CN101851002B - Method for synthesizing ordered mesoporous indium oxide - Google Patents
Method for synthesizing ordered mesoporous indium oxide Download PDFInfo
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- CN101851002B CN101851002B CN200910081409XA CN200910081409A CN101851002B CN 101851002 B CN101851002 B CN 101851002B CN 200910081409X A CN200910081409X A CN 200910081409XA CN 200910081409 A CN200910081409 A CN 200910081409A CN 101851002 B CN101851002 B CN 101851002B
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Abstract
The invention relates to a method for synthesizing ordered mesoporous indium oxide. The method comprises the following steps of: pre-synthesizing mesoporous silicon oxide with relatively big hole-wall connecting holes; removing surfactant in ducts of the holes by adopting extraction treatment; and preparing the ordered mesoporous indium oxide by taking the extracted mesoporous silicon oxide as a hard template. In the method of the invention, the extraction treatment is adopted to reduce the conventional cost of the mesoporous silicon oxide preparation by using 'common' mesoporous silicon oxide and the size of the connecting holes is increased to improve the connectivity of the mesoporous silicon oxide after the extraction, so ordered mesoporous oxide materials can be prepared by using the mesoporous silicon oxide as the hard template.
Description
Technical field
The invention belongs to the inorganic porous material field, specifically relating to a kind of mesopore silicon oxide with extraction treatment is the method that hard template is come synthesizing ordered mesoporous Indium sesquioxide.
Background technology
The scientist of Mobil company in 1992 has synthesized M41S series silicon-based mesoporous material, thereby has expanded to the hole dimension scope of ordering rule porous material mesoporous from micropore; Synthetic SBA such as Stucky series silicon-based mesoporous material further promoted the hole dimension scope especially afterwards; The physicochemical property that the pore passage structure of its high-sequential, huge specific surface area and pore volume, adjustable aperture etc. are unique; Make this material at aspects such as photoelectric device, separation purification, biomaterial, catalysis, advanced composite materials huge application potential arranged, having very at numerous areas such as chemical engineering, information engineering, biotechnology, environmental energy, important use is worth.
The mesoporous material research range expands to non-silica-base material such as MOX from silicon-based mesoporous material gradually.Compare with silicon-based mesoporous material, non-silicon-based mesoporous material particularly MOX has range of application more widely owing to the variety of its component and the polytropy of valence state.The former has had a series of synthesis mechanism (like liquid crystal templated mechanism, cooperation mechanism) and preparation method (, sol-gel method synthetic like hydro-thermal): normally utilize tensio-active agent as structure directing agent; Utilize the interface interaction between itself and the silicon species to accomplish self assembling process, these class methods also are collectively referred to as soft template method.But soft template method is at non-silicon-based mesoporous material; Run into difficulty in the preparation like metal oxide materials; Because the extremely difficult control of the hydrolysis of metals ion in soft template method; The mesoporous material of every kind of MOX all needs the reaction system and the strict reaction conditions of different compound methods, complicacy, and this has restricted the research work such as Application and Development of non-silicon-based mesoporous oxide material greatly.
Scientists constantly attempts developing the method for synthetic non-silicon-based mesoporous material in recent years, and relatively more outstanding is hard template method.This method utilizes the inorganic mesoporous material (like mesopore silicon oxide etc.) of moulding as hard template; The object inorganic precursor is incorporated in the duct of mesoporous material of main part through host-guest interaction; Through a series of aftertreatments; Again inorganic template is removed, just can obtain mesoporous material with the material of main part anti-phase.But this method requires to pass through in advance the synthesizing ordered mesoporous silicon oxide of tensio-active agent, the tensio-active agent in its duct is removed could be used it as other ordered mesoporous materials of template for preparing then.
At present common tensio-active agent remove method have calcination processing (like Chinese patent 200710036694.4), micro-wave digestion handle (like Chinese patent ZL 200410066450.7) and extraction treatment (like document 1:D.Margolese, J.A.Melero, S.C.Christiansen, B.F.Chmelka and G.D.Stucky; Chem.Mater., 2000,12; 2448 with document 2:D.Grosso, A.R.Balkenende, P.A.Albouy; A.Ayral, H.Amenitsch and F.Babonneau, Chem.Mater.; 2001,13,1848) etc.Compare with other two kinds of methods that remove tensio-active agent, extraction treatment be unique not failure surface promoting agent, can the recycling tensio-active agent the method that removes.Because tensio-active agent is one type of relatively expensive reagent, if not the failure surface promoting agent, with its recycling, the reduction of cost in practical application has special value for non-silicon-based mesoporous material.
Chinese patent 200710036694.4 has reported that with Chinese patent ZL 200410066450.7 mesopore silicon oxide that adopts calcination processing or micro-wave digestion to handle prepares ordered mesoporous metal oxide as hard template.But up to the present, also there is not directly to use the mesopore silicon oxide of extraction treatment to prepare the bibliographical information of other ordered mesoporous material as hard template.At document 3:Shixi Liu, Bin Yue, Kun Jiao; Yan Zhou; Heyong He Mater.Lett.2006,60, the method that discloses among the 154-158 is in the SBA-15 mesopore silicon oxide after the solution with iron nitrate and zinc nitrate is filled into extraction treatment; After calcining, the dissolved oxygen silicon template, the product that obtains is isolated zinc ferrite nano wire.Because extraction treatment can not remove the tensio-active agent in the mesopore silicon oxide duct usually fully; Make that the mesopore silicon oxide connectivity of extraction treatment is relatively poor so be filled in that oxide compound lacks connection each other in the mesoporous main aperture road; Thereby the normally isolated nano wire of the product that obtains, have the meso-hole structure that interconnects skeleton and can not form.
Summary of the invention:
The object of the present invention is to provide a kind of compound method of ordered mesoporous indium oxide; It is through synthesize the mesopore silicon oxide with bigger hole wall linked hole in advance; Remove the tensio-active agent in its duct with extraction treatment then; Use the mesopore silicon oxide of this extraction treatment to prepare ordered mesoporous indium oxide again as hard template; Method of the present invention utilizes extraction process to reduce the cost that " common " mesopore silicon oxide at present prepares order mesoporous oxide compound, increases the linked hole size to improve the connectivity of extraction back mesopore silicon oxide, can prepare orderly mesopore oxide material thereby guarantee to use it to make hard template.
The present invention provides a kind of compound method of ordered mesoporous indium oxide, and its mesopore silicon oxide of handling with SX is that hard template is come synthesizing ordered mesoporous Indium sesquioxide, comprises the steps:
1) has the preparation of the mesopore silicon oxide of hole wall linked hole greatly: tensio-active agent, water and mixed in hydrochloric acid are stirred to tensio-active agent all dissolve; Add tetraethoxy and stirring then; Leave standstill the back in 130 ℃ of hydro-thermal reaction 1-5 days; Cooling back suction filtration, washing, drying get a white powder;
In an embodiment of the invention, the preparation of said mesopore silicon oxide is according at document 4:Abdelhamid Sayari, Bao-Hang Han; Yong Yang; J.AM.CHEM.SOC., 2004,126; Disclosed method among the 14348-14349, concrete steps are: with 8.0g tensio-active agent HO (CH
2CH
2O)
20(CH
2CH (CH
3) O)
70(CH
2CH
2O)
20H (hereinafter to be referred as P123, EO
20PO
70EO
20, BASF, Pluronic P123); 60g water mixes under 35 ℃ with 240g 2M hydrochloric acid, stirs all to dissolve and be uniformly dispersed up to tensio-active agent in 1-12 hour, adds 16.72g tetraethoxy (TEOS) then; Stir after 5 minutes, transfer in the tetrafluoroethylene bottle and in 35 ℃ of baking ovens, left standstill 20 hours, then at 130 ℃ of hydro-thermal reaction 1-5 days; Naturally cooling gets a white powder after suction filtration washs behind the natural drying at room temperature;
2) mesopore silicon oxide use solvent extraction 1) obtains having the mesopore silicon oxide that the aperture is the hole wall linked hole of 3-10 nanometer to remove tensio-active agent wherein;
Described solvent can be but be not limited to be selected from one or more mixture of methyl alcohol, ethanol, terepthaloyl moietie, propyl alcohol, butanols, ether, acetonitrile, acetone, THF, perhaps the mixed solvent of they and water;
The mass ratio of said mesopore silicon oxide and said solvent is 1: 5-1: 200;
3) with step 2) in the ordered meso-porous silicon oxide handled be hard template, it is joined in the indium salts solution and stirs flood, so that in the duct of indium salts solution entering mesopore silicon oxide; Continue stirring until after solvent volatilizees fully, in air, calcine;
Said indium salt is indium nitrate or indium chloride;
The mass ratio of said indium salt and mesopore silicon oxide is 2-6: 1;
In technical scheme of the present invention, also can according to the pore volume of mesopore silicon oxide regulate and control add the content of indium in the indium salt, make the indium salt that is added change into the 20%-40% that volume behind the Indium sesquioxide accounts for the pore volume of mesopore silicon oxide fully.In an embodiment of the invention, the pore volume of mesopore silicon oxide is 1.00cm
3/ g, the 0.60g mesopore silicon oxide can hold 0.60cm
3Material in its duct, therefore add 1.8g In (NO
3)
34.5H
2O, last decomposition and inversion fully becomes 0.65g In
2O
3(In
2O
3Theoretical density be 7.2g/cm
3), promptly volume is 0.091cm
3, can occupy mesopore silicon oxide pore volume 15%; In like manner, add 1.4g In (NO for the second time
3)
34.5H
2O, the In that changes at last
2O
3Occupy mesopore silicon oxide pore volume 12%; It is 37% of the mesopore silicon oxide pore volume that added that the indium nitrate that is added for twice changes into volume behind the Indium sesquioxide fully;
The temperature of said stirring dipping is 5-80 ℃;
Described calcining temperature is 150-300 ℃, and temperature rise rate is 1-2.5 ℃/min, and calcination time is 2-10h;
4) repeating step 3) once or once;
5) add sodium hydroxide solution in the product after calcining, stir back centrifuging, obtain xanchromatic ordered mesoporous indium oxide material to remove the mesopore silicon oxide template;
The concentration of described sodium hydroxide solution is 2-10M.
The characteristics of present method are preparation mesopore silicon oxides under higher hydrothermal temperature; Make mesopore silicon oxide have bigger hole wall linked hole; Thereby handling, SX can more fully remove the tensio-active agent in the duct; Strengthen the duct connectivity of the mesopore silicon oxide after the extraction treatment significantly, can be relatively easy to get into the duct and reach higher duct compactedness to guarantee indium salt, and finally synthesize high-quality ordered mesoporous indium oxide material.
In addition, compared with prior art, other advantage of the present invention is:
1, use the extraction mesopore silicon oxide to make template, and adopt the SX mode to remove the tensio-active agent in the mesopore silicon oxide duct, can not destroy expensive tensio-active agent, can the recycling tensio-active agent, practice thrift cost;
2, perhaps adding extra oxygenant comes the breakdown surface-active agent to need not high-temperature calcination, saves energy, environmental friendliness;
3, the mesopore silicon oxide surface of extraction has abundant silicon hydroxyl, and it is easier to make inorganic precursors be loaded into mesopore orbit, obtains easily higher duct compactedness, and it is higher to remove the material degree of order that obtains after the silicon oxide template.
Description of drawings
The TEM picture of Fig. 1 embodiment 1 gained mesoporous indium oxide;
The TEM picture of Fig. 2 embodiment 2 gained mesoporous indium oxides;
The TEM picture of Fig. 3 embodiment 3 gained mesoporous indium oxides.
Embodiment:
Come the present invention is done further elaboration through embodiment below:
Embodiment 1
8.0g tensio-active agent P123,60g water and 240g concentration are that the hydrochloric acid of 2M mixes under 35 ℃, stir all to dissolve and be uniformly dispersed up to tensio-active agent in 1-12 hour; Add 16.72g tetraethoxy TEOS then, stir after 5 minutes, transfer in the tetrafluoroethylene bottle and in 35 ℃ of baking ovens, left standstill 20 hours; Follow 130 ℃ of hydro-thermal reactions 1 day; Naturally cooling gets a white powder after suction filtration washs behind the natural drying at room temperature.
Tensio-active agent P123 removes through solvent extraction method: the powdered sample that the 1.0g front obtains joins (concentrated hydrochloric acid that contains 16 milliliters of 36wt%) in 200 milliliters of ethanol, and 70 ℃ are stirred 24h in reflux, filters washing, drying.The ordered meso-porous silicon oxide specific surface area 478m of gained
2/ g, pore volume 1.00cm
3/ g, the linked hole size is greater than 4nm.
Mesopore silicon oxide with the above-mentioned processing of 0.6g is a hard template; It is distributed in the 10 g ethanol; Add the 1.8g indium nitrate, stir dipping, so that the indium salts solution gets in the duct of mesopore silicon oxide at 40 ℃; After continue stirring solvent flashing, in air in 250 ℃ of calcinings 4 hours (the calcining temperature rise rate be 2.5 ℃/min); The powder that obtains is distributed in the 10g ethanol again, adds the 1.4g indium nitrate, 40 ℃ stir dipping and continue to stir solvent flashing after, in air in 250 ℃ of calcinings 4 hours (the calcining temperature rise rate be 2.5 ℃/min); Add 2M NaOH solution in the product after calcining, stir back centrifuging, promptly obtain ordered mesoporous indium oxide material of the present invention, the specific surface area 126m of this mesoporous indium oxide to remove the silicon oxide template
2/ g, pore volume 0.45cm
3/ g.As shown in Figure 1, the ordered mesoporous material that the indium oxide nano thread array constitutes is obtained, and the diameter of nano wire is at 4-8nm.
Embodiment 2
8.0g tensio-active agent P123,60g water and 240g concentration are that the hydrochloric acid of 2M mixes under 35 ℃, stir all to dissolve and be uniformly dispersed up to tensio-active agent in 1-12 hour; Add 16.72g tetraethoxy TEOS then, stir after 5 minutes, transfer in the tetrafluoroethylene bottle and in 35 ℃ of baking ovens, left standstill 20 hours; Then 130 degree hydro-thermal reactions are 1 day; Naturally cooling gets a white powder after suction filtration washs behind the natural drying at room temperature.Tensio-active agent P123 removes through solvent extraction method: the powdered sample that the 1.0g front obtains joins (concentrated hydrochloric acid that contains 16 milliliters of 36wt%) in 200 milliliters of ethanol, and 70 ℃ are stirred 24h in reflux, filters washing, drying.The ordered meso-porous silicon oxide specific surface area 478m of gained
2/ g, pore volume 1.00cm
3/ g, the linked hole size is greater than 4nm.
Mesopore silicon oxide with the above-mentioned processing of 0.6g is a hard template; It is distributed in the 10g ethanol; Add the 1.8g indium nitrate, stir dipping, so that the indium salts solution gets in the duct of mesopore silicon oxide at 40 ℃; After continue stirring solvent flashing, in air in 250 ℃ of calcinings 4 hours (the calcining temperature rise rate be 2.5 ℃/min); The powder that obtains is distributed in the 10g ethanol again, adds the 1.4g indium nitrate, 40 ℃ stir dipping and continue to stir solvent flashing after, in air in 250 ℃ of calcinings 4 hours (the calcining temperature rise rate be 2.5 ℃/min); The powder that obtains is distributed in the 10g ethanol again, adds the 1.0g indium nitrate, 40 ℃ stir dipping and continue to stir solvent flashing after, in air in 250 ℃ of calcinings 4 hours (the calcining temperature rise rate be 2.5 ℃/min); Add 2M NaOH solution in the product after calcining, stir back centrifuging, promptly obtain ordered mesoporous indium oxide material of the present invention, the specific surface area 53m of this mesoporous indium oxide to remove the silicon oxide template
2/ g, pore volume 0.21cm
3/ g.As shown in Figure 2, the ordered mesoporous material that indium oxide nano thread constitutes is obtained, and the diameter of nano wire is approximately 8nm.
Embodiment 3
8.0g tensio-active agent P123,60g water mixes under 35 ℃ with the hydrochloric acid of 240g 2M, stirs all to dissolve and be uniformly dispersed up to tensio-active agent in 1-12 hour; Add 16.72g tetraethoxy TEOS then, stir after 5 minutes, transfer in the tetrafluoroethylene bottle and in 35 ℃ of baking ovens, left standstill 20 hours; Then 130 degree hydro-thermal reactions are 5 days; Naturally cooling gets a white powder after suction filtration washs behind the natural drying at room temperature.Tensio-active agent P123 removes through solvent extraction method: the powdered sample that the 1.0g front obtains joins (concentrated hydrochloric acid that contains 16 milliliters of 36wt%) in 200 milliliters of ethanol, and 70 ℃ are stirred 24h in reflux, filters washing, drying.The ordered meso-porous silicon oxide specific surface area 365m of gained
2/ g, pore volume 1.21cm
3/ g, the linked hole size is greater than 8nm.
Mesopore silicon oxide with the above-mentioned processing of 0.6g is a hard template; It is distributed in the 10g ethanol; Add the 1.8g indium nitrate, stir dipping, so that the indium salts solution gets in the duct of mesopore silicon oxide at 40 ℃; After continue stirring solvent flashing, in air in 250 ℃ of calcinings 4 hours (the calcining temperature rise rate be 2.5 ℃/min); The powder that obtains is distributed in the 10g ethanol again, adds the 1.4g indium nitrate, 40 ℃ stir dipping and continue to stir solvent flashing after, in air in 250 ℃ of calcinings 4 hours (the calcining temperature rise rate be 2.5 ℃/min); Add 2M NaOH solution in the product after calcining,, stir back centrifuging to remove the silicon oxide template, promptly obtain ordered mesoporous indium oxide material of the present invention, the specific surface area 69m of this mesoporous indium oxide
2/ g, pore volume 0.25cm
3/ g.As shown in Figure 3, the ordered mesoporous material that indium oxide nano thread constitutes is obtained, and the diameter of nano wire is about 9nm.
Claims (1)
1. the compound method of an ordered mesoporous indium oxide:
1) with 8.0g tensio-active agent P123; 60g water and 240g concentration are that the hydrochloric acid of 2M mixes under 35 ℃, stir all to dissolve and be uniformly dispersed to tensio-active agent in 1-12 hour, add the 16.72g tetraethoxy then; Stir after 5 minutes; Transfer in the tetrafluoroethylene bottle and in 35 ℃ of baking ovens, left standstill 20 hours, then 130 ℃ of hydro-thermal reactions 1 day, naturally cooling after behind the suction filtration, washing, natural drying at room temperature a white powder;
2) tensio-active agent P123 removes through solvent extraction method: the white powder that the 1.0g step 1) is obtained joins in 200 milliliters of ethanol; The concentrated hydrochloric acid that wherein contains 16 milliliters of 36wt%; 70 ℃ are stirred 24h in reflux; Filtration, washing, drying, the specific surface area of gained ordered meso-porous silicon oxide are 478m
2/ g, pore volume 1.00cm
3/ g, the linked hole size is greater than 4nm;
3) with 0.6g step 2) mesopore silicon oxide handled is hard template; It is distributed in the 10g ethanol, adds the 1.8g indium nitrate, stir dipping at 40 ℃; The indium salts solution is got in the duct of mesopore silicon oxide; After continuing to stir solvent flashing, in air,, calcine 2.5 ℃/min of temperature rise rate in 250 ℃ of calcinings 4 hours;
4) powder that step 3) is obtained is distributed in the 10g ethanol again, adds the 1.4g indium nitrate, at 40 ℃ of stirring dippings and after continuing to stir solvent flashing, in air, in 250 ℃ of calcinings 4 hours, calcines 2.5 ℃/min of temperature rise rate;
5) add 2M NaOH solution in the product after the step 4) calcining, stir back centrifuging to remove the silicon oxide template, promptly obtain ordered mesoporous indium oxide, its specific surface area is 126m
2/ g, pore volume 0.45cm
3/ g, this ordered mesoporous indium oxide is made up of the indium oxide nano thread array, and the diameter of nano wire is at 4-8nm.
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| CN102642863B (en) * | 2012-03-31 | 2014-03-19 | 中国检验检疫科学研究院 | Preparation method for indium oxide sequential nano mesoporous materials doping with metal |
| CN102680528B (en) * | 2012-05-24 | 2014-04-02 | 宁夏大学 | Silver and indium oxide composite nanorod array formaldehyde air-sensitive material and preparation method thereof |
| CN104495912B (en) * | 2014-12-15 | 2016-09-28 | 宁夏大学 | A kind of triple mesoporous indium oxide formaldehyde gas sensitive materials and preparation method thereof |
| CN106248747A (en) * | 2016-06-29 | 2016-12-21 | 燕园众欣纳米科技（北京）有限公司 | A kind of preparation method of Graphene mesoporous indium oxide nano composite material |
| CN108508155B (en) * | 2018-04-03 | 2021-04-06 | 宁夏大学 | High-specific-surface-area ordered large-mesoporous nickel oxide acetone gas-sensitive material and preparation method thereof |
| KR20220000433A (en) * | 2020-06-25 | 2022-01-04 | 현대자동차주식회사 | Catalyst for conversion of carbon dioxide to methanol by hydrogenation, and method for preparing the same |
| CN112551572B (en) * | 2020-12-11 | 2023-08-18 | 广西晶联光电材料有限责任公司 | Preparation method of nano indium oxide with large specific surface area |
| 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 |
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Non-Patent Citations (2)
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| Dongyuan Zhao et al..Nonionic Triblock and Star Diblock Copolymer and Oligomeric Surfactant Syntheses of Highly Ordered, Hydrothermally Stable, Mesoporous Silica Structures.《 J. Am. Chem. Soc》.1998,第120卷(第24期),第6024-6036页. * |
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