CN109879308A - A method of preparing lanthanium titanate - Google Patents
A method of preparing lanthanium titanate Download PDFInfo
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- CN109879308A CN109879308A CN201910136160.1A CN201910136160A CN109879308A CN 109879308 A CN109879308 A CN 109879308A CN 201910136160 A CN201910136160 A CN 201910136160A CN 109879308 A CN109879308 A CN 109879308A
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Abstract
The present invention provides a kind of methods for preparing lanthanium titanate: first, under surfactant-free, without catalysts conditions, synthesize pyridine -2,5- dicarboxylic acids rare earth coordination polymer sub-micron medicine ball by microwave method, then prepares nano-TiO (OH) with sluggish precipitation2, then by lanthanum polymerization of olefin using catalyst polymer and nano-TiO (OH)2It is ground uniformly under certain mass ratio, obtained sample is placed in Muffle furnace, calcines 5h at 1000 DEG C, is cooled to room temperature to obtain lanthanium titanate powder.This method 1., which has, prepares Product yields height, can amplification quantity production；2. side reaction is few, product purity is high；3. morphology controllable on the one hand can be obtained using coordination polymer as reactant, on the other hand the rare earth lanthanium titanate haveing excellent performance effectively reduces reaction temperature, shortens the reaction time, have low energy consumption, the series of advantages such as energy utilization rate height.
Description
Technical field
The present invention relates to rare earth titanates, and in particular to the preparation method of lanthanium titanate.
Background technique
Semiconductor light-catalyst because its solar energy conversion, medicine optical dynamic therapy and in terms of extensively answer
With and by scientists and engineers extensive concern.Perovskite type photocatalyst is made of the shared octahedra network in angle, is had
Efficient carrier mobility, thus photocatalytic activity with higher.In the research of various perovskite type catalysts, rare earth
Titanate La2Ti2O7(LTO) due to its unique two-dimensional layered structure, strong redox ability, high stability, hypotoxicity etc.
Advantage is always primary study object.More research work is carried out to LTO both at home and abroad at present, on the one hand it can make
For the centre of luminescence (Pr3+, Eu3+) host material, be used to prepare to obtain fluorescent powder by rare earth doped element；On the other hand it
Band gap magnitude Eg be 3.8eV, can be used as optical catalysts, accelerate the drop of chemical reaction (decomposition of such as water) and toxic organic compound
Solution.But finding more low power consuming and the easier method synthesis uniform lanthanium titanate haveing excellent performance of pattern is always a challenge.
In recent years, has the LTO that many document reports differently prepare function admirable with different raw materials
Material.Wherein according to the difference of preparation means, preparation method can be divided into: molten-salt growth method, coprecipitation, hydrothermal synthesis method, pulse
Laser deposition and sol-gal process (sol-gel) etc..Wherein hydrothermal synthesis method and molten-salt growth method are most common methods, such as:
Tetsuro Majima is recently reported a kind of one step hydro thermal method, by La (NO3)3·6H2O and Ti (SO4)2It is dissolved in ultrapure water
In, after a certain amount of NaOH solution is added dropwise, mixture is transferred in ptfe autoclave, it is small that 24 are reacted at 230 DEG C
When, obtain the smooth and non-uniform LTO nano flake of 100~600nm.Kazunari Dome and his partner are in Paul
It is improved in the method for A.Fuiere et al., by La2O3And TiO2Mixing in ethanol, the NaCl and KCl of quality such as adds,
5h is calcined under 1423K, is cooled to room temperature and fused salt is washed with deionized water again is obtained LTO brick-shaped of the basic size at 1 μm or more
Structure.Above-mentioned this hydrothermal synthesis method is although easy to operate but very time consumption and energy consumption, and although this fused salt shortens reaction
Time, but operating procedure is relatively cumbersome while needing higher temperature that could complete series reaction.
Coordination polymer (CP) has good structure sanction property, Yi Gong as a kind of novel functionalization molecular material
The characteristics such as energyization.Research is found by that, come nano materials, can optimize the shape of material using coordination polymer as presoma
Looks and performance.In recent years, applicant is prepared for series of rare earth coordination polymer micro/nano material and using it as precursor preparation
Rare earth oxide, rare earth nitride, rare-earth oxide sulfate and its composite material etc..In addition, applicant is also with cerium basigamy
Position polymer is that presoma uses one-step calcination method to be prepared for the adjustable more shell ceria hollow spheres of shell, and this more shells
Ceria shows extraordinary catalytic performance relative to other bulk cerias.The result shows that coordination polymers is to prepare
Ideal presoma with the micro Nano material that pattern is controllable and has excellent performance, and contain in coordination polymer nonmetallic
Element, such as C, N, P, S etc. can also be remained in the synthesis process by different modes, play the work for improving property
With.But rare earth titanate is prepared as presoma using coordination polymer and is but had not been reported.
Summary of the invention
For this purpose, the present invention provides a kind of new method for preparing lanthanium titanate, this method can get nanometer to micron-sized LTO
Powder.
Firstly, efficiently synthesizing lanthanum polymerization of olefin using catalyst using no pressure microwave method under conditions of no catalyst and surfactant
Polymer (LaCP).Then, nano-TiO (OH) is prepared by simply sluggish precipitation2.Finally, the lanthanum polymerization of olefin using catalyst that will be obtained
Polymer and nano-TiO (OH)2Lanthanium titanate powder is obtained than calcining by certain mass.The step of this method, is summarized as follows:
(1) lanthanum nitrate, pyridine -2,5- dicarboxylic acids are dissolved in organic solvent, solution is placed in microwave reaction device,
It is reacted under counterflow condition, isolates solid matter after the reaction was completed, obtain lanthanum polymerization of olefin using catalyst polymer；
(2) sodium hydroxide is dissolved in water, is heated to 60~100 DEG C, titanium tetrachloride solution is added dropwise while stirring,
Then pH to 8~10 is adjusted, the white precipitate of generation is separated, nano-TiO (OH) is obtained2；
(3) by the nano-TiO (OH) of the lanthanum polymerization of olefin using catalyst polymer of step (1) and step (2)2After mixing, 800~
A period of time is handled at 1000 DEG C, obtains lanthanium titanate (LTO powder).
In step (1), organic solvent can be n,N-Dimethylformamide (DMF).
In step (1), the power of microwave reaction device can be 80~400W.
In step (2), NH can be used3·H2O adjusts pH=8~10.
In step (3), lanthanum polymerization of olefin using catalyst polymer and nano-TiO (OH)2Mass ratio can be 3:0.4.
In step (3), the processing time can be 5h.
Step (1) synthesizes LaCP using microwave heating method, and due to microwave method homogeneous heating, thermal gradient is small and shaping speed
Fastly, lanthanum polymerization of olefin using catalyst polymer sub-micron sphere can be formed under conditions of no template, the coordination polymer size of synthesis is uniform
And partial size is smaller.Step (2) prepares nano-TiO (OH) using sluggish precipitation2, this process is past with extremely slow speed while stirring
Titanium tetrachloride solution is added in sodium hydroxide, equably releases configurational ion；It is same that other alkali are added dropwise with extremely slow speed again, it allows
OH-With TiO2+It generates TiO (OH)2, that is, precipitate.Rate of addition is controlled, can accomplish that control generates the rate of precipitating, it can be suitable
When obtained in the supersaturated solution in range size tunable, single-size, not largely reunite, purity is high nano-TiO (OH)2。
The present invention is by the selection to composition of raw materials, with the TiO (OH) generated under unformed LaCP and low temperature2For reaction
Object, mainly since (i) coordination polymer not only has the topological structure type of multiplicity, but also in optics, magnetics, absorption point
Potential application value is shown in fields from, catalysis etc., can be used as the ideal forerunner of inorganic metal micro-/ nano composite material
Body；(ii) select unformed coordination polymer as reactant, this inferior stable state LaCP is easier to participate in reaction, can be effective
Ground reduces reaction temperature and shortens the reaction time；(iii) the poor TiO of selective freezing (OH)2Without selecting rutile-type
Titanium dioxide, mainly due to TiO (OH)2With more open crystal structure, it is equally more advantageous to the generation of reaction.
In coordination polymer, selection with pyridine -2,5- dicarboxylic acids for organic linker, mainly due to 1) pyridine -2,
A kind of n-heterocyclic ligand of the 5- dicarboxylic acids as similar terephthalic acid (TPA) is provided simultaneously with more carboxyl ligands and aromatic ligand
Advantage；2) pyridine -2,5- dicarboxylic acids not only can completely deprotonation again can part deprotonation, can there are many acidity coordination
Mode；3) pyridine -2,5- dicarboxylic acids can be not only coordinated with oxygen coordination but also with nitrogen, possessed coordination mode abundant and be conducive to be built with
Machine metallic framework.
Method of the invention needs not move through heat treatment process, directly by LaCP and nano-TiO (OH)2It is uniformly mixed it
Afterwards, it is calcined in Muffle furnace, 1000 DEG C of calcination temperature, calcination time 5h.The LTO nanometer sheet of synthesis be average thickness be 60nm,
Width is 500nm or so brick-shaped structure.By to calcination temperature adjust can in various degree control LTO nanometer sheet shape
Looks and purity.
Method of the invention is not only simple, but also rapidly and efficiently, has homogeneous heating, energy utilization rate high and the reaction time
The series of advantages such as short can effectively reduce cost and save the energy；The LTO morphology microstructure more importantly synthesized is uniform,
Applications in various fields performance can be improved；For LTO powder subsequent applications (as prepared LTO piezoelectric ceramics, rare earth doped element
LTO fluorescent powder, LTO, LTON of excellent properties and its compound photochemical catalyst etc.) it lays a good foundation.It adopts compared with the prior art
With the method for hydrothermal synthesis, method of the invention, which is provided simultaneously with, to be shortened the reaction time, increases products collection efficiency and the lower, shape that consumes energy
The advantages that looks are more evenly, performance is more superior.
Detailed description of the invention
Fig. 1 is the XRD spectrum of lanthanium titanate (LTO) nanometer sheet prepared by embodiment 1.
Fig. 2 is the scanning electron microscope (SEM) photograph of LTO nanometer sheet prepared by embodiment 1.
Fig. 3 is the scanning electron microscope (SEM) photograph of LaCP sub-micron ball prepared by embodiment 1.
Fig. 4 is nano-TiO (OH) prepared by embodiment 12Transmission electron microscope picture.
Fig. 5 is the XRD spectrum of LTO nanometer sheet prepared by embodiment 2.
Fig. 6 is the scanning electron microscope (SEM) photograph of LTO powder prepared by embodiment 2.
Specific embodiment
Embodiment 1:
Step 1: by 0.1mmol La (NO3)3·6H2O and 0.3mmol pyridine -2,5- dicarboxylic acids is dissolved in 32mL N-N bis-
In the solvent of methylformamide.After ultrasonic dissolution is complete, obtained mixed solution is transferred in round-bottomed flask and is placed in experiment again
In the microwave reaction device of room, 5min is reacted in the case where power is 240W counterflow condition, cooling centrifuge washing after reaction, 60 DEG C dry
To lanthanum polymerization of olefin using catalyst polymer sub-micron medicine ball.
Step 2: 25mmol sodium hydroxide solution is heated to 95 DEG C, 25mmol tetrachloro is added dropwise while stirring
Change titanium solution, after completion of dropwise addition, keep 15min at this temperature, is further continued for that ammonium hydroxide (25mmol) adjusting pH=8, stirring is added
20min cools down centrifuge washing after reaction, and finally by white precipitate, 60 DEG C of dry 12h obtain nano-TiO in vacuum drying oven
(OH)2。
Step 3: by drying sample lanthanum polymerization of olefin using catalyst polymer sub-micron medicine ball obtained above and nano-TiO (OH)2It presses
Mass ratio after mixing, is placed in Muffle furnace for 3:0.4, handles 5h at a temperature of 1000 DEG C, obtain LTO after being cooled to room temperature
Powder.
Embodiment 2:
Step 1: by 0.1mmol La (NO3)3·6H2O and 0.3mmol pyridine -2,5- dicarboxylic acids is dissolved in 32mL N-N bis-
In the solvent of methylformamide, after ultrasonic dissolution is complete, obtained mixed solution is transferred in round-bottomed flask and is placed in experiment again
In the microwave reaction device of room, 5min is reacted in the case where power is 240W counterflow condition, cooling centrifuge washing after reaction, 60 DEG C dry
To lanthanum polymerization of olefin using catalyst polymer sub-micron medicine ball.
Step 2: 25mmol sodium hydroxide solution is heated to 95 DEG C, 25mmol tetrachloro is added dropwise while stirring
Change titanium solution, after completion of dropwise addition, keep 15min at this temperature, is further continued for that ammonium hydroxide (25mmol) adjusting pH=8, stirring is added
20min cools down centrifuge washing after reaction, and finally by white precipitate, 60 DEG C of dry 12h obtain nano-TiO in vacuum drying oven
(OH)2。
Step 3: by LaCP sub-micron medicine ball obtained above and nano-TiO (OH)2It is mixed in mass ratio for 3:0.4
It after uniformly, is placed in Muffle furnace, handles 5h at a temperature of 900 DEG C, be cooled to room temperature and obtain LTO powder.
The LTO powder of Examples 1 and 2 is analyzed respectively, XRD diffraction pattern Rigaku/Max-3A X-ray diffraction
Instrument measurement (CuK α radiation,).Transmission electron microscope picture is in Japanese JEOL-2010 transmission electron microscopy
It is obtained on mirror, acceleration voltage 200kV.
Fig. 1 is the XRD diagram of the lanthanium titanate powder of embodiment 1, it can be seen that the almost all of peak of sample and monoclinic phase
The standard card (JCPDS 28-0517) of LTO fits like a glove, and illustrates lanthanum polymerization of olefin using catalyst polymer and TiO (OH) after calcining2Turn completely
LTO is turned to, determines that final product is LTO.
Fig. 2 is the SEM figure of the LTO powder of embodiment 1, and the LTO nanometer sheet synthesized as can be seen from Figure 2 is to be by average thickness
60nm, width are 500nm or so laminated structure composition.LTO nanometers of leaf length known to being examined in Fig. 2 (a) and 2 (b) from
Several hundred nanometers are differed to tens microns, and some of nanometer sheets have some be adhered.
Fig. 3 is the scanning electron microscope (SEM) photograph of the LaCP sub-micron medicine ball of embodiment 1, it can be seen that LaCP is by a large amount of
Diameter is distributed in the uniform sub-micron medicine ball composition of 150~300nm.By examining discovery, the surface of sub-micron ball
It is very smooth.
Fig. 4 is the nano-TiO (OH) of embodiment 12Transmission electron microscope picture, as can be seen from Figure 4 it is synthesized go out TiO (OH)2Particle
Crystallinity is poor, and pattern is the nano particle of irregular shape.
Fig. 5 is the XRD diagram of lanthanium titanate powder prepared by embodiment 2.It can be seen that the diffraction maximum of sample in addition to monocline
Identical outer also other diffraction maximums of the standard card (JCPDS 28-0517) of the LTO of phase.Illustrate LaCP and TiO (OH)2After calcining
It is partially converted into LTO.
Fig. 6 is the SEM figure of LTO powder prepared by embodiment 2, and the LTO synthesized as can be seen from Figure 6 is irregular sheet knot
Structure.The laminated structure length known to examining in figure μm is differed from tens nanometers to 2, some to be adhered and pattern is irregular.
In conclusion the present invention passes through the Asia that the method rapid synthesis of microwave heating is uniform under the conditions of flowing back no pressure
The spherical lanthanum polymerization of olefin using catalyst polymer (LaCP) of micron, then uniform TiO (OH) is prepared by simple coprecipitation2Nanoparticle
Son, with the LaCP and TiO (OH) prepared2For raw material, 5h is handled at a temperature of 800~1000 DEG C using solid phase method, is obtained
LTO powder body material.
Claims (6)
1. a kind of method for preparing lanthanium titanate, includes the following steps:
(1) lanthanum nitrate, pyridine -2,5- dicarboxylic acids are dissolved in organic solvent, solution is placed in microwave reaction device, flowed back
Under the conditions of react, isolate solid matter after the reaction was completed, obtain lanthanum polymerization of olefin using catalyst polymer；
(2) sodium hydroxide is dissolved in water, is heated to 60~100 DEG C, titanium tetrachloride solution is added dropwise while stirring, then
PH to 8~10 or so is adjusted, the white precipitate of generation is separated, nano-TiO (OH) is obtained2；
(3) by the nano-TiO (OH) of the lanthanum polymerization of olefin using catalyst polymer of step (1) and step (2)2After mixing, 800~1000
A period of time is handled at DEG C, obtains lanthanium titanate.
2. according to the method described in claim 1, it is characterized by: in step (1), organic solvent N, N- dimethyl formyl
Amine.
3. according to the method described in claim 1, it is characterized by: in step (1), the power of microwave reaction device is 80~
400W。
4. according to the method described in claim 1, it is characterized by: using NH in step (2)3·H2O adjusts pH to 8~10.
5. according to the method described in claim 1, it is characterized by: in step (3), lanthanum polymerization of olefin using catalyst polymer and nano-TiO
(OH)2Mass ratio be 3:0.4.
6. according to the method described in claim 1, it is characterized by: the processing time is 5h in step (3).
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2019
- 2019-02-25 CN CN201910136160.1A patent/CN109879308B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20110281111A1 (en) * | 2010-05-11 | 2011-11-17 | Board Of Regents Of The Nevada System Of Higher Education, On Behalf Of The University Of Nevada, | Synthesis of pyrochlore nanostructures and uses thereof |
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| JP2012184136A (en) * | 2011-03-04 | 2012-09-27 | Seiko Epson Corp | Method for producing lanthanum titanate particle, lanthanum titanate particle and lanthanum titanate particle dispersion |
| CN105645469A (en) * | 2016-03-09 | 2016-06-08 | 武汉科技大学 | Nano rodlike lanthanum titanate powder and preparation method thereof |
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