CN115646531B - Rapid energy-saving synthesis method of high-acidity active site copper doped mesoporous silicon oxide - Google Patents
Rapid energy-saving synthesis method of high-acidity active site copper doped mesoporous silicon oxide Download PDFInfo
- Publication number
- CN115646531B CN115646531B CN202211278125.1A CN202211278125A CN115646531B CN 115646531 B CN115646531 B CN 115646531B CN 202211278125 A CN202211278125 A CN 202211278125A CN 115646531 B CN115646531 B CN 115646531B
- Authority
- CN
- China
- Prior art keywords
- copper
- mesoporous silica
- doped
- active site
- synthesis method
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 155
- 239000010949 copper Substances 0.000 title claims abstract description 49
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 36
- 238000001308 synthesis method Methods 0.000 title claims abstract description 21
- 229910052814 silicon oxide Inorganic materials 0.000 title claims abstract description 9
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 150000001879 copper Chemical class 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 230000001105 regulatory effect Effects 0.000 claims abstract description 6
- 238000000967 suction filtration Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 7
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 abstract description 39
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 39
- 239000000463 material Substances 0.000 abstract description 35
- 238000002360 preparation method Methods 0.000 abstract description 5
- 239000007810 chemical reaction solvent Substances 0.000 abstract 1
- 230000001276 controlling effect Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000011148 porous material Substances 0.000 description 17
- 238000004458 analytical method Methods 0.000 description 13
- 238000001179 sorption measurement Methods 0.000 description 12
- 239000013335 mesoporous material Substances 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 239000011973 solid acid Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000003917 TEM image Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 241000530268 Lycaena heteronea Species 0.000 description 3
- 229910003849 O-Si Inorganic materials 0.000 description 3
- 229910003872 O—Si Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- -1 MCM-41 Chemical compound 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000002059 diagnostic imaging Methods 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001988 small-angle X-ray diffraction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a rapid energy-saving synthesis method of high-acidity active site copper doped mesoporous silicon oxide, and belongs to the technical field of inorganic nonmetallic material preparation. The method comprises the following steps: dispersing mesoporous silica and soluble copper salt in water, placing in a microwave reaction kettle, heating to 85-100 ℃ at a speed of 12-15 ℃/min under certain microwave power and initial pressure, regulating and controlling the process pressure, carrying out microwave reaction for 0.5-1h, naturally cooling to room temperature after the reaction is finished, and carrying out suction filtration, washing and drying on the product to obtain the copper-doped mesoporous silica molecular sieve. The method of the invention realizes that the copper element is uniformly doped in the framework structure of the mesoporous silica through the selection of raw materials and the control of reaction solvent, reaction environment and parameters, and the whole reaction treatment process is simple, controllable, energy-saving, time-saving and low in cost.
Description
Technical Field
The invention belongs to the technical field of inorganic nonmetallic material preparation, and particularly relates to a mesoporous silica molecular sieve, in particular to a rapid energy-saving synthesis method of high-acidity active site copper doped mesoporous silica.
Background
The highly ordered mesoporous material represented by porous silicon oxide has great specific surface area, regular pore size distribution (2-50 nm) and easy functionalized mesoporous wall, so that the mesoporous material has important application value in the aspects of new energy development and utilization, selective adsorption and separation, macromolecular catalysis, optical sensing, nano medical imaging and treatment and the like, and becomes a hot spot material for research in recent years. However, pure mesoporous silica lacks chemical activity and has limited application in the chemical industry. The most common method for activating mesoporous silica is doping modification, namely, introducing transition metal elements to replace Si atoms in the skeleton structure of the mesoporous silica, so that high-density chemical active sites and acid centers are generated, and good catalytic activity is shown.
In recent years, cu doped mesoporous silica has proved to be an excellent catalyst, and Cu (II) on the framework of the catalyst has excellent catalytic oxidation activity and can effectively convert H 2 O 2 Is decomposed into OH, thereby realizing phenol hydroxylation and high-efficiency degradation of organic pollutants, and having wider application prospect in the catalysis field. At present, the method for synthesizing the copper doped mesoporous silicon oxide mainly comprises a direct synthesis method and a post-treatment method. The direct synthesis method is to directly introduce a copper source in the synthesis process of mesoporous silicon oxide so that copper ions replace Si atoms in a framework structure; for example, patent CN108285152B, "a copper doped SBA-15 mesoporousIn the green high-efficiency synthesis method of the molecular sieve material, copper acetate is used as a precursor under neutral conditions to prepare Cu doped SBA-15, cu/Si can reach 0.12, but other Cu doped mesoporous silica (such as MCM-41, KIT-6, MCM-48 and the like) cannot be synthesized by the method. The post-treatment method is to add a copper source into the synthesized mesoporous silica suspension, and then to synthesize copper doped mesoporous silica through subsequent treatment; for example, in patent CN109046439B, "a method for synthesizing high-doping high-acidity mesoporous silica solid acid catalyst", acetate is used to promote doping of copper element in mesoporous silica skeleton, and copper element doped solid acid catalyst is prepared. However, in the method, ethanol is required as a dispersing agent, the copper salt utilization rate and the doping rate are low, namely about 45 percent and 13.9 percent respectively, so that the cost is high; the water is used as a dispersing agent to destroy the mesoporous structure of the mesoporous silica, so that the pore canal collapses; and the reaction is carried out for 14 to 16 hours at the temperature of between 70 and 80 ℃, the reaction is naturally cooled to the room temperature after the reaction is finished, the product is filtered, washed and dried, the obtained powdery substance is heated to the temperature of between 480 and 550 ℃ at the speed of between 1 and 2 ℃/min and calcined for 4 to 6 hours, and finally the product is the copper doped mesoporous silica molecular sieve, which takes time (not less than 24 hours) and consumes energy.
The prior art at home and abroad is searched, and the method for synthesizing the copper doped mesoporous silica molecular sieve has low cost (water is a dispersing agent, copper salt utilization rate is high), low energy consumption (85-100 ℃), short time (0.5-1 h) and high copper salt doping efficiency, which is not yet used for promoting the doping of copper elements in the mesoporous silica framework by utilizing a microwave auxiliary method.
Disclosure of Invention
Aiming at various defects existing in the existing method for preparing the copper-doped mesoporous silica molecular sieve material, the invention aims to provide a rapid energy-saving synthesis method of high-acidity active site copper-doped mesoporous silica.
In order to achieve the technical aim, the inventor combines the research experience of mesoporous silica molecular sieve for many years, and finally obtains the following technical scheme through a great deal of experimental research: a rapid energy-saving synthesis method of high-acidity active site copper doped mesoporous silicon oxide comprises the following steps:
(1) Dispersing mesoporous silica and soluble copper salt in water to obtain mixed suspension, wherein the molar ratio of the mesoporous silica to the copper salt is 1 (4.39-83.4);
(2) Placing the mixed suspension in a microwave reaction kettle, setting the microwave power to be 3-4W and the initial pressure to be 0.2-0.3MPa, heating to 85-100 ℃ at the speed of 12-15 ℃/min, regulating the pressure in the process to be 0.4-0.5MPa, carrying out microwave reaction for 0.5-1h, naturally cooling to room temperature after the reaction is finished, and carrying out suction filtration, washing and drying on the product to obtain the copper-doped mesoporous silicon oxide.
Further preferred is a rapid energy-saving synthesis method of high-acidity active site copper-doped mesoporous silica as described above, wherein the molar concentration of the soluble copper salt in the mixed suspension is 0.005-0.063mol/L.
Still further preferably, a rapid energy-saving synthesis method of high-acidity active site copper-doped mesoporous silica as described above, wherein the soluble copper salt is selected from one or more of the following: copper chloride, copper sulfate, copper acetate, and copper nitrate.
Further preferably, the rapid energy-saving synthesis method of the high-acidity active site copper-doped mesoporous silica is as described above, wherein the mesoporous silica is SBA-15, MCM-41, FDU-5, KIT-6, HMS or MSU.
Further preferred is a rapid energy-saving synthesis method of high acid active site copper doped mesoporous silica as described above, wherein the ratio of mesoporous silica to water is 1g: (40-60) mL.
Further preferably, the rapid energy-saving synthesis method of the high-acidity active site copper-doped mesoporous silica is as described above, wherein the drying temperature in the step (2) is 60-80 ℃.
Further preferably, as described above, the method for rapid energy-saving synthesis of high-acidity active site copper-doped mesoporous silica has a copper doping ratio of 0.94-17.01% in the copper-doped mesoporous silica molecular sieve obtained in the step (2), a copper salt utilization ratio of 80-90%, and a specific surface area of 612-968cm 2 /g。
Compared with the prior art, the invention has the following technical effects:
(1) According to the method, the rapid and effective doping of copper elements in the mesoporous silica skeleton is realized through the assistance of microwaves, the traditional reaction time is shortened to 0.5-1h, so that the energy consumption and the time are less than those of the traditional method, and the synthesis efficiency is higher; meanwhile, the utilization rate of copper salt can reach 80-90%.
(2) The method realizes the controllable adjustment of the doping amount of copper element in the mesoporous silica skeleton, the atomic ratio of Cu/Si is 0.0094-0.205, and the doping rate of copper (molar percentage of copper) is 0.93-17.01%.
(3) The method of the invention uses low-cost water to replace organic solvent as dispersing agent, which not only reduces production cost, but also is more green and environment-friendly, and simultaneously the obtained copper doped mesoporous silica maintains higher order degree, and the specific surface area reaches 612-968cm 2 /g。
(4) The invention has simple and controllable treatment process, energy and time saving and low cost.
Drawings
FIG. 1 is an XRD pattern of a copper-doped SBA-15 mesoporous material according to example 1 of the present invention;
FIG. 2 is a TEM image of a copper-doped SBA-15 mesoporous material according to example 1 of the present invention;
FIG. 3 shows the nitrogen adsorption and pore size distribution of the copper-doped SBA-15 mesoporous material of example 1 of the present invention;
FIG. 4 is a chart showing the solid ultraviolet absorption spectrum of the copper-doped SBA-15 mesoporous material in example 1 of the present invention;
FIG. 5 is a schematic diagram of a copper-doped SBA-15 mesoporous material NH according to example 1 of the present invention 3 -TPD chemisorption drawing;
FIG. 6 is a chart showing the process of the present invention for preparing a Cu-doped MCM-41 mesoporous material NH according to example 2 3 -TPD chemisorption drawing;
FIG. 7 is a TEM image of a copper-doped MCM-41 mesoporous material according to example 2 of the present invention;
FIG. 8 is a schematic diagram of a Cu-doped KIT-6 mesoporous material NH according to example 3 of the present invention 3 -TPD chemisorption drawing;
FIG. 9 is a TEM image of a copper-doped KIT-6 mesoporous material according to example 3 of the present invention;
FIG. 10 is an XRD pattern of the product obtained in comparative example 1;
FIG. 11 is a TEM image of the product obtained in comparative example 1.
Detailed Description
The technical solutions of the present invention will be clearly and completely described with reference to the following examples, which are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. In addition, the specific technical operation steps or conditions are not noted in the examples, and are carried out according to the techniques or conditions described in the literature in the field or according to the product specifications. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1 preparation of copper doped mesoporous silica molecular sieve material:
respectively dispersing 0.25g of SBA-15, MCM-41, FDU-5, KIT-6, HMS and MSU in 15mL of water, respectively adding 0.19g of cupric acetate monohydrate, and stirring for 1min; transferring the reaction system into a microwave reaction kettle, setting the microwave power to be 3W, presetting the initial pressure to be 0.3MPa, heating to 85 ℃ at the speed of 15 ℃/min, then regulating the process pressure to be 0.4MPa, carrying out microwave reaction for 1h, naturally cooling to room temperature after the reaction is finished, and carrying out suction filtration, washing and drying at 60 ℃ on the product for 12h to obtain the deep blue copper doped mesoporous silica molecular sieve.
The composition, mesoporous structure and microstructure of the prepared copper-doped SBA-15 mesoporous molecular sieve material are analyzed and characterized by the characterization means such as XRD, TEM, physical adsorption, solid ultraviolet, ICP-OES, chemical adsorption analysis and the like.
(1) Mesoporous structure analysis (Small angle XRD, TEM and physical adsorption)
As shown in FIG. 1A, in order to obtain an X-ray powder diffraction pattern of the copper doped SBA-15 mesoporous molecular sieve material, characteristic diffraction peaks of (100), (110) and (200) crystal faces appear in a low angle range of 0.5-4 degrees, and a highly ordered two-dimensional hexagonal mesoscopic structure is synthesized; as can be seen from the high angle XRD pattern 1B, cuO impurities were not formed.
As shown in a TEM image of the copper-doped SBA-15 mesoporous molecular sieve material in fig. 2, the copper-doped SBA-15 mesoporous molecular sieve material can be seen to have regular hexagonal pore channels in the direction of vertical pore channels, wherein black shadows are shown as pore walls, white is shown as pore channels, and oxide particles are not formed in the pore channels or outside the pore channels.
As shown in FIG. 3, the copper-doped SBA-15 mesoporous molecular sieve material has nitrogen adsorption and pore size distribution, and the specific surface area is 968cm 2 And/g. N can be seen in the figure 2 Adsorption/desorption isotherms are typical type IV curves with an H1 hysteresis loop due to N 2 The capillary condensation phenomenon of the molecules in the mesopores is caused, which shows that the pore size distribution of the sample is narrow and uniform, which is consistent with the result of the pore size distribution, and the average pore diameter is 6.2nm.
(2) Solid ultraviolet absorption Spectroscopy (UV-vis DRS) and ICP analysis
FIG. 4 shows a solid ultraviolet absorption spectrum of the copper-doped SBA-15 mesoporous molecular sieve material, wherein ultraviolet absorption peaks appear between 200 nm and 300nm, and the signals can be classified as tetrahedrally coordinated Cu species doped in a framework, which indicates that Cu element is doped in the framework structure. From ICP-OES analysis, cu/si=0.205, doping ratio 17.01%, copper salt utilization up to 90%.
(3)NH 3 TPD chemisorption analysis
As shown in FIG. 5, the mesoporous molecular sieve material NH of the copper doped SBA-15 3 TPD chemisorption diagram, NH according to copper doped SBA-15 3 TPD results show that a stronger NH is present in the accessory at 200 DEG C 3 The desorption peak proves that a Cu-O-Si bond is formed, and a high-density acid active site is generated, which shows that Cu element is successfully doped in the framework structure of SBA-15 to form a solid acid catalyst.
Analysis characterization of copper doped MCM-41, FDU-5, KIT-6, HMS and MSU mesoporous silica molecular sieve materials by XRD, SEM, TEM, ICP-OES, solid ultraviolet, physical adsorption and chemical adsorption respectively shows that Cu-MCM-41, 16.2% Cu-FDU-5, 16.9% Cu-KIT-6, 15.9% Cu-HMS and 15.9% Cu-MSU mesoporous molecular sieve materials with doping rates of 16.8% are successfully prepared.
In conclusion, the invention successfully prepares the copper-doped mesoporous silica solid acid catalyst with high acid active sites and high order.
In this example, copper acetate was also replaced with copper chloride, copper sulfate, and copper nitrate, respectively, and the remaining processes were the same, and the product was characterized and found to be the same as in the case of copper acetate.
Example 2 preparation of copper doped mesoporous silica molecular sieve material:
respectively dispersing 0.25g of SBA-15, MCM-41, FDU-5, KIT-6, HMS and MSU in 10mL of water, respectively adding 0.01g of cupric acetate monohydrate, and stirring for 1min; transferring the reaction system into a microwave reaction kettle, setting the microwave power to be 3W, presetting the initial pressure to be 0.3MPa, heating to 100 ℃ at the speed of 10 ℃/min, regulating the process pressure to be 0.5MPa, carrying out microwave reaction for 0.5h, naturally cooling to room temperature after the reaction is finished, and carrying out suction filtration, washing and drying at 60 ℃ on the product for 12h to obtain the blue copper doped mesoporous silica molecular sieve.
Analysis characterization of XRD, TEM, ICP-OES, solid ultraviolet, physical adsorption and chemical adsorption of the product shows that the copper doped mesoporous silica molecular sieve material is successfully prepared, the doping rate is 0.93% Cu-MCM-41,0.95% Cu-SBA-15,0.93% Cu-FDU-5,0.93% Cu-KIT-6,0.96% Cu-HMS and 0.96% Cu-MSU mesoporous molecular sieve material respectively, and copper oxide is not found in the prepared product. The above materials all create acid active sites. As shown in FIG. 6, the copper doped MCM-41 mesoporous molecular sieve material NH 3 TPD chemisorption, from which it is seen that strong NH is present in the attachments at 200℃and 350 DEG C 3 The desorption peak proves that a Cu-O-Si bond is formed and an acid active site is generated, which shows that Cu element is successfully doped in the MCM-41 framework structure to form the solid acid catalyst. As shown in fig. 7, which is a TEM image of a copper-doped MCM-41 mesoporous molecular sieve material, it can be seen that it has regular hexagonal cells in the vertical cell direction, where the black image is shown as cell walls, and the white color is shown as cells, and no oxide particles are formed in or outside the cells.
In conclusion, the invention successfully prepares the copper-doped highly ordered mesoporous silica solid acid catalyst.
In this example, copper acetate was also replaced with copper chloride, copper sulfate, and copper nitrate, respectively, and the remaining processes were the same, and the product was characterized and found to be the same as in the case of copper acetate.
Example 3 preparation of copper doped mesoporous silica molecular sieve material:
respectively dispersing 0.25g of SBA-15, MCM-41, FDU-5, KIT-6, HMS and MSU in 12mL of water, respectively adding 0.1g of cupric acetate monohydrate, and stirring for 1min; transferring the reaction system into a microwave reaction kettle, setting the microwave power to be 3W, presetting the initial pressure to be 0.3MPa, heating to 90 ℃ at the speed of 13 ℃/min, regulating the process pressure to be 0.5MPa, carrying out microwave reaction for 0.7h, naturally cooling to room temperature after the reaction is finished, and carrying out suction filtration, washing and drying at 60 ℃ on the product for 12h to obtain the blue copper doped mesoporous silica molecular sieve.
Analysis characterization of XRD, TEM, ICP-OES, solid ultraviolet, physical adsorption and chemical adsorption of the product shows that the copper doped mesoporous silica molecular sieve material is successfully prepared, the doping rate is 8.9% Cu-MCM-41,8.9% Cu-SBA-15,8.8% Cu-FDU-5,8.9% Cu-KIT-6,8.7% Cu-HMS and 8.7% Cu-MSU mesoporous molecular sieve material respectively, and copper oxide is not found in the prepared product. The above materials all create acid active sites. FIG. 8 shows a copper doped KIT-6 mesoporous molecular sieve material NH 3 TPD chemisorption, from which it is seen that strong NH is present in the attachments at 200℃and 350 DEG C 3 The desorption peak proves that a Cu-O-Si bond is formed, and an acid active site is generated, which shows that Cu element is successfully doped in the framework structure of KIT-6 to form a solid acid catalyst. As shown in a TEM image of the copper-doped KIT-6 mesoporous molecular sieve material in FIG. 9, the mesoporous molecular sieve material has regular hexagonal pore channels in the direction perpendicular to the pore channels, and oxide particles are not formed in or outside the pore channels.
In conclusion, the invention successfully prepares the copper-doped highly ordered mesoporous silica solid acid catalyst.
In this example, copper acetate was also replaced with copper chloride, copper sulfate, and copper nitrate, respectively, and the remaining processes were the same, and the product was characterized and found to be the same as in the case of copper acetate.
Comparative example 1
The treatment process and parameters were the same as in example 1 of the present invention, except that the microwave reaction was carried out for 1 hour at a process pressure of 0.6MPa to obtain a blue product, and XRD (fig. 10) and TEM (fig. 11) analysis of the product Cu-SBA-15 revealed that the mesoporous structure was destroyed, and the pore structure was not observed basically.
Comparative example 2
The treatment process and parameters were the same as in example 1 of the present invention, except that the process pressure was 0.2MPa, the microwave reaction was carried out for 1h, white products were obtained, and ICP-OES analysis of the products, respectively, showed that Cu/si=0, all the Cu-doped mesoporous silica molecular sieve materials were not formed.
Comparative example 3
The treatment process and parameters were the same as in example 1 of the present invention, except that the microwave power was set to 6W, both gray products were obtained, and CuO-loaded copper-doped mesoporous silica molecular sieve materials were possibly formed in the products.
Comparative example 4
The treatment process and parameters are the same as those of the embodiment 1, except that the gray product is obtained after the microwave reaction for 1.2 hours, and the copper-doped mesoporous silica molecular sieve material loaded by CuO may be formed in the product.
Comparative example 5
The treatment process and parameters were the same as in example 1 of the present invention, except that the microwave reaction was carried out for 10min to obtain a white product, and the ICP-OES analysis of the product showed that Cu/si=0, and no Cu-doped mesoporous silica molecular sieve material was formed.
Comparative example 6
The treatment process and parameters were the same as in example 1 of the present invention except that the white product was obtained by microwave reaction at 75 ℃ for 1 hour, and the ICP-OES analysis of the product, respectively, showed that Cu/si=0, and no Cu-doped mesoporous silica molecular sieve material was formed.
Comparative example 7
The treatment process and parameters are the same as those of the embodiment 1, except that the gray product is obtained after the microwave reaction for 1h at 110 ℃, and the copper-doped mesoporous silica molecular sieve material loaded by CuO can be formed in the product.
Comparative example 8
The treatment process and parameters were the same as in example 1 of the present invention, except that the white product was obtained in 15mL of ethanol as the solvent, and ICP-OES analysis of the product, respectively, showed that Cu/si=0, and no Cu-doped mesoporous silica molecular sieve material was formed.
Claims (7)
1. A rapid energy-saving synthesis method of high-acidity active site copper doped mesoporous silicon oxide is characterized by comprising the following steps:
(1) Dispersing mesoporous silica and soluble copper salt in water to obtain mixed suspension, wherein the molar ratio of the mesoporous silica to the copper salt is 1 (4.39-83.4);
(2) Placing the mixed suspension in a microwave reaction kettle, setting the microwave power to be 3-4W and the initial pressure to be 0.2-0.3MPa, heating to 85-100 ℃ at the speed of 12-15 ℃/min, regulating the pressure in the process to be 0.4-0.5MPa, carrying out microwave reaction for 0.5-1h, naturally cooling to room temperature after the reaction is finished, and carrying out suction filtration, washing and drying on the product to obtain the copper-doped mesoporous silicon oxide.
2. The rapid energy-saving synthesis method of high-acidity active site copper-doped mesoporous silica according to claim 1, wherein the molar concentration of the soluble copper salt in the mixed suspension is 0.005-0.063mol/L.
3. The rapid energy-saving synthesis method of high-acidity active site copper-doped mesoporous silica according to claim 2, wherein the soluble copper salt is selected from one or more of the following: copper chloride, copper sulfate, copper acetate, and copper nitrate.
4. The rapid energy-saving synthesis method of high-acidity active site copper-doped mesoporous silica according to claim 1, wherein the mesoporous silica is SBA-15, MCM-41, FDU-5, KIT-6, HMS or MSU.
5. The rapid energy-saving synthesis method of high-acidity active site copper-doped mesoporous silica according to claim 1, wherein the ratio of mesoporous silica to water is 1g: (40-60) mL.
6. The rapid energy-saving synthesis method of high-acidity active site copper-doped mesoporous silica according to claim 1, wherein the drying temperature is 60-80 ℃.
7. The rapid energy-saving synthesis method of high-acidity active site copper-doped mesoporous silica according to claim 1, wherein the copper doping ratio in the copper-doped mesoporous silica obtained in the step (2) is 0.94-17.01%, the copper salt utilization ratio is 80-90%, and the specific surface area is 612-968cm 2 /g。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211278125.1A CN115646531B (en) | 2022-10-19 | 2022-10-19 | Rapid energy-saving synthesis method of high-acidity active site copper doped mesoporous silicon oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211278125.1A CN115646531B (en) | 2022-10-19 | 2022-10-19 | Rapid energy-saving synthesis method of high-acidity active site copper doped mesoporous silicon oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115646531A CN115646531A (en) | 2023-01-31 |
| CN115646531B true CN115646531B (en) | 2023-12-01 |
Family
ID=84989401
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211278125.1A Active CN115646531B (en) | 2022-10-19 | 2022-10-19 | Rapid energy-saving synthesis method of high-acidity active site copper doped mesoporous silicon oxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115646531B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090124864A (en) * | 2008-05-31 | 2009-12-03 | 인하대학교 산학협력단 | Mesoporous silica substituted with metal and preparing method thereof |
| CN102001677A (en) * | 2010-09-14 | 2011-04-06 | 江苏大学 | Synthesis method of europium containing MCM-41 mesoporous molecular sieve |
| CN103433023A (en) * | 2013-08-15 | 2013-12-11 | 陕西科技大学 | Gd-doped BiVO4 photocatalyst as well as preparation method and application thereof |
| CN106315609A (en) * | 2016-07-29 | 2017-01-11 | 辽宁石油化工大学 | Preparation method of one-step method microporous/mesoporous composite molecular sieve with framework doped with rare earth in complexing mode |
| CN108054381A (en) * | 2017-12-29 | 2018-05-18 | 济南大学 | A kind of rear-earth-doped type lithium manganese silicate anode material and its microwave radiation technology preparation method |
| CN108355657A (en) * | 2018-02-07 | 2018-08-03 | 苏州科技大学 | A kind of method of metal-doped mesopore silicon oxide of the fabricated in situ with efficient catalytic degradation of methylene blue |
| CN109046439A (en) * | 2018-08-27 | 2018-12-21 | 宝鸡文理学院 | A kind of synthetic method of highly doped amount peracidity position mesopore silicon oxide solid acid catalyst |
| CN111135851A (en) * | 2020-01-03 | 2020-05-12 | 宝鸡文理学院 | Medium-low temperature rapid demoulding-copper doping method for mesoporous silicon oxide |
| CN112619663A (en) * | 2020-09-10 | 2021-04-09 | 何俊 | Cobalt or copper doped birnessite catalyst, preparation method and application thereof |
-
2022
- 2022-10-19 CN CN202211278125.1A patent/CN115646531B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090124864A (en) * | 2008-05-31 | 2009-12-03 | 인하대학교 산학협력단 | Mesoporous silica substituted with metal and preparing method thereof |
| CN102001677A (en) * | 2010-09-14 | 2011-04-06 | 江苏大学 | Synthesis method of europium containing MCM-41 mesoporous molecular sieve |
| CN103433023A (en) * | 2013-08-15 | 2013-12-11 | 陕西科技大学 | Gd-doped BiVO4 photocatalyst as well as preparation method and application thereof |
| CN106315609A (en) * | 2016-07-29 | 2017-01-11 | 辽宁石油化工大学 | Preparation method of one-step method microporous/mesoporous composite molecular sieve with framework doped with rare earth in complexing mode |
| CN108054381A (en) * | 2017-12-29 | 2018-05-18 | 济南大学 | A kind of rear-earth-doped type lithium manganese silicate anode material and its microwave radiation technology preparation method |
| CN108355657A (en) * | 2018-02-07 | 2018-08-03 | 苏州科技大学 | A kind of method of metal-doped mesopore silicon oxide of the fabricated in situ with efficient catalytic degradation of methylene blue |
| CN109046439A (en) * | 2018-08-27 | 2018-12-21 | 宝鸡文理学院 | A kind of synthetic method of highly doped amount peracidity position mesopore silicon oxide solid acid catalyst |
| CN111135851A (en) * | 2020-01-03 | 2020-05-12 | 宝鸡文理学院 | Medium-low temperature rapid demoulding-copper doping method for mesoporous silicon oxide |
| CN112619663A (en) * | 2020-09-10 | 2021-04-09 | 何俊 | Cobalt or copper doped birnessite catalyst, preparation method and application thereof |
Non-Patent Citations (10)
| Title |
|---|
| Acidic properties of CoCl2•6H2O and NiCl2•6H2O microwave ion exchanged NaY zeolite;Zendehdel, M等;ASIAN JOURNAL OF CHEMISTRY;第19卷(第3期);1802-1808 * |
| Application of microwave radiation in the grafting of acidic sites on SBA‑15 type material;Maciej Trejda等;Journal of Porous Materials;全文 * |
| Characterization of CoMCM-41 mesoporous molecular sieves obtained by the microwave irradiation method;Tingshun Jiang等;Journal of Solid State Chemistry;全文 * |
| Efficient Fenton-like treatment of high-concentration chlorophenol wastewater catalysed by Cu-Doped SBA-15 mesoporous silica;Huanting Hu等;Journal of Cleaner Production;第318卷;全文 * |
| Fe、Cu共掺杂SBA一15介孔氧化硅的绿色合成及其表征;裴霏等;化学与粘合;全文 * |
| Preparation and characterization of (SBA-15)–La2O3host–guest composite materials;Hui Yu等;Journal of Solid State Chemistry;第181卷;全文 * |
| Rapid synthesis of La–Ce–silica mesoporous SBA-15-type material via microwave technique;Guoqian Chen等;J Porous Mater;第16卷;361–365 * |
| 不同方法合成铈掺杂介孑L分子筛的结构性能;姜哲等;当代化工;全文 * |
| 微波条件下杂原子MCM．41介孔分子筛的合成;姜廷顺等;中国有色金属学报;全文 * |
| 铈掺杂氧化锌六角杯型结构纳米光催化剂的制备及其性能研究;郭凯妍等;浙江师范大学学报（自然科学版）;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115646531A (en) | 2023-01-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108993550B (en) | Surface oxygen vacancy modified bismuth oxybromide photocatalyst and preparation method thereof | |
| CN114534759A (en) | Monoatomic cobalt-supported tubular carbon nitride catalyst and preparation method and application thereof | |
| CN108821311B (en) | Preparation method of prussian white mesomorphic material with fine and adjustable ferromanganese component | |
| CN111533124A (en) | Two-dimensional nitrogen-doped nano porous carbon material and preparation method thereof | |
| CN112337461A (en) | Composite material of strontium-doped ordered mesoporous lanthanum manganate-loaded noble metal palladium, preparation method thereof and application thereof in catalytic oxidation of toluene | |
| CN110813300B (en) | Cobalt-zinc-loaded bimetallic nano-carbon material, preparation method thereof and application thereof in catalytic oxidation of magnesium sulfite | |
| CN115007182B (en) | Preparation method of potassium-oxygen co-doped graphite-phase carbon nitride photocatalyst | |
| CN112892521A (en) | Oxygen-enriched vacancy echinoid tungsten oxide and preparation method and application thereof | |
| CN108285152B (en) | Green and efficient synthesis method of copper-doped SBA-15 mesoporous molecular sieve material | |
| CN113058655A (en) | Preparation method and application of BiOCl/Fe-MOFs composite catalytic material | |
| CN115069290A (en) | Nitrogen-defect-containing porous carbon nitride-loaded monoatomic copper catalyst, preparation method thereof and application thereof in light nitrogen fixation | |
| CN113976155A (en) | Preparation method of porous carbon nitride-ferrite composite catalyst with nitrogen/oxygen-containing double defect structure and application of photocatalyst in nitrogen fixation | |
| CN110745864B (en) | Perovskite type lanthanum titanate material and preparation method and application thereof | |
| CN113332990B (en) | Perovskite catalytic material and green synthesis method and application thereof | |
| CN111250146A (en) | Preparation method of oxygen-enriched BiOI-BiOBr/SBA-16 composite photocatalytic material | |
| CN113736094B (en) | Synthesis method of hierarchical porous ZIF-9 | |
| CN113135578B (en) | Preparation method of silicon-germanium ISV zeolite molecular sieve | |
| CN115646531B (en) | Rapid energy-saving synthesis method of high-acidity active site copper doped mesoporous silicon oxide | |
| CN111186824B (en) | Preparation method of high-specific-surface-area defective carbon nitride | |
| CN109772419B (en) | Preparation method for constructing carbon nitride-based ultrathin nanosheet composite material in confined space | |
| EP3838843A1 (en) | Hierarchical zeolites and preparation method therefor | |
| CN113559920A (en) | ZSM-5 molecular sieve/titanium dioxide composite material and preparation method thereof | |
| CN111974428A (en) | Bi2O2CO3-Bi2WO6Preparation method of composite photocatalyst | |
| CN112871174A (en) | Preparation method and application of hexagonal flaky nano nickel oxide catalyst | |
| CN114685808B (en) | Hydrogen bond associated pseudo three-dimensional titanium-carbon-based micro complex with one-dimensional pores opened, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |