SILICATE MATERIAL ZEO-2 AND SILICATE MOLECULAR SIEVE ZEO-3 AND SYNTHESIS METHOD THEREFOR AND USE THEREOF

Abstract

The present invention relates to a one-dimensional silicate material ZEO-2 with a novel structure and a three-dimensional silicate molecular sieve ZEO-3 obtained by roasting ZEO-2 and a synthesis method therefor and a use thereof. The X-ray powder diffraction characteristics and crystal structures of the two silicate materials are represented. The one-dimensional silicate ZEO-2 can be synthesized by a simple method. The molecular sieve ZEO-3 can be obtained by calcining the one-dimensional silicate ZEO-2 to cause topological condensation. ZEO-2 can be used as a silicon source or a precursor in the synthesis of a novel molecular sieve. The molecular sieve ZEO-3 has good thermal stability and can be used as an adsorbent or a catalyst.

Claims

1. A silicate material, characterized in that the silicate material has the powder X-ray diffraction characteristics shown in the following table. TABLE-US-00005 Interplanar spacing range (?) Relative intensity I/I.sub.0 ? 100 16.246 ? 1.052 vs 12.282 ? 0.736 m-s 10.773 ? 0.737 w 9.706 ? 0.675 w 8.911 ? 0.671 w 8.158 ? 0.354 mw 7.476 ? 0.193 w 7.115 ? 0.101 w 6.891 ? 0.085 w-mw 6.556 ? 0.071 w 6.248 ? 0.053 w 6.136 ? 0.093 w-mw 5.786 ? 0.071 w 5.493 ? 0.063 w-mw 5.378 ? 0.061 w-mw 5.292 ? 0.037 w 5.024 ? 0.063 w 4.494 ? 0.043 w 4.771 ? 0.091 w 4.601 ? 0.039 w 4.284 ? 0.042 w-mw 4.072 ? 0.103 vs 3.914 ? 0.035 w 3.855 ? 0.027 w 3.806 ? 0.031 w 3.735 ? 0.029 w 3.642 ? 0.035 w 3.575 ? 0.028 w-mw 3.420 ? 0.040 w-mw 3.368 ? 0.022 w-mw 3.275 ? 0.031 w 3.073 ? 0.026 w 2.967 ? 0.027 w 2.833 ? 0.028 w 2.597 ? 0.020 w 2.448 ? 0.013 w

2. The silicate material according to claim 1, characterized in that the crystal structure of the silicate material has a regular, long-range ordered, one-dimensional silica chain structure.

3. The silicate material according to claim 1, characterized in that the silicate material has a chemical composition SiO.sub.2.2H.sub.0.4.Math.(OSDA).sub.y, where OSDA is an organic template having a tetrahedral spatial configuration represented by the following general formula: ##STR00012## wherein R.sub.1 is cyclohexyl; R.sub.2 and R.sub.3 are phenyl or cyclohexyl; R.sub.4 is C.sub.1-8 alkyl, preferably C.sub.1-4 alkyl, more preferably C.sub.1-2 alkyl; n=3-8, preferably 5-7, more preferably 6; X is phosphorus or nitrogen, preferably phosphorus, wherein y=0.075-0.125.

4. A silicate molecular sieve, characterized in that the molecular sieve has the powder X-ray diffraction characteristics shown in the following table. TABLE-US-00006 Interplanar spacing range (?) Relative intensity I/I.sub.0 ? 100 14.669 ? 1.055 vs 11.447 ? 0.486 m-vs 9.049 ? 0.253 m-s 8.423 ? 0.168 w 7.403 ? 0.194 w 6.843 ? 0.132 w 6.458 ? 0.123 w 5.965 ? 0.073 w 5.738 ? 0.122 w 4.994 ? 0.10 w-mw 4.901 ? 0.075 w-mw 4.697 ? 0.078 w 4.519 ? 0.079 w-mw 4.360 ? 0.047 w 4.194 ? 0.057 w 4.058 ? 0.070 w 3.970 ? 0.045 w 3.785 ? 0.086 w 3.673 ? 0.073 w-mw 3.623 ? 0.075 w-mw 3.548 ? 0.048 w 3.419 ? 0.042 w 3.376 ? 0.045 w 3.218 ? 0.032 w 3.171 ? 0.031 w 3.029 ? 0.041 w 2.977 ? 0.024 w 2.870 ? 0.28 w 2.660 ? 0.29 w 2.497 ? 0.033 w

5. The molecular sieve according to claim 4, characterized in that the molecular sieve has in its crystal structure a three-dimensional intersecting channel system of 16?14?14-membered rings.

6. The molecular sieve according to claim 4, characterized in that the T atoms in the framework of the molecular sieve have the topological characteristics shown in the following table: TABLE-US-00007 N1 N2 N3 N4 N5 N6 N7 N8 N9 N10 N11 N12 VS T1 4 11 18 27 34 54 81 113 140 159 181 224 4.5(2).5.5.5.6 T2 4 10 19 27 39 53 80 109 139 166 192 224 4.6.4.14.5.5 T3 4 8 15 26 39 55 73 102 135 169 194 227 4.4.4.5.4.14(5) T4 4 10 19 28 38 54 77 111 140 166 191 224 4.6.4.14(5).5.5 T5 4 11 18 25 36 54 85 110 134 157 188 230 4.5(2).5.5.5.6 T6 4 12 17 25 38 58 80 113 135 156 192 231 5.5.5.6.5(2).14(3) T7 4 8 15 26 38 54 76 105 131 165 196 228 4.4.4.5.4.14 T8 4 9 15 24 39 57 80 103 127 156 204 240 4.5.4.5.4.14 T9 4 12 15 22 40 62 84 107 122 152 200 250 5.5.5.5.5(2).16(9) T10 4 12 19 28 36 52 82 115 144 162 186 218 5.5.5(2).14(6).6.6 T11 4 9 15 25 40 55 77 102 134 163 196 229 4.5.4.5.4.14(5) where T=Si.

7. The molecular sieve according to claim 4, characterized in that said molecular sieve has a chemical composition of SiO.sub.2.

8. A method for the synthesis of the silicate material according to claim 1, comprising: (1) mixing a silicon source, an organic template and water to obtain a mixture; (2) crystallizing the mixture to obtain the silicate material product; wherein the organic template has a tetrahedral spatial configuration represented by the following general formula: ##STR00013## wherein R.sub.1 is cyclohexyl; R.sub.2 and R.sub.3 are phenyl or cyclohexyl; R.sub.4 is C.sub.1-8 alkyl, preferably C.sub.1-4 alkyl, more preferably C.sub.1-2 alkyl; n=3-8, preferably 5-7, more preferably 6; X is phosphorus or nitrogen, preferably phosphorus.

9. The method according to claim 8, characterized in that the organic template is any one or more selected from the following: ##STR00014## preferably any one or more selected from the following: ##STR00015## more preferably any one or more selected from the following: ##STR00016##

10. The method according to claim 8, characterized in that: step (1) specifically comprises: under stirring, mixing a silicon source, an organic template and water uniformly in proportion, and forming a reaction gel by the obtained mixture with a chemical composition of rROH:SiO.sub.2:wH.sub.2O, wherein R represents the positive charge group of the organic template; the corresponding value intervals of r and w are: r=0.05-5.0, w=1-100; step (2) specifically comprises: placing the reaction gel under an infrared lamp or in an oven, after the removal of excess solvent, transferring the reaction gel to a stainless steel reaction kettle to react for 1-60 days, preferably 2-45 days, under sealed condition and at a temperature of 80-240? C., preferably 120-220? C., for crystallization; and the method further comprises: (3) washing and drying the crystallized product.

11. The method according to claim 10, characterized in that in the chemical composition rROH:SiO.sub.2:wH.sub.2O of the reaction gel, preferably the corresponding value intervals of r and w are: r=0.1-2.0, w=1-30.

12. The method according to claim 8, characterized in that the silicon source is at least one selected from the group consisting of silicic acid, silica gel, silica sol, tetraalkyl silicate and water glass.

13. The method according to claim 8, characterized in that crystallization conditions in step (2) include: crystallization temperature of 80? C. to 240? C., preferably 120? C. to 220? C., more preferably 140? C. to 210? C.; and crystallization time of 1 to 60 days, preferably 2 to 50 days, more preferably 3 to 45 days.

14. The method for the synthesis of the molecular sieve according to claim 4, comprising: calcining the silicate material of claim 1 or the silicate material synthesized by the method according to claim 8 to remove the template in the silicate material and cause topological condensation of the framework structure, to thereby obtain a molecular sieve product.

15. The method according to claim 14, characterized in that the calcination temperature is 300? C. to 1000? C.

16. (canceled)

17. (canceled)

18. (canceled)

Description

DESCRIPTION OF DRAWINGS

[0025] FIG. 1 is an X-ray powder diffraction pattern of the silicate material ZEO-2 of the present invention (the light source is Cu target K? rays).

[0026] FIG. 2 is an X-ray powder diffraction pattern of the silicate molecular sieve ZEO-3 of the present invention (the light source is Cu target K? rays).

[0027] FIG. 3 is a relative intensity comparison of the X-ray powder diffraction patterns of the silicate material ZEO-2 and the silicate molecular sieve ZEO-3 of the present invention.

[0028] FIG. 4 is a scanning electron microscope (SEM) image of the silicate material ZEO-2 of the present invention.

[0029] FIG. 5 is a scanning electron microscope (SEM) image of the silicate molecular sieve ZEO-3 of the present invention.

[0030] FIG. 6 is a diagram of the framework structure of the silicate material ZEO-2 after removing the organic template.

[0031] FIG. 7 is a diagram of the channel structure of extra-large pore molecular sieve ZEO-3.

DETAILED DESCRIPTION OF THE INVENTION

[0032] The crystal structure of the inorganic framework of the silicate material ZEO-2 of the present invention is shown in FIG. 6. The crystal structure of the silicate material ZEO-2 has a regular, long-range ordered, one-dimensional silica chain structure that extends infinitely along the c-axis direction.

[0033] The crystal structure of the molecular sieve ZEO-3 of the present invention is shown in FIG. 7. As can be seen from FIG. 7, there are penetrating 14-membered ring channels in both the (a+b)-axis direction and the (a-b)-axis direction of the ZEO-3 crystal structure. In addition, there are 16-membered ring channels in the c-axis direction of the ZEO-3 crystal structure. Therefore, the structure is described as a three-dimensional intersecting channel system of 16?14?14-membered rings.

[0034] The molecular sieve ZEO-3 of the present invention is subjected to structural analysis and topology analysis. The molecular sieve framework structure has 11 topologically independent T atoms, 20 topologically different edges (lines constituted by adjacent T atom and T atom), 16 topologically different planes (planes constituted by T atoms), and 8 topologically different building blocks constituted by T atoms. Among them, the topological properties (including coordination sequences and vertex symbols) of the 11 topologically independent T atoms of the framework structure of the molecular sieve ZEO-3 are shown in Table 3.

TABLE-US-00003 TABLE 3 N1 N2 N3 N4 N5 N6 N7 N8 N9 N10 N11 N12 VS T1 4 11 18 27 34 54 81 113 140 159 181 224 4.5(2).5.5.5.6 T2 4 10 19 27 39 53 80 109 139 166 192 224 4.6.4.14.5.5 T3 4 8 15 26 39 55 73 102 135 169 194 227 4.4.4.5.4.14(5) T4 4 10 19 28 38 54 77 111 140 166 191 224 4.6.4.14(5).5.5 T5 4 11 18 25 36 54 85 110 134 157 188 230 4.5(2).5.5.5.6 T6 4 12 17 25 38 58 80 113 135 156 192 231 5.5.5.6.5(2).14(3) T7 4 8 15 26 38 54 76 105 131 165 196 228 4.4.4.5.4.14 T8 4 9 15 24 39 57 80 103 127 156 204 240 4.5.4.5.4.14 T9 4 12 15 22 40 62 84 107 122 152 200 250 5.5.5.5.5(2).16(9) 10 4 12 19 28 36 52 82 115 144 162 186 218 5.5.5(2).14(6).6.6 T11 4 9 15 25 40 55 77 102 134 163 196 229 4.5.4.5.4.14(5)

[0035] T1 to T11 represent the 11 topologically different T atoms of the framework structure of the extra-large pore molecular sieve ZEO-3 of the present invention; N1 to N12 represent the coordination sequences of these T atoms from the first layer to the twelfth layer. Due to the different order of naming of T atoms, the 11 topologically independent T atoms named in a different order may not correspond one-to-one to the coordination sequences and vertex symbols of the T atoms in the order in this table, but the structures belonging to the ZEO-3 topology all include and only include the coordination sequences and vertex symbols of the 11 topologically independent T atoms in this table, and the coordination sequences and vertex symbols correspond one-to-one.

[0036] The silicate ZEO-2 of the present invention has a chemical composition SiO.sub.2.2H.sub.0.4.Math.(OSDA).sub.y, where OSDA is an organic template, and y=0.075-0.125.

[0037] The extra-large pore silicate molecular sieve ZEO-3 of the present invention has a chemical composition of SiO.sub.2.

[0038] In the method for the synthesis of the silicate material ZEO-2 of the present invention, specific examples of the organic templates include but are not limited to any one or more shown in Table 4:

TABLE-US-00004 TABLE 4 No. Structural diagram No. Structural diagram 1 [00002] 6 [00003] 2 [00004] 7 [00005] 3 [00006] 8 [00007] 4 [00008] 9 [00009] 5 [00010] 10 [00011]

[0039] The organic template is preferably any one or more selected from the group consisting of template 1, template 6, template 8 and template 10, more preferably any one or more selected from the group consisting of template 6 and template 10.

[0040] In the method for the synthesis of the silicate material ZEO-2 of the present invention, step (1) may specifically comprise: under static or dynamic stirring, mixing a silicon source, an organic template and water uniformly in proportion, and forming a reaction gel by the obtained mixture with a chemical composition of rROH:SiO.sub.2:wH.sub.2O, wherein R represents the positive charge group of the organic template; the corresponding value intervals of r and w are: r=0.05-5.0, w=1-100; step (2) may specifically comprise: placing the reaction gel under an infrared lamp or in an oven, after the removal of excess solvent, transferring the reaction gel to a stainless steel reaction kettle to react for 1-60 days, preferably 2-45 days, under sealed condition and at a temperature of 80-240? C., preferably 120-220? C., for crystallization; and the method may further comprise: (2) washing, centrifuging, and drying the crystallized product, to obtain the silicate material ZEO-2 product.

[0041] In step (1), in the chemical composition rROH:SiO.sub.2:wH.sub.2O of the reaction gel, preferably the corresponding value intervals of r and w are: r=0.1-2.0, w=1-30.

[0042] The silicon source can be at least one selected from the group consisting of silicic acid, silica gel, silica sol, tetraalkyl silicate and water glass, preferably water glass, silica sol or tetraethyl orthosilicate.

[0043] In the preparation method of the present invention, germanium or germanium-containing compounds are not used.

[0044] Before the preparation of the reaction gel, all of the organic cationic templates can be exchanged into hydroxide form via an ion exchange resin, and their concentration is calibrated by 0.1M hydrochloric acid solution for later use, or they may be introduced directly in the form of a chloride salt, a bromide salt or an iodide salt.

[0045] Crystallization conditions in step (2) may include, for example: crystallization temperature of 80? C. to 240? C., preferably 120? C. to 220? C., more preferably 140? C. to 210? C.; and crystallization time of 1 to 60 days, preferably 2 to 50 days, more preferably 3 to 45 days.

[0046] In step (3), washing, centrifuging and drying can be performed in any manner conventionally known in the art. For example, washing can be performed multiple times with water or ethanol; and drying can be done by oven drying.

[0047] In the method for the synthesis of the extra-large pore zeolite molecular sieve ZEO-3 of the present invention, the calcination temperature is 300? C. to 1000? C.

[0048] The binder in the molecular sieve composition of the present invention can be any binder known in the art that can be used for catalysts or adsorbents, as long as it does not adversely affect the molecular sieve ZEO-3 of the present invention.

EXAMPLES

[0049] In order to illustrate the present invention more clearly, the following examples are provided. These examples do not limit the protection scope of the present invention in any way.

Example 1: Preparation of Template

[0050] Template 6 was taken as an example to illustrate the general process for the synthesis of a template. 28.04 g of tricyclohexylphosphine and 150 ml of acetonitrile were mixed in a 250 ml round bottom flask. At normal temperature, 21.29 g of methyl iodide was added dropwise to the mixed liquid. The system reacted for two days under stirring at normal temperature, and the solvent was removed from the reaction mixture by rotary evaporation to obtain a crude product, which was recrystallized with ethanol to obtain 40.55 g of product, with a yield of 96%. The product was characterized by liquid NMR (CDCl3) and electrospray mass spectrometry, and confirmed to be the target compound.

[0051] The resulting product was dispersed in 400 ml of deionized water, and the pretreated 717 strong base-type anion exchange resin (manufacturer: Sinopharm Group, China) was used for column exchange to exchange the obtained aqueous solution of template agent 6. An appropriate amount of this solution was weighed, and calibrated with a 0.1 mol/L solution of hydrochloric acid, using phenolphthalein as an indicator. The calibrated structure confirmed an exchange efficiency of iodide salt to hydroxide radical up to 97%.

Example 2: Preparation of Template

[0052] Template 10 was taken as an example to illustrate the general process for the synthesis of a template. 28.04 g of tricyclohexylphosphine and 150 ml of acetonitrile were mixed in a 250 ml round bottom flask. 12.20 g of 1,6-dibromohexane was added dropwise to the mixed liquid. The system reacted for two days under stirring and under reflux, and the solvent was removed from the reaction mixture by rotary evaporation to obtain a crude product, which was recrystallized with ethanol to obtain 38.23 g of product, with a yield of 95%. The product was characterized by liquid NMR (D20) and electrospray mass spectrometry, and confirmed to be the target compound.

[0053] The resulting product was dispersed in 400 ml of deionized water, and the pretreated 717 strong base-type anion exchange resin (manufacturer: Sinopharm Group, China) was used for column exchange to exchange the obtained aqueous solution of template agent 10. An appropriate amount of this solution was weighed, and calibrated with a 0.1 mol/L solution of hydrochloric acid, using phenolphthalein as an indicator. The calibrated structure confirmed an exchange efficiency of iodide salt to hydroxide radical up to 96%.

Example 3 Preparation of ZEO-2 and ZEO-3

[0054] According to the molar ratio of 0.5 ROH:SiO.sub.2:10 H.sub.2O, a gel for the synthesis of molecular sieve was prepared by the following general steps: an appropriate amount of the solution of template in Example 1 after exchange was weighed, 4 mmol (0.833 g) of tetraethyl orthosilicate was added therein, and stirred at normal temperature for about two hours so that tetraethyl orthosilicate was completely dissolved, then the mixed gel was placed under an infrared lamp or in an oven at 80? C., to remove the excess solvent. The finally obtained reaction gel was transferred to a 5 ml stainless steel reaction kettle with polytetrafluoroethylene lining, and reacted at 175? C. for 28 days under sealed condition, the product was washed twice with water and twice with ethanol, and oven dried for use. The product was directly subjected to phase identification by X-ray powder diffraction, and was confirmed to be ZEO-2.

[0055] An appropriate amount of the sample was calcined in a muffle furnace at 600? C. in an air atmosphere for 2 hours to remove the template, the product was washed with water, centrifuged, and dried. The product was subjected to phase identification by X-ray powder diffraction, and was confirmed to be ZEO-3. EDS elemental analysis showed that it had solicon element and oxygen element and had a molecular formula SiO.sub.2.

Example 4 Preparation of ZEO-2 and ZEO-3

[0056] According to the molar ratio of 0.3 ROH:SiO.sub.2:5 H.sub.2O, a gel for the synthesis of molecular sieve was prepared by the following general steps: an appropriate amount of the solution of template in Example 2 after exchange was weighed, 2 mmol (0.417 g) of tetraethyl orthosilicate was added therein, and stirred at normal temperature for about two hours so that tetraethyl orthosilicate was completely dissolved, then the mixed gel was placed under an infrared lamp or in an oven at 80? C., to remove the excess solvent.

[0057] The finally obtained reaction gel was transferred to a 5 ml stainless steel reaction kettle with polytetrafluoroethylene lining, and reacted at 175? C. for 30 days under sealed condition, the product was washed twice with water and twice with ethanol, and oven dried for use. The product was directly subjected to phase identification by X-ray powder diffraction, and was confirmed to be ZEO-2.

[0058] An appropriate amount of the sample was calcined in a muffle furnace at 600? C. in an air atmosphere for 2 hours to remove the template, the product was washed with water, centrifuged, and dried. The product was subjected to phase identification by X-ray powder diffraction, and was confirmed to be ZEO-3. EDS elemental analysis showed that it had solicon element and oxygen element and had a molecular formula SiO.sub.2.

Example 5 Preparation of ZEO-2 and ZEO-3

[0059] According to the molar ratio of 0.5 ROH:SiO.sub.2:10 H.sub.2O, a gel for the synthesis of molecular sieve was prepared by the following general steps: an appropriate amount of the solution of template 8 in Table 6 after exchange was weighed, 1 mmol (0.208 g) of tetraethyl orthosilicate was added therein, and stirred at normal temperature for about two hours so that tetraethyl orthosilicate was completely dissolved, then the mixed gel was placed under an infrared lamp or in an oven at 80? C., to remove the excess solvent. The finally obtained reaction gel was transferred to a 5 ml stainless steel reaction kettle with polytetrafluoroethylene lining, and reacted at 175? C. for 38 days under sealed condition, the product was washed twice with water and twice with ethanol, and oven dried for use. The product was directly subjected to phase identification by X-ray powder diffraction, and was confirmed to be ZEO-2.

[0060] An appropriate amount of the sample was calcined in a muffle furnace at 600? C. in an air atmosphere for 2 hours to remove the template, the product was washed with water, centrifuged, and dried. The product was subjected to phase identification by X-ray powder diffraction, and was confirmed to be ZEO-3. EDS elemental analysis showed that it had solicon element and oxygen element and had a molecular formula SiO.sub.2.

Example 6 Preparation of ZEO-2 and ZEO-3

[0061] According to the molar ratio of 0.5 ROH:SiO.sub.2:10 H.sub.2O, a gel for the synthesis of molecular sieve was prepared by the following general steps: the solution of template in Example 1 in 6 mmol after exchange was weighed, 12 mmol (2.500 g) of tetraethyl orthosilicate was added therein, and stirred at normal temperature overnight so that tetraethyl orthosilicate was completely hydrolyzed and the hydrolysis product ethanol was volatized, the mixed gel was placed under an infrared lamp or in an oven at 85? C., to remove the excess solvent. The finally obtained reaction gel was transferred to a 30 ml stainless steel reaction kettle with polytetrafluoroethylene lining, and reacted at 190? C. for 30 days under sealed condition, the product was washed twice with water and twice with ethanol, and oven dried for use. The product was directly subjected to phase identification by X-ray powder diffraction, and was confirmed to be ZEO-2. EDS elemental analysis showed that it had silicon, phosphorus, oxygen and carbon elements. Fourier Transform Infrared Spectrum data showed that there was SiOH bond stretching vibration and this peak was a strong peak, indicating that ZEO-2 was a type of silicate material with silanol groups and had a large content of silanol groups.

[0062] An appropriate amount of the sample was calcined in a muffle furnace at 600? C. in an air atmosphere for 2 hours to remove the template, the product was washed with water, centrifuged, and dried. The product was subjected to phase identification by X-ray powder diffraction, and was confirmed to be ZEO-3. EDS elemental analysis showed that it had solicon element and oxygen element only and had a molecular formula SiO.sub.2. Fourier Transform Infrared Spectrum data showed that there was no SiOH bond stretching vibration, and there was SiO bond stretching vibration only, indicating that ZEO-3 was a type of silicate material without silanol groups and without defects.

Example 7 Structural Analysis

[0063] The molecular sieves ZEO-2 of Examples 3-6 were subjected to continuous rotation electron diffraction (cRED) test, and the structural analysis results showed that the ZEO-2 molecular sieve structure had monoclinic symmetry with C2/c space group, the unit cell parameters obtained after refinement of the powder X-rays with copper target (Ka) as light source (FIG. 1) were: a=23.539 (9) ?, b=24.744 (9) ?, c=14.398 (9) ?, ?=115.19 (9)?.

[0064] The molecular sieves ZEO-3 of Examples 3-6 were subjected to continuous rotation electron diffraction (cRED) test, and the structural analysis results showed that the ZEO-3 molecular sieve structure had monoclinic symmetry with C2/c space group, the unit cell parameters obtained after refinement of the powder X-rays with copper target (Ka) as light source (FIG. 2) were: a=21.505 (9) ?, b=21.274 (9) ?, c=14.463 (9) ?, ?=108.72 (9?).

[0065] Topological analysis was performed using the crystallographic information file (CIF file) obtained after the cRED test. The topological analysis software was based on ToposPro 5.3.0.2, and the analysis process and method were based on the operation manual given on the official website of the software (see ToposPro official website: https://topospro.com/software/).

[0066] The results of analysis of the crystal structure of ZEO-3 showed that the framework structure of the molecular sieve had 11 topologically independent T atoms, 20 topologically different edges, 16 topologically different planes, and 8 topologically different structural units constituted by T atoms. The more specific topological characteristics of the framework structure of ZEO-3 molecular sieve were shown in the above Table 3.