B
In, the condition of the drying are as follows: 100 ~ 150 DEG C, 24 ~ 48h.
9. the preparation method of double mesoporous Co-TUD-1 molecular sieves according to claim 4, which is characterized in that the step C
In, the condition of the crystallization are as follows: 145 ~ 155 DEG C, 6 ~ 10h.
10. the preparation method of double mesoporous Co-TUD-1 molecular sieves according to claim 4, which is characterized in that the step C
In, the condition of the roasting are as follows: 500 ~ 600 DEG C, 3 ~ 5h.
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