CN103816900B - A kind of metal oxide/TiO 2nanocatalyst and preparation method thereof - Google Patents
A kind of metal oxide/TiO 2nanocatalyst and preparation method thereof Download PDFInfo
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- CN103816900B CN103816900B CN201410102106.2A CN201410102106A CN103816900B CN 103816900 B CN103816900 B CN 103816900B CN 201410102106 A CN201410102106 A CN 201410102106A CN 103816900 B CN103816900 B CN 103816900B
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Abstract
The invention discloses a kind of metal oxide/TiO
2nanocatalyst and preparation method thereof.The method is take metallo-organic compound as template, then through introducing titanium source, the hydrolysis of titanium source, removing template step, obtained metal oxide/TiO
2nanocatalyst.Described metallo-organic compound is the one in CuBTC, MIL-101 (Cr) or MIL-101 (Fe), and described titanium source is isopropyl titanate or butyl titanate.Introduced as a kind of template by metallo-organic compound, its advantage is easy to prepare, simple and easy to get, and is easy to remove in the later stage.Wherein, the aperture of template that the most key is can be adjusted flexibly by the kind and number changing part, thus can prepare the high-ratio surface TiO with metallo-organic compound complementary structure of different pore size
2material.Through the TiO that the inventive method is obtained
2there is more excellent structure, larger specific area, its breakthrough in multi-field application can be realized.
Description
Technical field
The invention belongs to field prepared by high surface area catalysts, be specifically related to a kind of metal oxide/TiO
2nanocatalyst and preparation method thereof.
Background technology
TiO
2a kind of indispensable inorganic functional material, because there is with low cost, non-toxic stable and strong oxidizing property and being widely used in multiple fields such as new forms of energy battery, purification and fast-response probe.Research shows, by necessarily processing the TiO of rear preparation
2photochemical catalyst, Be very effective in the improvement of organic degraded, purification of air and contaminant water, this is also TiO
2become one of reason of welcome functional material in recent years.But, TiO prepared by prior art
2had specific area can not reach the requirement of experiment, therefore find a kind of method that can increase its specific surface for widening TiO
2vital effect is played in the further application of functional material.Traditional method mainly contains two kinds: one reduces TiO
2the particle diameter of particle, the less then corresponding specific area of size is larger, but for TiO
2when particle diameter exists the experiment explicitly called for, this method is limited to; Second method prepares mesoporous material by hard template method, and the open defect that this method exists is fixing as the aperture of the hard mould agent of template, has no idea freely to regulate as required.Therefore, a kind of method that can overcome above problem is found will to be a significant breakthrough of tool.
Coordination polymer or metallo-organic compound (Metal-OrganFrameworks, MOFs) be with active force self assemblies such as coordinate bonds, there is periodic network skeleton by metal ion or metal cluster and multiple tooth organic ligand, and there is the new material of the feature such as porous, high-specific surface area, be a study hotspot of technical field of material chemistry in the world at present.In the bibliographical information of in the past 10 years, by changing geometry, size and the ligand species in composition, people obtain the MOFs material different more than 20000 kinds.These materials have superelevation porosity (up to 90%) and super large specific surface knot (some can more than 6000m
2/ g), single with regard to these two aspects, its performance is considerably beyond the conventional porous materials of such as molecular sieve and so on.So far, can enrich in the not same sex had of degree and material and diversity in duct without any porous material and compare favourably with MOFs material.This material feature structurally makes it have extraordinary advantage: can obtain maximum aperture and the structure of minimum density keeping the ability changing scantling and MOF architectural characteristic under the similar prerequisite of pattern, this just selectively can comprise large molecule (as Cobastab
12), in conjunction with traditional template, expand TiO further for this characteristic metal-organic
2specific surface has had again new progress.
A kind of method with metallo-organic compound being Template preparation has a high-ratio surface material rarely has bibliographical information, so this is also of the present invention one to create greatly a little, introduced as a kind of template by metallo-organic compound, its advantage is easy to prepare, simple and easy to get, and be easy to remove in the later stage.Wherein, the aperture of template that the most key is can be adjusted flexibly by the kind and number changing part, thus can prepare the high-ratio surface TiO with metallo-organic compound complementary structure of different pore size
2material, from this point, a kind of method with metallo-organic compound being Template preparation has a high-ratio surface material will have more advantage and challenge meaning.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, a kind of metal oxide/TiO is provided
2nanocatalyst and preparation method thereof.The TiO that the method is obtained
2there is more excellent structure, larger specific area, effectively improve the utilization rate of material for solar energy, and then widened its application in environment and photocatalysis field.The porous material prepared through the inventive method can realize its breakthrough in multi-field application.
For achieving the above object, the present invention adopts following technical scheme:
A kind of metal oxide/TiO
2the preparation method of nanocatalyst take metallo-organic compound as template, then through introducing titanium source, the hydrolysis of titanium source, removing template step, obtained metal oxide/TiO
2nanocatalyst.
Described metallo-organic compound is the one in CuBTC, MIL-101 (Cr) or MIL-101 (Fe).
Described titanium source is isopropyl titanate or butyl titanate.
Described metal oxide/TiO
2the preparation method of nanocatalyst, comprises the steps:
(1) synthesis of template: take slaine and organic ligand, and to be dissolved in water, ethanol and nitrogen dimethylformamide volume ratio be in the mixed solvent of 1:1:1, at 80-120 DEG C of reaction 5-10h, then product is dissolved in carrene, under room temperature after centrifugal 2-4 time, get dry 12 ~ 24h at being deposited in 60-100 DEG C and obtain metallo-organic compound;
(2) titanium source is introduced: the metallo-organic compound that step (1) is obtained is heated to 140-250 DEG C under vacuo, and keeps 12-24 hour; After being down to room temperature, in metallo-organic compound, adding titanium source vacuumize 20-50min, then stir 35-45h under vacuum conditions, to ensure that titaniferous materials fully enters in metal-organic duct; Take out product, after absolute ethyl alcohol centrifuge washing 2-5 time, in 60-100 DEG C of oven dry;
(3) titanium source hydrolysis: moved in water heating kettle by product obtained for step (2), add ethanol and the water mixed solvent of equal-volume proportioning, at 200 DEG C of reaction 20h; Take out product, after absolute ethyl alcohol centrifugal treating 2-4 time, to ensure that metal-organic surface can remove the titaniferous materials of adhesion completely, at 60-100 DEG C, dry 10-24 hour;
(4) template is removed: the product that step (3) is obtained is placed in Muffle furnace, take programmed temperature method that temperature is risen to 360 DEG C, organic principle in metallo-organic compound is subsided, carbonizes and volatilize, the metal ingredient in such template is separated with organic principle and becomes oxide and be attached to TiO
2in the duct of the complementary structure formed, obtained metal oxide/TiO
2nanocatalyst.
Slaine described in step (1) is the one in mantoquita, chromic salts or molysite, and described organic ligand is the one in 1,3,5-benzoic acid, terephthalic acid (TPA).
In step (1), the mol ratio of slaine and organic ligand is 1.5-3.0:1.
In step (2), the volume ratio in metallo-organic compound and titanium source is 1:3-5.
Its rotating speed centrifugal described in step (1), (2) is 3500-4500r/min, and centrifugation time is 1-3min.
Metal oxide/TiO that preparation method as above obtains
2nanocatalyst.
Beneficial effect of the present invention is:
(1) the template metallo-organic compound selected by the present invention is different from other any one conventional template agent, the well-regulated duct of metallo-organic compound tool and regulatable aperture size, thus by TiO prepared by metallo-organic compound
2also there is the structure complementary mutually with metallo-organic compound, and TiO
2pore size can experimentally condition and template used metallo-organic compound and carry out Reasonable Regulation And Control;
(2) metallo-organic compound used by the present invention is easy to preparation, Stability Analysis of Structures, aperture is adjustable, and metal ingredient remaining after destroying its structure can serve as a kind of active component of composite and improve photochemical catalysis activity, and the metallo-organic compound therefore in the present invention has double effects;
(3) template is removed by the mode of roasting by the present invention, and the metal ingredient of template can be made like this to change the form load of oxide at the prepared TiO with complementary structure
2duct in, thus formed decentralization high, the composite oxides that associativity is good;
(4) TiO has been widened by method of the present invention
2application, make it breach to be mainly used in the restriction in photocatalytic applications, be applied on traditional thermocatalytic, be greatly improved too in nature, apply more extensive;
(5) equipment arrived involved in the present invention is simple, is widely used, and is easy to realize, and more meets the requirement of contemporary chemical industrie.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the copper base metal organic compound (CuBTC) of preparation in embodiment 1;
Fig. 2 is the scanning electron microscope (SEM) photograph of the product after introducing titanium source, hydrothermal treatment consists in embodiment 1;
Fig. 3 is for burning the scanning electron microscope (SEM) photograph of the product that template obtains by roasting in embodiment 1;
Fig. 4 is the nitrogen adsorption desorption curve of the product after introducing titanium source hydro-thermal in embodiment 1;
Fig. 5 is for burning the nitrogen adsorption desorption curve of the product that template obtains by roasting in embodiment 1;
Fig. 6 is for burning by roasting the product (a) and traditional catalyst (b) carbon monoxide oxidation activity figure that template obtains in embodiment 1.
Detailed description of the invention
The present invention's the following example further illustrates the present invention, but protection scope of the present invention is not limited to the following example.For setting forth experimental implementation of the present invention and result thereof further, this part makes a more detailed description in conjunction with inventive embodiment.
embodiment 1
With metallo-organic compound trimesic acid copper (CuBTC) for template, take isopropyl titanate as metal oxide/TiO that the preparation of titanium source has metallo-organic compound complementary structure
2nanocatalyst.
(1) synthesis of template: the Gerhardite aqueous solution is mixed with trimesic acid/ethanolic solution (volume ratio is 1:1) and moves into water heating kettle and reacts 10 hours at 80 DEG C; Be dissolved in dichloromethane solvent by product obtained above, take off metallo-organic compound dry 12h at 100 DEG C that layer precipitates under room temperature after centrifugal 3 times, centrifugal process chooses rotating speed 4000 revs/min, and centrifugation time is 2 minutes;
(2) titanium source is introduced: the said goods is heated to 140 DEG C under vacuo, and keep 18 hours, in 2g product, 10ml isopropyl titanate is added after being down to room temperature, and continue to vacuumize, maintaining the dynamic vacuum time is 30 minutes, under stirring, then maintains permanent vacuum environment 40 hours to ensure that isopropyl titanate fully enters in metal-organic duct; The product of above-mentioned process is shifted out vacuum environment, after taking out with alcohol solvent centrifuge washing 4 times to ensure that metal-organic surface can remove the isopropyl titanate of adhesion completely, centrifugal process chooses rotating speed 4000 revs/min, centrifugation time is 2 minutes, is dried by the product cleaned at 100 DEG C;
(3) titanium source hydrolysis: moved into by above-mentioned oven dry product in the water heating kettle containing second alcohol and water (volume ratio 1:1) solvent, 200 DEG C of reactions 20 hours; Dry 24 hours at 60 DEG C with after solvent centrifugal treating 3 times after product is taken out.
(4) template is removed: by TiO obtained above
2the compound of filling metallorganic framework puts into Muffle furnace, take programmed temperature method temperature to be risen to 360 DEG C the organic principle in metallo-organic compound is subsided, to carbonize and volatilize, the metal ingredient in such template is separated with organic principle and becomes oxide and be attached to TiO
2in the duct of the complementary structure formed, form metal oxide and TiO
2composite oxide material.
The sample obtained is analyzed accordingly and tests: Fig. 1 is the scanning electron microscope (SEM) photograph of the trimesic acid copper of preparation, and obviously can find that it is regular octahedron structure by figure, this conforms to bibliographical information.The Sample Scan Electronic Speculum figure filled after isopropyl titanate is shown in Fig. 2, as can be seen from Figure, still keep the structure of the regular octahedron of template, but the specific area making nitrogen adsorption desorption test to obtain due to filling effect reduces (see figure 4), Fig. 3 gets rid of through roasting the scanning electron microscope (SEM) photograph obtained after template, its structure obviously has the complementary characteristic of trimesic acid copper, and BET specific surface area reaches 270m
2/ g(is shown in Fig. 5), the product of final gained is carried out on catalyzing carbon monoxide oxidation activity evaluating apparatus the data that active testing obtains and see Fig. 6 (a), relatively, the material that the present invention obtains has very outstanding catalytic activity, reach 100% at about 140 DEG C its CO conversion, this is considerably beyond other non-precious metal catalysts even activity of some noble metal catalysts.
embodiment 2
With metallo-organic compound trimesic acid copper (FeBDC) for template, take isopropyl titanate as metal oxide/TiO that the preparation of titanium source has metallo-organic compound complementary structure
2nanocatalyst.
(1) synthesis of template: the Iron(III) chloride hexahydrate aqueous solution is mixed with terephthalic acid (TPA)/DMF solution (volume is 15mL) and moves into water heating kettle and reacts 7 hours at 120 DEG C; By product obtained above 60 DEG C of alcohol immersion 3 hours, take off metallo-organic compound dry 24h at 60 DEG C that layer precipitates after centrifugal 3 times, centrifugal process chooses rotating speed 4500 revs/min, and centrifugation time is 1 minute;
(2) titanium source is introduced: the said goods is heated to 250 DEG C under vacuo, and keep 12 hours, in 600mg product, 4ml isopropyl titanate is added after being down to room temperature, and continue to vacuumize, maintaining the dynamic vacuum time is 30 minutes, under stirring, then maintains permanent vacuum environment 40 hours to ensure that isopropyl titanate fully enters in metal-organic duct; The product of above-mentioned process is shifted out vacuum environment, after taking out with alcohol solvent centrifuge washing 4 times to ensure that metal-organic surface can remove the isopropyl titanate of adhesion completely, centrifugal process chooses rotating speed 4000 revs/min, centrifugation time is 2 minutes, is dried by the product cleaned at 100 DEG C;
(3) titanium source hydrolysis: moved into by above-mentioned oven dry product in the water heating kettle containing second alcohol and water (volume ratio 1:1) solvent, 200 DEG C of reactions 20 hours; Dry 10 hours at 100 DEG C with after solvent centrifugal treating 3 times after product is taken out.
(4) template is removed: by TiO obtained above
2the compound of filling metallorganic framework puts into Muffle furnace, take programmed temperature method temperature to be risen to 550 DEG C the organic principle in metallo-organic compound is subsided, to carbonize and volatilize, the metal ingredient in such template is separated with organic principle and becomes oxide and be attached to TiO
2in the duct of the complementary structure formed, form metal oxide and TiO
2composite oxide material.
The foregoing is only preferred embodiment of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (5)
1. metal oxide/TiO
2the preparation method of nanocatalyst, is characterized in that: take metallo-organic compound as template, then through introducing titanium source, the hydrolysis of titanium source, removing template step, obtained metal oxide/TiO
2nanocatalyst; Described metallo-organic compound is the one in CuBTC, MIL-101 (Cr) or MIL-101 (Fe); Described titanium source is isopropyl titanate or butyl titanate;
Specifically comprise the steps:
(1) synthesis of template: take slaine and organic ligand, and to be dissolved in water, ethanol and nitrogen dimethylformamide volume ratio be in the mixed solvent of 1:1:1, at 80-120 DEG C of reaction 5-10h, then product is dissolved in carrene, under room temperature after centrifugal 2-4 time, get dry 12 ~ 24h at being deposited in 60-100 DEG C and obtain metallo-organic compound;
(2) titanium source is introduced: the metallo-organic compound that step (1) is obtained is heated to 140-250 DEG C under vacuo, and keeps 12-24 hour; After being down to room temperature, in metallo-organic compound, adding titanium source vacuumize 20-50min, then stir 35-45h under vacuum conditions; Take out product, after absolute ethyl alcohol centrifuge washing 2-5 time, in 60-100 DEG C of oven dry;
(3) titanium source hydrolysis: moved in water heating kettle by product obtained for step (2), add ethanol and the water mixed solvent of equal-volume proportioning, at 200 DEG C of reaction 20h; Take out product, after absolute ethyl alcohol centrifugal treating 2-4 time, at 60-100 DEG C, dry 10-24 hour;
(4) template is removed: the product that step (3) is obtained is placed in Muffle furnace, takes programmed temperature method that temperature is risen to 360 DEG C, obtained metal oxide/TiO
2nanocatalyst.
2. metal oxide/TiO according to claim 1
2the preparation method of nanocatalyst, is characterized in that: the slaine described in step (1) is the one in mantoquita, chromic salts or molysite, and described organic ligand is the one in 1,3,5-benzoic acid, terephthalic acid (TPA).
3. metal oxide/TiO according to claim 1
2the preparation method of nanocatalyst, is characterized in that: in step (1), the mol ratio of slaine and organic ligand is 1.5-3.0:1.
4. metal oxide/TiO according to claim 1
2the preparation method of nanocatalyst, is characterized in that: in step (2), the volume ratio in metallo-organic compound and titanium source is 1:3-5.
5. metal oxide/TiO according to claim 1
2the preparation method of nanocatalyst, is characterized in that: its rotating speed centrifugal described in step (1), (2) is 3500-4500r/min, and centrifugation time is 1-3min.
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|---|---|---|---|---|
| CN107068419A (en) * | 2017-02-27 | 2017-08-18 | 河南师范大学 | MIL‑101(Cr)@TiO2Application in electrode material |
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|---|---|---|---|---|
| CN104475165B (en) * | 2014-12-12 | 2016-08-17 | 哈尔滨工业大学 | A kind of preparation method of oxidation-desulfurizing catalyst |
| CN104741151B (en) * | 2015-04-02 | 2017-03-29 | 哈尔滨工业大学 | A kind of preparation method and application of carbon-doped nano metal composite oxide |
| CN105693506A (en) * | 2016-02-02 | 2016-06-22 | 南京众力盛强新材料科技有限公司 | Synthesis method of porous titanium crystal metal organic framework material |
| CN107583671B (en) * | 2017-10-25 | 2020-11-03 | 安徽工程大学 | Core-shell structure nano composite material and preparation method thereof |
| CN109289927A (en) * | 2018-11-21 | 2019-02-01 | 南京大学 | The preparation method and applications of the iron-based MOF visible light composite catalyst of nano-titanium dioxide@ |
| CN109402661B (en) * | 2018-11-29 | 2020-06-26 | 江苏大学 | MIL-100(Fe)/TiO2Preparation method and application of composite photoelectrode |
| CN110665492A (en) * | 2019-09-24 | 2020-01-10 | 安徽工程大学 | TiO 22/Cr2O3/C nano material and preparation method thereof |
| CN112624143B (en) * | 2020-12-11 | 2022-05-03 | 北京科技大学 | Method for preparing TS-1 molecular sieve catalyst by taking MOFs as titanium source |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080063591A1 (en) * | 2006-09-07 | 2008-03-13 | Samsung Sdi Co., Ltd. | Porous carbon material and method of manufacturing the same |
| CN101190799A (en) * | 2006-03-29 | 2008-06-04 | 三星Sdi株式会社 | Porous metal oxide and method of preparing the same |
-
2014
- 2014-03-19 CN CN201410102106.2A patent/CN103816900B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101190799A (en) * | 2006-03-29 | 2008-06-04 | 三星Sdi株式会社 | Porous metal oxide and method of preparing the same |
| US20080063591A1 (en) * | 2006-09-07 | 2008-03-13 | Samsung Sdi Co., Ltd. | Porous carbon material and method of manufacturing the same |
Non-Patent Citations (3)
| Title |
|---|
| "Metal-Organic Framework Templated Synthesis of Fe2O3/TiO2 Nanocomposite for Hydrogen Production";Kathryn E. deKrafft，et al;《ADVANCED MATERIALS》;20120319;第24卷;第2014-2015页，2017-2018页"Experimental Section"部分，图1-3 * |
| "Synthesis of Different Copper Oxide Nano-Structures From Direct Thermal Decomposition of Porous Copper(ΙΙ) Metal-Organic Framework Precursors";N. Nasihat Sheno，et al;《Int. J. Nanosci. Nanotechnol》;20120630;第8卷(第2期);全文 * |
| "金属_有机骨架化合物为前驱体制备CuO/CeO2催化剂及在富氢条件下催化CO的氧化";徐力，等;《高等学校化学学报》;20130831;第34卷(第8期);全文 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107068419A (en) * | 2017-02-27 | 2017-08-18 | 河南师范大学 | MIL‑101(Cr)@TiO2Application in electrode material |
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