CN102583545B - Preparation method of three-dimensional ordered mesoporous molybdenum oxide - Google Patents
Preparation method of three-dimensional ordered mesoporous molybdenum oxide Download PDFInfo
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- CN102583545B CN102583545B CN201210057554.6A CN201210057554A CN102583545B CN 102583545 B CN102583545 B CN 102583545B CN 201210057554 A CN201210057554 A CN 201210057554A CN 102583545 B CN102583545 B CN 102583545B
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Abstract
The invention provides a preparation method of three-dimensional ordered mesoporous molybdenum oxide and belongs to the technical field of solid mesoporous material preparation. The existing mesoporous molybdenum oxide has the problems that the pore passage structure is undeveloped, the specific surface area is small, the preparation method is single, and the like. The method provided by the invention uses ethyl orthosilicate as raw materials, triblock copolymer (EO)20(PO)70(EO)20 as a template agent and normal butanol as auxiliary solution, cubic phase three-dimensional mesoporous monox powder KIT-6 is synthesized through hydrothermal reaction, then, the cubic phase three-dimensional mesoporous monox powder KIT-6 is used as a hard template agent, cane sugar is used as a carbon source, and three-dimensional mesoporous carbon with high specific surface area and developed pore structure is synthesized. Finally, the three-dimensional mesoporous carbon is used as a template agent, a vacuum and ultrasonic method is utilized in an auxiliary way, ammonium heptamolybdate in different concentrations is used as a metal precursor, and the three-dimensional ordered mesoporous molybdenum oxide with high specific surface area is synthesized through different-time ultrasonic irradiation at different evaporating temperatures. The preparation method has the advantages that the cost is low, the operation is simple, the pore diameter distribution of the prepared three-dimensional ordered mesoporous molybdenum oxide is narrow, the specific surface area is large, and the like.
Description
Technical field
The present invention relates to a kind of technology of preparing of solid mesoporous material, be specifically related to a kind ofly with three-dimensional meso-hole silicon oxide powder KIT-6, produce three-dimensional meso-hole carbon, the three-dimensional meso-hole carbon of then take utilizes vacuum to add the ultrasonic method of preparing three-dimensional ordered mesoporous molybdenum oxide as hard template is auxiliary.
Background technology
Molybdic oxide has been widely applied to every field, catalyzer, and sensor, audio-video materials, electrode materialss etc. are also made into the material that various patterns have various characteristics.In recent years, nanoparticle and ordered porous materials technology of preparing have obtained development rapidly, make this type of material of controlledly synthesis become possibility.Because mesopore oxide material not only has some special propertys such as the mutability of higher specific surface area and pore volume but also component and valence state and crystal network structure, become the important research object of the aspects such as surface tissue and heterogeneous catalyst, be widely used separated from the gas, heterogeneous catalyst, energy storage, electromagnetism, the various fields such as photoelectricity.Therefore the preparation method who researches and develops the mesopore metal oxide of high-specific surface area has great practical value.
The at present preparation of mesoporous molybdenum oxide adopts dissipation of heat method conventionally, is about to molybdenum oxide and mesoporous silicon template and after high-temperature roasting, makes after by long grinding again.For example, the people such as Li is distributed to molybdic oxide in mesoporous silica molecular sieve MCM-41 and obtains MoO by dissipation of heat method
3/ MCM-41.(Z.Li，et?al.，Appl.Catal.A，2002，236：163)。The people such as Pavel Topka adopt heat treating process that molybdenum oxide is made to the molybdenum oxide of silicon template carrying with MCM-41 and SBA-16 respectively according to certain ratio ground and mixed, heating equally.(P.Topka，et?al.，Micropor.Mesopor.Mater.，2006，96：44)。Also having a kind of conventional method is sol-gel method, utilize desired precursor and soft template to form colloidal sol, activate at a certain temperature precursor, then remove under certain conditions organic soft template, finally obtain having the target product of meso-hole structure.Such as: Shubhangi B. etc., with tetraethyl silicate-40, be soft template, ammonium molybdate is molybdenum source, and constantly roasting 12 hours at 500 ℃ after stirring synthesizes the high-specific surface area MoO of template
3/ SiO
2catalyzer (Journal of Molecular Catalysis A:Chemical 310 (2009) 150-158).The people such as Sarkar adopt ZrO
2cl
2, molybdate and cats product, through self assembling process, synthesized mesoporous ZrO
2-MoO
3, its surface-area and aperture are respectively 288m
2/ g and 3.65nm (A.Sarkar, et al., Micropor.Mesopor.Mater., 2007,115:426).The oxide compound that heat treating process obtains is carried on mesoporous silicon, because itself does not have hole, catalytic activity is reduced greatly.And during the synthesising mesoporous oxide compound of sol-gel method, due to when calcination, crystallization and the removal template, duct easily subsides and the specific surface area of product is reduced greatly, and pore passage structure is that worm channel is unordered mostly.In recent years, adopting the synthesising mesoporous oxide compound of hard template method also to cause widely pays close attention to.
Summary of the invention
The object of the invention is to solve the problems of the prior art, overcome the shortcomings such as other organic formwork method gained sample well compound with regular structure degree was poor in the past, duct easily subsides, method universality is poor, and provide a kind of pore passage structure flourishing, the synthetic method of the three-dimensional ordered mesoporous molybdenum oxide that specific surface area is higher.
Method provided by the present invention is that first to take tetraethoxy (TEOS) be raw material, with triblock copolymer (EO)
20(PO)
70(EO)
20(PluronicP123) be template, take propyl carbinol as assisted solution, by hydro-thermal reaction, synthesize Emission in Cubic three-dimensional meso-hole silicon oxide powder (KIT-6), then take it as hard mould agent, sucrose is carbon source, synthesizes the three-dimensional meso-hole carbon of high-specific surface area and flourishing pore structure, finally take three-dimensional meso-hole carbon as hard mould agent, take Ammonium Heptamolybdate as metal precursor, the three-dimensional ordered mesoporous molybdenum oxide of synthesizing high specific surface area
1. a method for synthetic three-dimensional ordered mesoporous molybdenum oxide, is characterized in that, concrete building-up process is as follows:
1) first synthesize hard mould agent three-dimensional meso-hole silicon oxide powder;
2) take step 1) in the three-dimensional meso-hole silicon oxide powder of preparation be hard template, sucrose is carbon source, prepares three-dimensional meso-hole carbon;
3) by step 2) in preparation three-dimensional meso-hole carbon dust vacuumize, after exhausting vacuum, vacuum pump is turned off, the ammonium molybdate aqueous solution that is 0.02-0.04mol/L by concentration is again added drop-wise in three-dimensional meso-hole carbon by dropping funnel under vacuum state, wherein, and mesoporous carbon powder and (NH
4)
6mo
7o
24mol ratio be 1: 0.01-0.02.After dropwising, under vacuum state, ultrasonic wave disperses to make for 80-120 minute (NH
4)
6mo
7o
24molecule fully enters in the duct of three-dimensional meso-hole carbon;
4) after last 40-60 ℃ of heating evaporated its moisture completely, in the tube furnace of the stream of nitrogen gas that is 100ml/min in volumetric flow rate by the solid of gained, with the speed of 1 ℃/min, rise to 500 ℃ and calcination 2 hours, the air draught that again stream of nitrogen gas is changed into 100ml/min continues speed with 1 ℃/min and is warming up to 550 ℃ and constant temperature calcination 2 hours, obtains three-dimensional ordered mesoporous molybdenum oxide.
Concrete steps are as follows:
1) take tetraethoxy (TEOS) is raw material, triblock copolymer polyethylene glycol-propylene glycol-polyoxyethylene glycol (EO)
20(PO)
70(EO)
20(PluronicP123) be soft template, take propyl carbinol as assisted solution, by hydro-thermal reaction, synthesize three-dimensional meso-hole silicon oxide powder KIT-6 (seeing document " Freddy K., et al.Chem.Commun., 2003,2136 ");
2) take step 1) in the three-dimensional meso-hole silicon oxide powder of preparation be hard template, sucrose is carbon source, with reference to patented method (CN101117222), prepares three-dimensional meso-hole carbon.Its building-up process is: KIT-6 is joined by sucrose: deionized water: massfraction is that 98% vitriol oil mol ratio is 1: 0.219: 20: in 0.0875 mixed solution forming, magnetic agitation makes the evaporation of moisture in this mixed solution completely, then it is put into the successively constant temperature processing of baking oven 6 hours of 80 ℃ and 160 ℃.In the powder of gained, add again by sucrose: deionized water: vitriol oil mol ratio is that the mixed solution that forms at 0.132: 20: 0.05 repeats magnetic agitation and drying operation once again.The solid obtaining in nitrogen atmosphere with the speed temperature programming to 900 of 1 ℃/min ℃ constant temperature calcination 2 hours at this temperature, with massfraction be 10%HF solution washing gained pressed powder to remove silicon template, more obtain three-dimensional meso-hole carbon after seasoning;
3) by step 2) in the three-dimensional meso-hole carbon dust of preparation put into divergent ends and connect the Erlenmeyer flask that the vacuum pump the other end is connected with the dropping funnel of piston, under 90KPa, vacuumize 60 minutes, wherein, between Erlenmeyer flask and vacuum pump, be connected with surge flask to guarantee the vacuum tightness in Erlenmeyer flask.After exhausting vacuum, vacuum pump is turned off, then (the NH that is 0.02-0.04mol/L by concentration
4)
6mo
7o
24the aqueous solution is slowly added drop-wise in three-dimensional meso-hole carbon by dropping funnel under vacuum state.After dropwising, continue to keep its vacuum tightness ultrasonic wave to disperse to make for 80-120 minute in duct that molecule fully enters three-dimensional meso-hole carbon Erlenmeyer flask;
4) after last 40-60 ℃ of heating evaporated its moisture completely, in the tube furnace of the stream of nitrogen gas that is 100ml/min in volumetric flow rate by the solid of gained, with the speed of 1 ℃/min, rise to 500 ℃ and calcination 2 hours, the air draught that again stream of nitrogen gas is changed into 100ml/min continues speed with 1 ℃/min and is warming up to 550 ℃ and constant temperature calcination 2 hours, obtains three-dimensional ordered mesoporous molybdenum oxide.
Utilize X-ray diffraction (XRD), N
2the physical properties of the characterized by techniques products therefroms such as adsorption-desorption, transmission electron microscope (TEM) and selected area electron diffraction (SAED).Result shows, adopting the prepared sample of the inventive method is the mesoporous molybdic oxide with orderly pore passage structure and high-specific surface area, and specific surface area is 233-262m
2/ g, aperture is 8-9.2nm.
The present invention utilizes three-dimensional meso-hole carbon for hard mould agent, conveniently finally remove template and obtain mesopore oxide, having avoided adopting silicon template to prepare mesoporous molybdenum oxide need remove template and destroy the shortcoming of molybdic oxide with NaOH or HF, can effectively overcome prior art deficiency, the method cost providing is low, operating process is simple, target product pore size distribution is narrow, specific surface area is large, and pattern that can be by modulation mesoporous carbon and meso-hole structure etc. are realized the control to molybdenum oxide particle morphology, pore structure and specific surface area.Also do not have at present document and patent report to cross method of the present invention.
Accompanying drawing explanation:
In order further to understand the present invention, with embodiment, elaborate below, and provide accompanying drawing and describe the high specific surface area ordered mesoporous molybdic oxide that the present invention obtains, wherein:
Fig. 1 uses while being synthesizing ordered mesoporous molybdic oxide vacuumizes immersion system.
Fig. 2 A, 2B are respectively the three-dimensional meso-hole silicon oxide KIT-6 of synthesized and as the TEM photo of the synthetic three-dimensional meso-hole carbon of hard mould agent.
Fig. 3 is the XRD spectra of embodiment 1 sample three-dimensional ordered mesoporous molybdenum oxide, and wherein a is wide-angle XRD spectra, and b is little angle XRD spectra.
Fig. 4 A, 4B, 4C are respectively the TEM picture of embodiment 1, embodiment 2 and embodiment 3 samples.
Embodiment:
Case study on implementation one
1) synthetic three-dimensional meso-hole silicon oxide powder KIT-6: at room temperature, add 2.7g triblock copolymer (EO) in phase 100mL 0.5mol/L hydrochloric acid soln
20(PO)
70(EO)
20(PluronicP123), be stirred to dissolving, slowly (2 ℃/min) are warming up to 35 ℃, under stirring state, add 2.8g propyl carbinol, and keep 35 ℃ to stir 1 hour, then (mol ratio of each material is: tetraethoxy: triblock copolymer (EO) to above-mentioned solution, to add 5.8g tetraethoxy
20(PO)
70(EO)
20: hydrochloric acid: deionized water: propyl carbinol=1: 0.017: 1.83: 195: 1.31), keep 35 ℃ to stir 24 hours, proceed to self-pressure still 100 ℃ of hydro-thermals 24 hours, after filtration, dry at 60 ℃ after deionized water and washing with alcohol, then at retort furnace Program, heat up (1 ℃/min) to 550 ℃ and calcination 4 hours at 550 ℃, obtain three-dimensional meso-hole silicon oxide (KIT-6) white powder.The specific surface area of gained KIT-6 is 780m
2/ g, mean pore size is 3nm;
2) synthetic three-dimensional ordered mesoporous carbon: it is in the mixed solution that forms of 98% the vitriol oil that three-dimensional meso-hole silicon oxide powder is joined to sucrose, deionized water and massfraction, after magnetic agitation evaporates the moisture in mixed solution, the baking oven that it is put into 80 ℃ and 160 ℃ successively respectively constant temperature is processed 6 hours.Repeat above-mentioned steps 2-3 time, in the stream of nitrogen gas that is 100ml/min in volumetric flow rate by the pressed powder finally obtaining with the speed temperature programming to 900 of 1 ℃/min ℃ constant temperature calcination 2 hours at this temperature, with massfraction, be that 10%HF solution washing gained pressed powder is to remove silicon template KIT-6,, then after seasoning, obtain three-dimensional meso-hole carbon;
3) by 0.5g step 2) in the three-dimensional meso-hole carbon dust of preparation put into divergent ends and connect the Erlenmeyer flask that the vacuum pump the other end is connected with the dropping funnel of piston, under 90KPa, vacuumize 60 minutes, wherein, between Erlenmeyer flask and vacuum pump, be connected with surge flask to guarantee the vacuum tightness in Erlenmeyer flask.After exhausting vacuum, vacuum pump is turned off, then (the NH that is 0.02mol/L by 20ml concentration
4)
6mo
7o
24the aqueous solution is slowly added drop-wise in three-dimensional meso-hole carbon by dropping funnel under vacuum state.After dropwising, continue to keep its vacuum tightness ultrasonic wave to disperse to make for 80 minutes in duct that molecule fully enters three-dimensional meso-hole carbon Erlenmeyer flask;
4) after last 40 ℃ of heating are evaporated its moisture completely, in the tube furnace of the stream of nitrogen gas that is 100ml/min in volumetric flow rate by the solid of gained, with the speed of 1 ℃/min, rise to 500 ℃ and calcination 2 hours, the air draught that again stream of nitrogen gas is changed into 100ml/min continues speed with 1 ℃/min and is warming up to 550 ℃ and constant temperature calcination 2 hours, obtains three-dimensional ordered mesoporous molybdenum oxide.Its specific surface area is 233m
2/ g, mean pore size is 8nm.
Case study on implementation two
1) three-dimensional meso-hole silicon oxide powder KIT-6's is synthetic with the step 1 in embodiment mono-);
2) three-dimensional ordered mesoporous carbon is synthetic with the step 2 in embodiment mono-);
3) by 0.5g step 2) in the three-dimensional meso-hole carbon dust of preparation put into divergent ends and connect the Erlenmeyer flask that the vacuum pump the other end is connected with the dropping funnel of piston, under 90KPa, vacuumize 60 minutes, wherein, between Erlenmeyer flask and vacuum pump, be connected with surge flask to guarantee the vacuum tightness in Erlenmeyer flask.After exhausting vacuum, vacuum pump is turned off, then (the NH that is 0.032mol/L by 20ml concentration
4)
6mo
7o
24the aqueous solution is slowly added drop-wise in three-dimensional meso-hole carbon by dropping funnel under vacuum state.After dropwising, continue to keep its vacuum tightness ultrasonic wave to disperse to make for 100 minutes in duct that molecule fully enters three-dimensional meso-hole carbon Erlenmeyer flask;
4) after last 50 ℃ of heating are evaporated its moisture completely, in the tube furnace of the stream of nitrogen gas that is 100ml/min in volumetric flow rate by the solid of gained, with the speed of 1 ℃/min, rise to 500 ℃ and calcination 2 hours, the air draught that again stream of nitrogen gas is changed into 100ml/min continues speed with 1 ℃/min and is warming up to 550 ℃ and constant temperature calcination 2 hours, obtain three-dimensional ordered mesoporous molybdenum oxide, its specific surface area is 259m
2/ g, mean pore size is 9.2nm.
Case study on implementation three
1) silicon template KIT-6's is synthetic with the step 1 in embodiment mono-);
2) carbon template is synthetic with the step 2 in embodiment mono-);
3) by 0.5g step 2) in the three-dimensional meso-hole carbon dust of preparation put into divergent ends and connect the Erlenmeyer flask that the vacuum pump the other end is connected with the dropping funnel of piston, under 90KPa, vacuumize 60 minutes, wherein, between Erlenmeyer flask and vacuum pump, be connected with surge flask to guarantee the vacuum tightness in Erlenmeyer flask.After exhausting vacuum, vacuum pump is turned off, then (the NH that is 0.04mol/L by 20ml concentration
4)
6mo
7o
24the aqueous solution is slowly added drop-wise in three-dimensional meso-hole carbon by dropping funnel under vacuum state.After dropwising, continue to keep its vacuum tightness ultrasonic wave to disperse to make for 120 minutes in duct that molecule fully enters three-dimensional meso-hole carbon Erlenmeyer flask;
4) after last 60 ℃ of heating are evaporated its moisture completely, in the tube furnace of the stream of nitrogen gas that is 100ml/min in volumetric flow rate by the solid of gained, with the speed of 1 ℃/min, rise to 500 ℃ and calcination 2 hours, the air draught that again stream of nitrogen gas is changed into 100ml/min continues speed with 1 ℃/min and is warming up to 550 ℃ and constant temperature calcination 2 hours, obtain three-dimensional ordered mesoporous molybdenum oxide, its specific surface area is 262m
2/ g, mean pore size is 8.5nm.
Claims (1)
1. a method for synthetic three-dimensional ordered mesoporous molybdenum oxide, is characterized in that, concrete building-up process is as follows:
1) first synthesize hard mould agent three-dimensional meso-hole silicon oxide powder;
2) take step 1) in the three-dimensional meso-hole silicon oxide powder of preparation be hard template, sucrose is carbon source, prepares three-dimensional meso-hole carbon;
3) by step 2) in preparation three-dimensional meso-hole carbon dust vacuumize, after exhausting vacuum, vacuum pump is turned off, the ammonium molybdate aqueous solution that is 0.02-0.04mol/L by concentration is again added drop-wise in three-dimensional meso-hole carbon by dropping funnel under vacuum state, wherein, and mesoporous carbon powder and (NH
4)
6mo
7o
24mol ratio be 1:0.01-0.02; After dropwising, under vacuum state, ultrasonic wave disperses to make for 80-120 minute (NH
4)
6mo
7o
24molecule fully enters in the duct of three-dimensional meso-hole carbon;
4) after last 40-60 ℃ of heating evaporated its moisture completely, in the tube furnace of the stream of nitrogen gas that is 100ml/min in volumetric flow rate by the solid of gained, with the speed of 1 ℃/min, rise to 500 ℃ and calcination 2 hours, the air draught that again stream of nitrogen gas is changed into 100mL/min continues speed with 1 ℃/min and is warming up to 550 ℃ and constant temperature calcination 2 hours, obtains three-dimensional ordered mesoporous molybdenum oxide.
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| CN106976910A (en) * | 2017-04-07 | 2017-07-25 | 中国科学院化学研究所 | A kind of porous carbon load molybdenum oxide nanoparticles composite and preparation method thereof |
| CN110729469B (en) * | 2019-10-14 | 2021-02-19 | 武汉理工大学 | High-purity high-crystallinity MoO2Preparation method of (1) |
| CN113501548A (en) * | 2021-06-10 | 2021-10-15 | 武汉大学 | Mesoporous metal oxide hollow material with high specific surface area and preparation method thereof |
| CN115417737B (en) * | 2022-09-28 | 2023-09-01 | 南京理工大学 | Molybdenum oxide-based thermite and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101007624A (en) * | 2007-01-22 | 2007-08-01 | 华东师范大学 | Method for synthesizing metal oxide mesoporous material by one-step vacuum perfusion |
| CN101117222A (en) * | 2007-07-13 | 2008-02-06 | 北京工业大学 | Method for synthesizing high specific surface area meso-porous carbon molecular sieve by using hard mould agent |
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| CN101007624A (en) * | 2007-01-22 | 2007-08-01 | 华东师范大学 | Method for synthesizing metal oxide mesoporous material by one-step vacuum perfusion |
| CN101117222A (en) * | 2007-07-13 | 2008-02-06 | 北京工业大学 | Method for synthesizing high specific surface area meso-porous carbon molecular sieve by using hard mould agent |
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| Title |
|---|
| JP特开2010-215470A 2010.09.30 |
| 介孔金属氧化物MOx(M=Cr,Fe,Co,Sm,Eu)制备及物化性质研究;夏云生;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20100930(第9期);第58页第3段至第59页第1段及图3-1 * |
| 夏云生.介孔金属氧化物MOx(M=Cr,Fe,Co,Sm,Eu)制备及物化性质研究.《中国博士学位论文全文数据库 工程科技Ⅰ辑》.2010,(第9期),第58页第3段至第59页第1段及图3-1. |
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