CN109368653B - Double mesoporous Co-TUD-1 molecular sieve and preparation method thereof - Google Patents
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Abstract
The invention discloses a double mesoporous Co-TUD-1 molecular sieve and a preparation method thereof, wherein the double mesoporous Co-TUD-1 molecular sieve has a double mesoporous structure: the mesoporous silicon material comprises small mesopores and large mesopores, wherein the aperture of each small mesopore is 7-8 nm, and the aperture of each large mesopore is 12-13 nm. The double mesoporous Co-TUD-1 molecular sieve has narrow silicon pore size distribution, large specific surface area and highly dispersed Co on the carrier2+And the structural characteristics of double mesopores thereof enable the Co-TUD-1 molecular sieve to become a nano catalytic material with great potential.
Description
Technical Field
The invention relates to the technical field of supported oxidation catalysts, in particular to a double mesoporous Co-TUD-1 molecular sieve and a preparation method thereof.
Background
The double mesoporous material is a novel porous material developed on the basis of a mesoporous molecular sieve in recent years. The material has two mesoporous structures with different apertures, and the large mesopores can allow molecules with larger sizes to enter and serve as a substance transmission channel, so that the material has smaller diffusion resistance; the small mesopores are used as adsorption points of substances and reaction sites, and have better shape-selective catalytic capability. The characteristic of the double mesoporous material makes it have great development potential in petrochemical industry, fine chemical industry, pharmaceutical industry, production of special polymer material, etc. At present, the research of people on the double mesoporous materials is still in the initial and exploration stage, and although people prepare the materials with the double-pore distribution characteristics under specific conditions by adjusting or changing the parameters of the traditional mesoporous material preparation system, how to effectively control the pore structures and the spatial distribution of pores of two kinds of mesopores and how to modify the pore structures to expand the application fields of the two kinds of mesopores still have problems to be solved. In addition, the synthesis of the double mesoporous material generally adopts a large amount of expensive surfactants as template agents, so that the cost is greatly improved, the preparation conditions are relatively harsh, and the factors greatly restrict the prospect of the double mesoporous molecular sieve in practical application.
The TUD-1 molecular sieve is one of representative novel mesoporous molecular sieves, and has potential application prospects in the field of heterogeneous catalysis due to the advantages of mild synthesis conditions, low cost and the like. The TUD-1 molecular sieve framework is composed of Si and O and is inert to most reactions, so that transition metals are required to be introduced into the pore channels of the molecular sieve framework as active components. The most common method of M-TUD-1 (M being a single metal or a plurality of metals) is hydrothermal synthesis (DHT) in which a precursor is directly added to the synthesis gel, but this method has disadvantages in that the structure of the molecular sieve is destroyed by the introduced more active components and the dispersion degree of the active components is reduced. The active component can also be loaded into the TUD-1 molecular sieve by impregnation, but this method does not ensure that the active component is uniformly loaded into the pores of the molecular sieve. In addition, although the literature reports Co-TUD-1, the existing Co-TUD-1 is a single mesoporous material and has a single structure, so that the research on the properties and the catalytic performance of the Co-TUD-1 has certain limitations.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a double mesoporous Co-TUD-1 molecular sieve and a preparation method thereof, aiming at solving the problems that the existing Co-TUD-1 material has a single structure, and the research on the properties and the catalytic performance of Co-TUD-1 has certain limitations.
The technical scheme of the invention is as follows:
a dual mesoporous Co-TUD-1 molecular sieve, wherein the dual mesoporous Co-TUD-1 molecular sieve has a dual mesoporous structure: the mesoporous silicon material comprises small mesopores and large mesopores, wherein the aperture of each small mesopore is 7-8 nm, and the aperture of each large mesopore is 12-13 nm.
The double mesoporous Co-TUD-1 molecular sieve is characterized in that the double mesoporous Co-TUD-1 molecular sieve consists of a carrier TUD-1 and an active component Co loaded on the carrier TUD-1, and the mass content of Co is 0.5-1%.
The double mesoporous Co-TUD-1 molecular sieve is characterized in that Co exists in a framework of TUD-1 in a four-coordination mode.
The preparation method of the double mesoporous Co-TUD-1 molecular sieve comprises the following steps:
step A, dissolving a trivalent cobalamine complex in deionized water, dropwise adding TEOS under stirring, then adding TEA, stirring for 1h, and then adding TEAOH;
b, aging and drying to obtain a crude product;
and step C, crystallizing the crude product, filtering, washing and finally roasting to obtain the catalyst.
The preparation method of the double mesoporous Co-TUD-1 molecular sieve comprises the step A, wherein the trivalent cobalamin complex is [ Co (NH)3)6]Cl3Or Co (en)3Cl3。
The preparation method of the double mesoporous Co-TUD-1 molecular sieve comprises the following steps of A, wherein in the step A, the molar ratio of TEOS, a trivalent cobalamin complex, deionized water, TEA and TEAOH is 1: 0.004-0.01: 4.13: 0.97-0.99: 0.85.
the preparation method of the double mesoporous Co-TUD-1 molecular sieve comprises the following steps of A, ageing, namely: and (5) at room temperature for 24-48 h.
The preparation method of the double mesoporous Co-TUD-1 molecular sieve comprises the following steps of: 100-150 ℃ for 24-48 h.
The preparation method of the double mesoporous Co-TUD-1 molecular sieve comprises the following steps of: 145-155 ℃ for 6-10 h.
The preparation method of the double mesoporous Co-TUD-1 molecular sieve comprises the following steps of: 500-600 ℃ for 3-5 h.
Has the advantages that: the invention provides a double mesoporous Co-TUD-1 molecular sieve and a preparation method thereof, wherein the double mesoporous Co-TUD-1 molecular sieve has narrow silicon pore size distribution, large specific surface area and highly dispersed Co on a carrier2+And the structural characteristics of double mesopores thereof enable the Co-TUD-1 molecular sieve to become a nano catalytic material with great potential.
Drawings
FIG. 1 is a small angle XRD contrast of Co-TUD-1 of different Co contents made in examples of the invention and comparative examples.
FIG. 2 is a wide angle XRD contrast of Co-TUD-1 of different Co contents made in examples of the invention and comparative examples.
FIG. 3 is a nitrogen adsorption and desorption curve of Co-TUD-1 with different Co contents prepared in examples and comparative examples according to the present invention.
FIG. 4 is a graph showing pore size distribution of Co-TUD-1 of different Co contents obtained in examples of the present invention and comparative examples.
FIG. 5 is a UV-VIS absorption spectrum of Co-TUD-1 having different Co contents according to examples of the present invention and comparative examples.
FIG. 6 is a laser Raman spectrum of Co-TUD-1 with different Co contents obtained in examples of the present invention and comparative examples.
Detailed Description
The invention provides a double mesoporous Co-TUD-1 molecular sieve and a preparation method thereof, and the invention is further explained in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a double mesoporous Co-TUD-1 molecular sieve, wherein the double mesoporous Co-TUD-1 molecular sieve has a double mesoporous structure: the mesoporous silicon material comprises small mesopores and large mesopores, wherein the aperture of each small mesopore is 7-8 nm, and the aperture of each large mesopore is 12-13 nm.
In this example, the double mesoporous Co-TUD-1 moleculeNarrow pore size distribution of sieve, large specific surface area and high dispersion of Co on carrier2+And the structural characteristics of double mesopores thereof enable the Co-TUD-1 molecular sieve to become a nano catalytic material with great potential.
In a preferred embodiment, the bi-mesoporous Co-TUD-1 molecular sieve consists of a carrier TUD-1 and an active component Co loaded on the carrier TUD-1, wherein the mass content of Co is 0.5-1%.
In a preferred embodiment, Co is present in the framework of TUD-1 in a tetra-coordinated form. This makes Co-TUD-1 molecular sieves suitable for use as catalysts in a variety of liquid and gas phase reactions.
The embodiment of the invention provides a preparation method of a double mesoporous Co-TUD-1 molecular sieve, which comprises the following steps:
step A, dissolving a trivalent cobalamine complex in deionized water, dropwise adding TEOS under stirring, then adding TEA, stirring for 1h, and then adding TEAOH;
b, aging and drying to obtain a crude product;
and step C, crystallizing the crude product, filtering, washing and finally roasting to obtain the catalyst.
According to the invention, a large amount of expensive surfactant is not needed, the trivalent cobalamin complex is used as an additive for the first time, the common triethanolamine is used for preparing the double mesoporous Co-TUD-1 molecular sieve, and the cost is low; the preparation method is simple, and the proportion of the two mesoporous structures in the material can be controlled by adjusting the addition amount of the trivalent cobalamin complex.
In a preferred embodiment, the cobaltous amine complex may be [ Co (NH)3)6]Cl3Or Co (en)3Cl3. Trivalent cobalamin complex [ Co (NH)3)6]Cl3、Co(en)3Cl3All are six-coordinate trivalent cobalt complexes, and the unique spatial configuration and size of the complexes provide possibility for preparing Co-TUD-1 molecular sieve with a double mesoporous structure. More optionally, the cobaltous amine complex is Co (en)3Cl3. Specifically, Co (en)3Cl3The preparation steps are as follows: adding ethylenediamine and dilute hydrochloric acid into a reactorFollowed by the addition of CoCl to the reactor2∙6H2An aqueous solution of O; introducing oxygen into the reaction liquid until the reaction liquid is orange; evaporating and concentrating, and adding concentrated hydrochloric acid and absolute ethyl alcohol into the concentrated reaction solution while the reaction solution is hot; cooling, filtering and drying to obtain orange solid Co (en)3Cl3(ii) a Wherein the concentration of the dilute hydrochloric acid is 6mol/L, and the CoCl2∙6H2The molar ratio of O, ethylenediamine and dilute hydrochloric acid is 1: 3-4: 1 to 1.2.
In a preferred embodiment, the molar ratio of TEOS, the cobaltous amine complex, the deionized water, TEA and TEAOH is 1: 0.004-0.01: 4.13: 0.97-0.99: 0.85. in the range of the molar ratio, the prepared Co-TUD-1 molecular sieve has the characteristic of a double mesoporous structure; and the proportion of the two mesoporous structures in the material can be controlled by adjusting the addition amount of the trivalent cobalt amine complex.
In a preferred embodiment, the aging conditions may be: and (5) at room temperature for 24-48 h. More preferably, the aging time is 24 h.
In a preferred embodiment, the drying conditions may be: 100-150 ℃ for 24-48 h. More preferably, the drying conditions are: 100 ℃ for 24 h.
In a preferred embodiment, the crystallization conditions may be: 145-155 ℃ for 6-10 h. More preferably, the crystallization conditions are: 150 ℃ and 6 h.
In a preferred embodiment, the firing conditions may be: 500-600 ℃ for 3-5 h. More preferably, the firing conditions are: 500 ℃ for 4 h. The roasting under the above conditions can completely remove water and organic matters in the product.
The present invention will be described in detail below with reference to examples.
Co(en)3Cl3Preparation of
A round bottom flask was charged with 12.0 mL of ethylenediamine and 8.5 mL of hydrochloric acid (6 mol/L); 12.0 g of CoCl was weighed out again2∙6H2O, dissolving in 38.5 mL of water; mixing the two solutions and introducing oxygen until the solution is orange; then evaporating and concentrating the reaction solution while the solution is stillAdding 7.5 mL of concentrated HCl and 15.0 mL of absolute ethyl alcohol into the reaction system; cooling, filtering, precipitating to orange yellow, and drying to obtain cobalt amine complex, namely, cobalt (III) chloride (III), which is abbreviated as Co (en)3Cl3。
Example 1
0.078g Co(en)3Cl3Dissolving in 3.57g deionized water, adding 10.0g Tetraethyl orthosilicate (TEOS) dropwise while stirring, adding 7.05g Triethanolamine (TEA), stirring at room temperature for 1h, adding 6.05g Tetraethylammonium hydroxide (TEAOH); aging at room temperature for 24h, and then drying at 100 ℃ for 24h to obtain a crude product; transferring the crude product into a high-pressure kettle (the inner lining is made of polytetrafluoroethylene) to crystallize for 6h at 150 ℃, performing suction filtration on the crystallized product on a vacuum pump, washing the crystallized product for 3 to 5 times by using deionized water, and finally putting the obtained solid into a high-temperature furnace to bake for 4h at 500 ℃; the Co content of the obtained Co-TUD-1 was 0.5wt%, and therefore the Co-TUD-1 obtained in this example was named Co-0.5.
Example 2
The difference from example 1 is that Co (en)3Cl3The amount of TEA added was 6.95 g and 0.155 g, and the other preparation conditions were the same as in example 1; the Co content of the obtained Co-TUD-1 was 1.0wt%, and therefore the Co-TUD-1 obtained in this example was named Co-1.
Comparative example 1
The difference from example 1 is that Co (en)3Cl3The amount of addition of (1) was 0.039 g, the amount of addition of TEA was 7.10g, and the other preparation conditions were the same as in example 1; the Co content of the obtained Co-TUD-1 was 0.25wt%, so that the Co-TUD-1 obtained in this comparative example was named Co-0.25.
Comparative example 2
The difference from example 1 is that Co (en)3Cl3The amount of TEA added was 6.74 g and the same preparation conditions as in example 1 were used; the Co content of the obtained Co-TUD-1 was 2.0wt%, and therefore the Co-TUD-1 obtained in this example was named Co-2.
X-ray diffraction (XRD) tests are carried out on the Co-0.25, the Co-0.5, the Co-1 and the Co-2 prepared in the above examples 1-2 and comparative examples 1-2, and the measured small-angle XRD contrast diagram is shown in figure 1, wherein the Co-0.25, the Co-0.5, the Co-1 and the Co-2 all have a strong diffraction peak near 2 theta =0.6 degrees, which indicates that the material has an ordered mesoporous structure, and the positions of the diffraction peaks gradually move towards the small-angle direction along with the increase of the Co content, which indicates that the average pore diameter of the mesoporous material gradually increases along with the increase of the addition amount of the trivalent cobalt amine complex; the measured wide-angle XRD contrast is shown in FIG. 2, and no diffraction peak of cobalt compound appears in Co-0.25, Co-0.5 and Co-1, which indicates that no large-grain crystallized cobalt oxide is generated in the samples Co-0.25, Co-0.5 and Co-1.
The results of the nitrogen desorption tests conducted on Co-0.25, Co-0.5, Co-1 and Co-2 obtained in examples 1 to 2 and comparative examples 1 to 2 are shown in FIG. 3, and it is found that Co-0.25 is only present in P/P0A sudden change in the adsorption capacity occurs between 0.5 and 0.8, for Co-2 only at P/P0Occurrence of N in the vicinity of = 0.852Sudden change of adsorption amount; while Co-0.5 and Co-1 are excluded from the P/P0In addition to a sudden change in the adsorption capacity between 0.5 and 0.8, in the higher relative pressure range (P/P)0= 0.8-0.9) also showed a mutation in the adsorption amount of another stage. The above analysis shows that Co-0.25 and Co-2 have single mesoporous structure, and the pore volume of the mesopores of the Co-0.25 and Co-2 is different; co-0.5 and Co-1 have double mesoporous structures.
The pore diameters of Co-0.25, Co-0.5, Co-1 and Co-2 obtained in examples 1-2 and comparative examples 1-2 were measured, and the pore diameter distributions of the 4 samples were as shown in FIG. 4, and it was found that as the content of cobalt in Co-TUD-1 increases, the change in pore diameter was: co-0.25 is single mesopore (7.1 nm); co-0.5 is a double mesopore (7.2 nm (more), 12.3nm (less)); co-1 is a double mesopore (7.2 nm (few), 12.6nm (many)); co-2 is single mesopore (13.0 nm). That is, as the cobalt content in Co-TUD-1 increases, the Co-TUD-1 has an ordered double mesoporous structure, and the proportion of the pore channels with large pore diameters in the material gradually increases with the increase of the content of the complex, and the pore volume also gradually increases. This is fully illustrated by: co (en)3Cl3The addition amount of (A) plays an important role in preparing Co-TUD-1 with a double mesoporous structure, and Co (en) is controlled3Cl3The addition amount of the mesoporous Co-TUD-1 can be controlled by not only the type of the Co-TUD-1 pore structure, but also the pore size of the single mesoporous Co-TUD-1 and the proportion of the large and small mesopores in the double mesoporous Co-TUD-1. Furthermore, the values of the structural characteristics of Co-0.25, Co-0.5, Co-1, Co-2 were measured as shown in Table 1, and Table 1 further confirms the above findings.
TABLE 1 structural characteristics of Co-0.25, Co-0.5, Co-1, Co-2
The UV-VISIBLE absorptions of Co-0.25, Co-0.5, Co-1 and Co-2 obtained in examples 1-2 and comparative examples 1-2 were measured by UV-VISIBLE absorptions and laser Raman spectroscopy, and the UV-VISIBLE absorptions are shown in FIG. 5, indicating that Co-0.25, Co-0.5 and Co-1 all showed three absorptions at about 520, 580 and 655nm, and that the feature is four-coordinate Co2+This demonstrates that cobalt substitutes for the framework ion (Co-0.25, Co-0.5, and Co-1 samples)2+) Exists in the form of (1); the measured laser Raman spectrum is shown in FIG. 6, which indicates that Co-0.25, Co-0.5 and Co-1 are in the range of 400-1200 cm-1Does not show any Co in the range3O4Raman peak of the crystal. The comprehensive analysis of XRD, ultraviolet-visible absorption spectrum and laser Raman spectrum of Co-0.25, Co-0.5, Co-1 and Co-2 shows that highly dispersed Co is in the Co-0.25, Co-0.5 and Co-1 samples2+Into SiO in the form of four coordinates2In the inorganic skeleton.
In conclusion, the invention provides a double mesoporous Co-TUD-1 molecular sieve and a preparation method thereof. The double mesoporous Co-TUD-1 molecular sieve has narrow silicon pore size distribution, large specific surface area and highly dispersed Co on the carrier2+The structural characteristics of the double mesopores of the Co-TUD-1 molecular sieve lead the Co-TUD-1 molecular sieve to become a nano catalytic material with great potential; the preparation method is simple, a large amount of expensive surfactant is not needed, the cost is low, the proportion of the two mesoporous structures in the material can be controlled by adjusting the addition amount of the trivalent cobalt amine complex, and the preparation method provides a new way for developing an industrial oxidation catalyst.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (9)
1. A bi-mesoporous Co-TUD-1 molecular sieve, wherein the bi-mesoporous Co-TUD-1 molecular sieve has a bi-mesoporous structure: the mesoporous material comprises small mesopores and large mesopores, wherein the aperture of each small mesopore is 7-8 nm, and the aperture of each large mesopore is 12-13 nm;
the double mesoporous Co-TUD-1 molecular sieve consists of a carrier TUD-1 and an active component Co loaded on the carrier TUD-1, wherein the mass content of Co is 0.5-1%;
the preparation of the double mesoporous Co-TUD-1 molecular sieve adopts a trivalent cobalamin complex as a cobalt source, wherein the trivalent cobalamin complex is [ Co (NH)3)6]Cl3Or Co (en)3Cl3。
2. The dual mesoporous Co-TUD-1 molecular sieve according to claim 1, wherein Co is present in a tetracoordinated form in the framework of TUD-1.
3. A method of preparing the dual mesoporous Co-TUD-1 molecular sieve according to claim 1 or 2, comprising:
step A, dissolving a trivalent cobalamine complex in deionized water, dropwise adding TEOS under stirring, then adding TEA, stirring for 1h, and then adding TEAOH;
b, aging and drying to obtain a crude product;
and step C, crystallizing the crude product, filtering, washing and finally roasting to obtain the catalyst.
4. The method for preparing a bi-mesoporous Co-TUD-1 molecular sieve according to claim 3, wherein in the step A, the trivalent cobalamin complex is [ Co (NH)3)6]Cl3Or Co (en)3Cl3。
5. The preparation method of the bi-mesoporous Co-TUD-1 molecular sieve according to claim 3, wherein in the step A, the molar ratio of TEOS, the trivalent cobalamin complex, deionized water, TEA and TEAOH is 1: 0.004-0.01: 4.13: 0.97-0.99: 0.85.
6. the method for preparing a bi-mesoporous Co-TUD-1 molecular sieve according to claim 3, wherein in the step B, the aging conditions are as follows: and (5) at room temperature for 24-48 h.
7. The method for preparing a bi-mesoporous Co-TUD-1 molecular sieve according to claim 3, wherein in the step B, the drying conditions are as follows: 100-150 ℃ for 24-48 h.
8. The method for preparing a bi-mesoporous Co-TUD-1 molecular sieve according to claim 3, wherein in the step C, the crystallization conditions are as follows: 145-155 ℃ for 6-10 h.
9. The method for preparing a bi-mesoporous Co-TUD-1 molecular sieve according to claim 3, wherein in the step C, the calcination conditions are as follows: 500-600 ℃ for 3-5 h.
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