CN101327952A - Preparation of Ce4Ti9O24 composite oxides - Google Patents

Preparation of Ce4Ti9O24 composite oxides Download PDF

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CN101327952A
CN101327952A CNA2008101201500A CN200810120150A CN101327952A CN 101327952 A CN101327952 A CN 101327952A CN A2008101201500 A CNA2008101201500 A CN A2008101201500A CN 200810120150 A CN200810120150 A CN 200810120150A CN 101327952 A CN101327952 A CN 101327952A
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composite oxides
preparation
deionized water
ceo
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蒋晓原
赵秀华
郑小明
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Zhejiang University ZJU
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Abstract

The invention relates to a preparation method of a Ce4Ti9O24 composite oxide comprising: uniformly mixing materials of titanium tetrachloride precursor and cerous nitrate solution according to the mol ratio of Ti and Ce 0.8:0.2, dropping ammonia while magnetic stirring till the solution pH value of titration end point is 10, obtaining precipitate of the Ce4Ti9O24 composite oxide precursor, calcining the precipitate at 700 DEG C for 2 hours after aging, pumping filtration, washing, drying to obtain the Ce4Ti9O24 composite oxide. The technology of the invention is simple, the catalyst of prepared Ce4Ti9O24 composite oxide supported CuO has a good catalytic activity for the NO+CO reaction.

Description

Ce 4Ti 9O 24The preparation method of composite oxides
Technical field
The present invention relates to a kind of carrier that in the NO+CO reaction, has better catalytic activity, Ce 4Ti 9O 24Composite oxides and preparation method.
Background technology
Oxynitride (NO x) be one of main source that causes topsoil.NO xDischarging brought serious harm to global environment.NO xRemoval methods liquid absorption method, active carbon adsorption, catalyzed oxidation, catalytic decomposition etc. are arranged, but all there is a lot of deficiencies in these methods, cause them not to be widely used.Through for many years exploration with discover, with CO, H 2Non-selective Reduction of NO for reductive agent xIn, TiO 2For the catalyzer of carrier has active high, advantages such as good, the anti-toxic of selectivity is strong, low temperature active good, surface acidity is adjustable, high temperature vattability.Specific surface area is less relatively, the acid amount is lower but also have, for high pressure and the disadvantageous shortcoming of macromolecular reaction; The interpolation of rare earth element ce then can overcome these deficiencies well, not only can increase the specific surface area of carrier, promotes the dispersion of active ingredient, can also increase the thermostability of carrier; Pass through Ce 3+/ Ce 4+Oxidation-reduction circulation, promote migration, the exchange of oxide species in the reaction, thereby improve the oxidation of CO, HC and the reduction efficiency of NO.Therefore, CeO 2-TiO 2The development of composite oxides has not only overcome single TiO 2And CeO 2The shortcoming of carrier also makes it show exclusive catalysis characteristics.So, CeO 2-TiO 2The research of composite oxides more and more receives publicity.LarssonP.O., Anderson A.Complete oxidation of CO, ethanol, and ethyl acetate over copper oxide supportedon titania and ceria modified titania.Journal of Catalysis, 1998,179:72-89 has investigated CuO/TiO 2And CuO/CeO 2-TiO 2To the oxidation activity of CO, ethanol and ethyl acetate, find CeO 2Interpolation not only improved the activity of CuO, and stablized TiO 2Specific surface area, its reason mainly is CeO 2Modification TiO 2Surface, the interaction between Cu and the Ce are improved the reducing power of active ingredient CuO greatly.Duan Zhigang, Zhu Zhongqi receives common vetch etc., CeO 2Doped Ti O 2The preparation of powder and performance thereof. the research material Leader, 2006,20:94-96 has studied CeO 2Addition to TiO 2The influence of crystalline structure, the result shows: under the certain situation of preparation condition, CeO 2When doping was the 50mol% left and right sides, faint TiO appearred in the XRD figure of sample 2Characteristic peak; Has only CeO during greater than 50mol% 2Characteristic peak occur,, TiO 2Be amorphous structure; Work as CeO 2Doping is during less than 15mol%, CeO 2Characteristic peak begin to disappear; At CeO 2Doping is in the catalyzer of 15mol-50mol%, TiO 2, CeO 2Show respectively anatase octahedrite mutually with cerianite mutually.Chen Linshen, Lv Guanglie, Hu Xiurong. middle temperature preparation CeO 2-TiO 2Composite oxides and structural research thereof. Chinese rare-earth journal, 2001,19 (4): 334-337, adopt sol-gel method, prepared CeTi 2O 6Composite oxides, it is TiO 6Distorted octahedron network layer and CeO 8Distortion dodecahedron layer alternately piles up the lamellar structure compound that forms along the z axle to be total to the rib mode.At TiO 6In the network layer, TiO 6Connect chaining along the y axle to be total to the top mode between distorted octahedron, chain connects to be total to the rib mode along the x direction of principal axis again.CeO 8In the layer, CeO 8Bipyramid distortion dodecahedron connects chaining along the y direction of principal axis in rib mode altogether, chain again along the x direction of principal axis with the mode of connection stratification that is arranged in parallel not mutually.The CeTi that the Sol-gel method obtains 2O 6Have 8% Ce omission in the structure, chemical formula can be write as Ce 0192Ti 2O 5.84Through 1300 ℃ of roastings, Ce is vacant to disappear, and the structure trend is complete.Sorapong Pavasupreea, Yoshikazu Suzukia, Sommai Pivsa-Artb, etal.Preparation andcharacterization of mesoporous TiO 2-CeO 2Nanopowders respond to visible wavelength.Journal of Solid StateChemistry, 2005,178:128-134 has studied interpolation CeO 2The specific surface area of back composite oxides, the result shows: the sample of 400 ℃ of roastings, a small amount of CeO 2Interpolation the specific surface area of sample is increased, and a large amount of CeO 2Interpolation the specific surface area of sample is reduced; Chen Zhengxiong, Zhu Wanpeng, the few rosy clouds .TiO of poplar 2-CeO 2The activity research of catalyzer wet oxidation phenol. Journal of Molecular Catalysis, 2005,19 (5): 338-342 studies show that: cerium titanium mol ratio is 1: 1 o'clock, and cerium mainly exists with the tetravalence form; Cerium titanium mol ratio is 1: 3 o'clock, and cerium is mainly with trivalent and tetravalence form and deposit; And the chemically adsorbing oxygen of high bound energy promotes with the increase of Ti content, and chemically adsorbing oxygen is strong oxide species, and its increase can promote the generation of strong oxidizing property free radical, thereby improves the catalytic activity of catalyzer.Francisco M.S.P., Mastelaro V.R., Nascente P.A.P., etal.Activity and Characterization by XPS, HR-TEM, Raman Spectroscopy, and BET Surface Area of CuO/CeO 2-TiO 2Catalysts J.Physical Chemistry B, 2001,105:10515-10522, Francisco M.S.P., Nascente P.A.P., Mastelaro V.A., etal.X-ray photoelectronspectroscopy, x-ray absorption spectroscopy, and x-ray diffraction charactcrization of CuO-TiO 2-CeO 2Catalystsystem Journal of Vacuum Science and Technology A, 2001,19 (4): 1150-1157, studied CuO-CeO 2-TiO 2Catalyzer, the result shows that doped Ce can make the increase of copper species ratio, the TiO of catalyst surface 2Grain-size diminishes.XPS detect to show to add behind the Ce and two kinds of Ti species occurred in the system.Luo M.F., Chen J., Chen L.etal.Structure and redoxproperities of Ce xTi 1-xO 2Solid solution[J] .Chemical Material, 2001,13:197-202 adopts sol-gel method to prepare the Ce of different proportionings xTi 1-xO 2Composite oxides, and characterize with means such as Raman, XRD and TPR, the result shows when x 〉=0.6, has formed the Ce of cube phase xTi 1-xO 2Sosoloid; When x≤0.5, formed mixed phase; When x=0.3, formed the monocline phase.TPR result shows, with TiO 2Be incorporated into CeO 2In, formed Ce xTi 1-xO 2Sosoloid, and improved the reducing power of body phase oxygen, make Ce 3+/ Ce 4+Oxidation-reduction circulation be more prone to, be a kind of oxygen agent of storing preferably.Yang Shaoxia, Chen Zhengxiong .CeO such as Zhu Wanpeng 2-TiO 2The surface tissue of catalyzer and wet oxidation activity [J] thereof. the catalysis journal, 2006,27 (4): 329-334, the mol ratio of having studied the preparation of sol-gel method and coprecipitation method is 1: 1 CeO 2-TiO 2Composite oxides.Result of study shows that the interaction between Ce and the Ti makes composite oxides CeO 2-TiO 2Catalyzer has little grain-size and high specific surface area, and catalyst surface chemisorption oxygen level increases, and the CeO that obtains of different preparation method 2-TiO 2Catalyst surface potential point difference, the catalyzer of coprecipitation method preparation more helps the absorption of acetate and phenol.In wet oxidation reaction, CeO 2-TiO 2Catalyzer has higher activity, and wherein the catalyst activity of coprecipitation method preparation is the highest.Francisco M.S.P., Mastelaro V.R., Nascente P.A.P., Florentino A.O.Activity and Characterization by XPS, HR-TEM, RamanSpectroscopy, and BET Surface Area of CuO/CeO 2-TiO 2Catalysts[J] .J.Physical Chemistry B, 2001,105:10515-10522 thinks that the copper species are with Cu 2+The form high dispersing at the surface of carrier, CuO/CeO 2-TiO 2Catalytic activity than the independent TiO that loads on of CuO 2Or CeO 2On all to get well, this mainly is because have strong interaction between CuO and the cerium-titanium composite oxide.Gargi Dutta, Umesh V.Waghmare, Tinku Baidya, etal.Origin of Enhanced Reducibility/OxygenStorage Capacity of Ce 1-xTi xO 2Compared to CeO 2Or TiO 2[J] .Chemical Materials.2006,18:3249-3256 has studied Ce 1-xTi xO 2(x=0.0-0.4) composite oxides, the result shows that composite oxides are than single CeO 2And TiO 2All have good oxidation-reduction ability and oxygen storage capacity, it can be by H in wider scope 2Reduction; Ce 1-xTi xO 2Have two kinds of oxygen species that strong and weak degree is different with valence state in the composite oxides, and the existence of the lower weak oxygen species of valence state is to cause it to have the major cause of good oxygen storage capacity.
Summary of the invention
The purpose of this invention is to provide a kind of carrier that in the NO+CO reaction, has better catalytic activity, Ce 4Ti 9O 24Composite oxides and preparation method thereof, its redox ability is highly beneficial for the NO+CO reaction.Be characterized in that the preparation method is simple, but condition control is very strict.
Ce provided by the invention 4Ti 9O 24Composite oxides, the mol ratio of Ti and Ce is 0.8: 0.2 in the component.
Ce provided by the invention 4Ti 9O 24The preparation method of composite oxides, its step is as follows:
1, in a container, adds deionized water, put it in the ice-water bath, after the system for the treatment of is stable, drip titanium tetrachloride (TiCl lentamente 4) solution, make the solution clarification, getting concentration is the presoma of 0.5mol/L titanium tetrachloride solution.
2, get a container in addition, add deionized water dissolving cerous nitrate (Ce (NO 3) 36H 2O) crystal, obtaining concentration is the 0.5mol/L cerium nitrate solution.
3, the cerium nitrate solution of step 2 speed with 1d/s is added drop-wise in the precursor solution of the titanium tetrachloride solution in step 2 ice-water bath, the mol ratio of control Ti and Ce is 0.8: 0.2, forms mixing solutions.
4, with the mixing solutions of step 2, under magnetic agitation, with the speed of 1d/s dropwise the volume ratio of dropping ammonia and mixing solutions be 1: 1 strong aqua, the pH=10 of titration end point solution obtains Ce 4Ti 9O 24The throw out of composite oxides precursor.
5, with the gained throw out in its mother liquor under room temperature still aging 24h, through suction filtration, with deionized water wash to there not being Cl -(use AgNO 3Solution check Cl -Exist), in 110 ℃ baking oven, dry by the fire 12h, change muffle furnace then over to, at 700 ℃ of following roasting 2h, obtain Ce 4Ti 9O 24Composite oxides.
Strong aqua concentration volume ratio of the present invention is 1: 1.
Ce after the present invention's oven dry 4Ti 9O 24The throw out of composite oxides precursor, the heat-up rate that changes the muffle furnace roasting over to is controlled at 3 ℃/min.
The invention provides Ce 4Ti 9O 24After the throw out oven dry of composite oxides precursor, change muffle furnace over to,, show: only occur not really significantly TiO in the catalyzer spectrogram of 500 ℃ of roastings through the XRD detection at 500 ℃, 600 ℃, 700 ℃ and 800 ℃ of following roasting 2h 2The anatase octahedrite characteristic diffraction peak.Along with the rising of maturing temperature, TiO 2The anatase octahedrite peak become obvious.Compare with the catalyzer spectrogram of 600 ℃ of roastings, more crystalline phase peak has appearred in the catalyzer spectrogram of 700 ℃ of roastings, and some peak that occurs in the catalyzer spectrogram of 700 ℃ of roastings disappears in the spectrogram of the catalyzer of 800 ℃ of roastings on the contrary, and this is because Ce occurred in the time of 700 ℃ 4Ti 9O 24Be transformed into rutile and cerianite when composite oxides, 800 ℃ of these composite oxides.
The Raman characterization result shows: the catalyzer of 500 ℃ of roastings mainly is to exist with unformed form.The catalyzer of 600 ℃ of roastings begins to have occurred five tangible absorption peaks (α, β, δ, γ and φ) and a unconspicuous κ peak, respectively at 365cm -1, 485cm -1, 560cm -1, 627cm -1, 760cm -1And 1610cm -1The place, the δ peak is CeO 2The crystalline phase peak, α and γ peak are the crystalline phase peaks of CuO, not being both because the environment difference at the two place of displacement occur.α, δ and φ peak are middle species Ce in the roasting process 4Ti 9O 24The absorption peak that occurs, along with μ and θ peak have appearred again in the rising of maturing temperature, μ and θ peak are final product CeTiO in the high-temperature calcination process 4The crystalline phase peak, the β peak is CeO 2The crystalline phase peak, γ is TiO 2The absorption peak of rutile phase.
Technological process of the present invention is simple, but each step needs through strictness control, the Ce that makes 4Ti 9O 24Can be used as the carrier of NO+CO reaction, this carrier has catalytic activity preferably, especially prepared Ce in 700 ℃ of preparation process 4Ti 9O 24Reaction had good catalytic activity to NO+CO after composite oxides, composite oxide supported CuO made catalyzer.
Description of drawings
The 12%CuO/Ce of the different maturing temperatures of Fig. 1 0.2Ti 0.8O 2XRD spectra
The 12%CuO/Ce of Fig. 2 differing temps roasting 0.2Ti 0.8O 2The Raman spectrogram
Embodiment
Embodiment 1
Ce 4Ti 9O 24The preparation method of composite oxides the steps include:
(1) in the beaker of 600ml, adds the 154ml deionized water, and put it in the ice-water bath, drip the TiCl of 9ml after the system for the treatment of is stable more lentamente 4Solution stirs, solution clarification (concentration is 0.5mol/L).
(2) get a beaker in addition and add the 41ml deionized water, the Ce (NO of dissolving 8.8g 3) 36H 2The O crystal forms the solution of clear, and this solution is added drop-wise to TiCl in the ice-water bath with the speed of 1d/s 4In the solution.
(3) mixed solution is under magnetic agitation, dropwise drips volume ratio and be 1: 1 ammoniacal liquor (1d/s) 203ml, the pH=10 of titration end point solution.With the gained yellow mercury oxide in its mother liquor under room temperature still aging 24h, through suction filtration, with deionized water wash to there not being Cl -(use AgNO 3Solution check Cl -Exist).
(4) sample survey does not have Cl -After the existence, change baking oven over to, in 110 ℃ baking oven, dry by the fire 12h, obtain CeO 2-TiO 2The composite oxides precursor.
(5) then with CeO 2-TiO 2The composite oxides precursor changes muffle furnace over to, and the control heat-up rate is 3 ℃/min, changes 700 ℃ of roasting 2h of muffle furnace over to, promptly gets Ce 4Ti 9O 24Composite oxides.
The results are shown in Figure 1 detects through XRD and to show: only occur not really significantly TiO in the catalyzer spectrogram of 500 ℃ of roastings 2The anatase octahedrite characteristic diffraction peak.Along with the rising of maturing temperature, TiO 2The anatase octahedrite peak become obvious.Compare with the catalyzer spectrogram of 600 ℃ of roastings, more crystalline phase peak has appearred in the catalyzer spectrogram of 700 ℃ of roastings, and some peak that occurs in the catalyzer spectrogram of 700 ℃ of roastings disappears in the spectrogram of the catalyzer of 800 ℃ of roastings on the contrary, and this is because Ce occurred in the time of 700 ℃ 4Ti 9O 24Be transformed into rutile and cerianite when composite oxides, 800 ℃ of these composite oxides.
Embodiment 2:
(1) TiCl 4The preparation of solution and preparation: configuration concentration is 0.5mol/L TiCl in the 600ml beaker 4Solution is got 9ml and is added drop-wise to (1d/s) in the 154ml deionized water, and the dropping process is carried out in ice-water bath, after being added dropwise to complete, stirs, and makes solution becomes clear.
(2) preparation of mixing solutions and preparation: the Ce (NO that takes by weighing 8.8g 3) 36H 2The O crystal adds the 41ml deionized water, and it is dissolved fully, forms the solution of clear, and concentration is 0.5mol, and this solution is added drop-wise to TiCl in the ice-water bath with the speed of 1d/s 4In the solution.
(3) mixing solutions is under magnetic agitation, dropwise drips volume ratio and be 1: 1 ammoniacal liquor (1d/s) 203ml, titration end point pH value of solution=10.With the gained yellow mercury oxide in its mother liquor under room temperature still aging 24h, through suction filtration, with deionized water wash to there not being Cl -(use AgNO 3Solution check Cl -Exist).
(4) sample with deionized water wash after, change baking oven over to, 110 ℃ of following oven dry 12h obtain CeO in baking oven 2-TiO 2The composite oxides precursor.
(5) change muffle furnace then over to, the control heat-up rate is 3 ℃/min, changes 700 ℃ of roasting 2h of muffle furnace over to, promptly gets Ce 4Ti 9O 24Composite oxides.
Fig. 2 Raman characterization result shows: the catalyzer of 500 ℃ of roastings mainly is to exist with unformed form.The catalyzer of 600 ℃ of roastings begins to occur five tangible absorption peaks (α, β, δ, γ and φ) and a unconspicuous κ peak, respectively at 365cm -1, 485cm -1, 560cm -1, 627cm -1, 760cm -1And 1610cm -1The place, the δ peak is CeO 2The crystalline phase peak, α and γ peak are the crystalline phase peaks of CuO, not being both because the environment difference at the two place of displacement occur.α, δ and φ peak are middle species Ce in the roasting process 4Ti 9O 24The absorption peak that occurs has occurred μ and θ peak again with the rising of maturing temperature, and μ and θ peak are final product CeTiO in the high-temperature calcination process 4The crystalline phase peak, the β peak is CeO 2The crystalline phase peak, γ is TiO 2The absorption peak of rutile phase.

Claims (4)

1, a kind of Ce 4Ti 9O 24The preparation method of composite oxides is characterized in that described Ce 4Ti 9O 24The mol ratio of component Ti and Ce is 0.8: 0.2 in the composite oxides, and preparation process is as follows:
1) add deionized water in a container, put it in the ice-water bath, after the system for the treatment of is stable, drip titanium tetrachloride solution lentamente, make the solution clarification, getting concentration is the presoma of 0.5mol/L titanium tetrachloride solution;
2) get adding deionized water dissolving cerous nitrate crystal in another container, obtaining concentration is the 0.5mol/L cerium nitrate solution;
3) cerium nitrate solution of step 2 is added drop-wise to the speed of 1d/s in the precursor solution of the titanium tetrachloride solution in the ice-water bath of step 1, and the mol ratio of control Ti and Ce is 0.8: 0.2, forms mixing solutions;
4) with the mixing solutions of step 2, under magnetic agitation, with the speed of 1d/s dropwise the volume ratio of dropping ammonia and mixing solutions be 1: 1 strong aqua, the pH=10 of titration end point solution obtains Ce 4Ti 9O 24The throw out of composite oxides precursor;
5) with the gained throw out in its mother liquor, still aging 24h under the room temperature, through suction filtration, with deionized water wash to there not being Cl -, in 110 ℃ baking oven, dry by the fire 12h, change muffle furnace then over to, at 700 ℃ of following roasting 2h, obtain Ce 4Ti 9O 24Composite oxides.
2, Ce according to claim 1 4Ti 9O 24The preparation method of composite oxides is characterized in that: the volume ratio of strong aqua concentration is 1: 1.
3, Ce according to claim 1 4Ti 9O 24The preparation method of composite oxides is characterized in that: the heat-up rate of muffle furnace roasting is controlled at 3 ℃/min.
4, Ce according to claim 1 4Ti 9O 24The preparation method of composite oxides is characterized in that: add the 154ml deionized water in the beaker of 600ml, put into ice-water bath, drip the TiCl of 9ml after the system for the treatment of is stable more lentamente 4Solution stirs, and getting concentration is the presoma of 0.5mol/L titanium tetrachloride solution; Other gets a beaker and adds the 41ml deionized water, the Ce (NO of dissolving 8.8g 3) 36H 2The O crystal forms the solution of clear, and this solution is added drop-wise to TiCl in the ice-water bath with the speed of 1d/s 4Form mixing solutions in the solution; Under magnetic agitation, dropwise dripping volume ratio with the speed of 1d/s is 1: 1 ammoniacal liquor 203ml, the pH=10 of titration end point solution; With the gained yellow mercury oxide in its mother liquor under room temperature still aging 24h, through suction filtration, with deionized water wash to there not being Cl -, in 110 ℃ baking oven, dry by the fire 12h, change muffle furnace then over to, at 700 ℃ of following roasting 2h, heat-up rate is controlled at 3 ℃/min, promptly obtains Ce 4Ti 9O 24Composite oxides.
CNA2008101201500A 2008-07-24 2008-07-24 Preparation of Ce4Ti9O24 composite oxides Pending CN101327952A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101807445A (en) * 2010-03-19 2010-08-18 清华大学 Preparation method of quadrivalent uranium-cerium-oxygen solid solution
CN102962074A (en) * 2012-11-19 2013-03-13 北京化工大学 Denitration catalyst of wide activity temperature window as well as preparation method and application thereof
WO2019096335A1 (en) * 2017-11-20 2019-05-23 首凯汽车零部件（江苏）有限公司 Composite thermistor material, and preparation method therefor and application thereof
CN111389388A (en) * 2020-04-14 2020-07-10 江西国瓷博晶新材料科技有限公司 Preparation method of cerium-titanium composite oxide with large specific surface area
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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101807445A (en) * 2010-03-19 2010-08-18 清华大学 Preparation method of quadrivalent uranium-cerium-oxygen solid solution
CN102962074A (en) * 2012-11-19 2013-03-13 北京化工大学 Denitration catalyst of wide activity temperature window as well as preparation method and application thereof
CN102962074B (en) * 2012-11-19 2014-11-26 北京化工大学 Denitration catalyst of wide activity temperature window as well as preparation method and application thereof
WO2019096335A1 (en) * 2017-11-20 2019-05-23 首凯汽车零部件（江苏）有限公司 Composite thermistor material, and preparation method therefor and application thereof
GB2582185A (en) * 2017-11-20 2020-09-16 Sook Automotive Components (Jiangsu) Co Ltd Composite thermistor material, and preparation method therefor and application thereof
GB2582185B (en) * 2017-11-20 2021-03-24 Sook Automotive Components Jiangsu Co Ltd High Temperature Negative Temperature Coefficient Thermistor Material and Preparation Method Thereof
CN111389388A (en) * 2020-04-14 2020-07-10 江西国瓷博晶新材料科技有限公司 Preparation method of cerium-titanium composite oxide with large specific surface area
CN113231759A (en) * 2021-05-17 2021-08-10 内蒙古工业大学 Rare earth-containing stainless steel welding rod for welding high-strength armored steel and preparation method thereof
CN113231759B (en) * 2021-05-17 2022-11-11 内蒙古工业大学 Rare earth-containing stainless steel electrode for welding high Jiang Zhuangjia steel and preparation method thereof
CN113884619A (en) * 2021-09-30 2022-01-04 眉山博雅新材料股份有限公司 Titration method
CN113884619B (en) * 2021-09-30 2024-02-02 眉山博雅新材料股份有限公司 Titration method

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