CN110589890B - Method for simultaneously preparing spinel type and perovskite type manganese titanate nanoparticles and application - Google Patents
Method for simultaneously preparing spinel type and perovskite type manganese titanate nanoparticles and application Download PDFInfo
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Abstract
The invention provides a method for simultaneously preparing spinel-type and perovskite-type manganese titanate nanoparticles and application thereof, and relates to the field of catalyst synthesis 2 Nanosheets as a Mn precursor, titanic acidSelective hydrolysis of tetrabutyl ester as Ti source in MnO 2 The surface of the nano sheet forms a continuous coating layer, thereby generating MnO 2 /TiO 2 Calcining the obtained composite nanosheet in flowing argon at different temperatures to respectively obtain spinel-type and perovskite-type manganese titanate nanoparticles; the invention utilizes tetrabutyl titanate in a sol-gel system of pure ethanol in MnO 2 Selectively hydrolyzing the surface of the nano sheet to generate amorphous titanium oxide, and calcining the amorphous titanium oxide in an argon atmosphere to promote titanium oxide and MnO 2 Solid-phase reaction to obtain MnTi 2 O 4 And MnTiO 3 The nano-particles do not need to be prepared into manganese titanate nano-particles of each crystal form by two different methods, the method has less steps, and no intermediate product harmful to the environment is generated.
Description
Technical Field
The invention relates to the field of catalyst synthesis, in particular to a method for simultaneously preparing spinel type and perovskite type manganese titanate nanoparticles and application thereof.
Background
The perovskite type titanate and the spinel type titanate have wide application prospects in the fields of photocatalytic degradation of organic pollutants, dye-sensitive solar cells, nano sensors, lithium ion batteries and the like. In recent years, a series of techniques for preparing manganese titanate have been developed, such as solid-phase reaction, hydrothermal preparation, sol-gel, complexing agent-assisted precipitation, and coprecipitation, among others. However, in the presently disclosed manganese titanate preparation methods, spinel-type and perovskite-type manganese titanates can only be prepared separately by different routes, and there is no method that can prepare manganese titanates of both structures simultaneously.
For example, patent CN108423713A discloses a method for preparing a pure perovskite type manganese titanate nanosheet material, and application of the manganese titanate nanosheet as a catalyst in degrading pollutants in heterogeneous fenton-like, which solves the problems of large particle size and few surface active sites of manganese titanate prepared by the existing method, and the method comprises the following steps: firstly, dissolving manganese salt and titanium salt in deionized water to obtain manganese salt and titanium salt solution; secondly, dissolving organic alkali in manganese salt and titanium salt solution; thirdly, dissolving caustic alkali in deionized water to form a caustic alkali solution, adding the caustic alkali solution into the manganese salt and titanium salt solution, and reacting to generate manganese titanium hydroxideA precursor; transferring the manganese titanium hydroxide precursor into a hydrothermal kettle, and heating to obtain manganese titanate nanosheets with different shapes; fifthly, washing and drying the manganese titanate nanosheet material to obtain a finished product; the method improves the uniformity of pure perovskite type manganese titanate nanosheet particles and particle size, and has the advantages of large specific surface area and abundant surface active centers. Also, as disclosed in patent CN102989446A, a hydrothermal synthesis method is adopted, in which titanate nanowires are used as Ti source, and MnCl is used as 2 Mn source and NaF source are adopted, and MnTiO with a sheet structure and uniform appearance and diameter is prepared under the condition of adding NaOH 3 And F-MnTiO 3 The method and the application of the two materials in the catalytic degradation of the organic dye rhodamine B under the condition of visible light irradiation.
Both of the preparation methods disclosed in the above two patents adopt a hydrothermal method to directly prepare single crystal form of perovskite type manganese titanate, both methods cannot be applied to preparation of spinel type manganese titanate, other methods such as a solid phase reaction method, a sol-gel method and the like are also required to prepare spinel type manganese titanate, when two crystal forms of manganese titanate are required to perform a comparative test, different methods are required to prepare two crystal forms of manganese titanate, and the process steps are complicated.
Disclosure of Invention
The invention aims to provide a method for simultaneously preparing spinel-type and perovskite-type manganese titanate nanoparticles and application thereof, wherein tetrabutyl titanate is used in a sol-gel system of pure ethanol in MnO 2 The surface of the nano sheet is selectively hydrolyzed to generate amorphous titanium oxide, and then the amorphous titanium oxide is heated in an argon atmosphere to promote titanium oxide and manganese dioxide to generate solid phase reaction to obtain spinel type manganese titanate and perovskite type manganese titanate, and the manganese titanate nano particles with different crystal forms are not required to be prepared by two methods respectively.
In order to achieve the above purpose, the invention provides the following technical scheme: a method for simultaneously preparing spinel-type and perovskite-type manganese titanate nanoparticles comprises the following steps:
s1, adding MnO 2 Dispersing the nano-sheet in ethanol to obtain MnO 2 A nanosheet suspension;
s2 MnO Conditioning S1 under stirring 2 The pH of the nanosheet suspension is alkaline;
s3, dropwise adding ethanol solution of tetrabutyl titanate into alkaline MnO of S2 2 In the nano-sheet suspension, stirring is continued until tetrabutyl titanate is in MnO 2 Fully reacting the surface of the nanosheet;
s4, filtering the reaction solution of S3, taking a solid product, alternately centrifuging and washing the solid product by using ethanol and deionized water respectively, and drying the washed solid product to obtain a titanium-manganese compound nanosheet;
and S5, calcining the titanium-manganese compound nanosheet obtained in the step S4 in an argon environment at different temperatures to respectively obtain spinel type manganese titanate nanoparticles and perovskite type manganese titanate nanoparticles.
Further, in said S2, to MnO 2 Adding ammonia water into nanosheet suspension to adjust MnO 2 The nanosheet suspension is alkaline; MnO adjustment by ammonia water 2 The purpose of the alkaline nanosheet suspension is to preset an alkaline environment for the ethanol solution of the tetrabutyl titanate S3 and slow down the reaction of the tetrabutyl titanate in MnO 2 Hydrolysis in the nanosheet suspension.
Further, the calcination temperature of the spinel-type manganese titanate nanoparticles prepared in S5 is 450 ℃, and the calcination temperature of the perovskite-type manganese titanate nanoparticles prepared is 650 ℃.
Further, the calcination process for preparing the manganese titanate nanoparticles comprises the following steps: setting the calcining temperature, the heating rate to be 10 ℃/min, and calcining for 2h at the constant temperature under the set calcining temperature.
Further, in the step S1, MnO is pulverized by an ultrasonic pulverization method 2 The nano-sheets are uniformly dispersed in ethanol, so that the ethanol solution of tetrabutyl titanate is uniformly adsorbed and hydrolyzed in MnO 2 And (3) the surface of the nanosheet.
Further, the ethanol is a pure ethanol solvent.
Further, in the step S3, the concentration of the ethanol solution of tetrabutyl titanate is 10mL/L to 100mL/L, and the ethanol solution of tetrabutyl titanate is to avoid direct hydrolysis of tetrabutyl titanate, and the too high solubility of the solution is likely to be directly hydrolyzed by contacting with air, and the too low solubility reaction efficiency is low.
The invention also discloses a method for preparing spinel and perovskite manganese titanate nanoparticles simultaneously by using the manganese titanate nanoparticles as a catalyst to selectively catalyze and reduce NH 3 The application of the direction.
According to the technical scheme, the method for simultaneously preparing spinel-type and perovskite-type manganese titanate nanoparticles and the application thereof have the following beneficial effects:
the invention discloses a method for simultaneously preparing spinel-type and perovskite-type manganese titanate nanoparticles and application thereof, wherein MnO is used in a sol-gel system of pure ethanol 2 Ultrathin nanosheets as Mn precursors, tetrabutyl titanate (TBOT) as a Ti source, selectively hydrolyzed in MnO 2 The surface of the nano sheet forms a continuous coating layer, thereby generating MnO 2 /TiO 2 And (3) compounding the nano sheets, and calcining the obtained compounded nano sheets in flowing argon to obtain the manganese titanate nano particles. Spinel-type MnTi is prepared in turn by changing the calcination temperature 2 O 4 Nanoparticles and perovskite-type MnTiO 3 And (3) nanoparticles. The invention utilizes tetrabutyl titanate in a sol-gel system of pure ethanol in MnO 2 Selectively hydrolyzing the surface of the nano sheet to generate amorphous titanium oxide, and then heating the amorphous titanium oxide and MnO in an argon atmosphere to promote titanium oxide and MnO 2 Solid-phase reaction to obtain MnTi 2 O 4 And MnTiO 3 The method has the advantages that the method does not need two different methods to prepare the manganese titanate nanoparticles with different crystal forms respectively, the method has few steps, the solvent is ethanol, and no intermediate product harmful to the environment is generated.
The invention adopts the MnTi prepared by the method 2 O 4 And MnTiO 3 Selective catalytic reduction of NH by nanoparticles 3 Application experiments show that the spinel MnTi has low crystallinity 2 O 4 Nanoparticles to NH at a temperature below 240 DEG C 3 The selective catalytic reduction of the catalyst has excellent performance, and the NO conversion efficiency reaches 96 percent; perovskite type MnTiO 3 Compared with spinel MnTi 2 O 4 Nanoparticles, at temperatures below 160 ℃, have relatively low conversion efficiency for NO.
It should be understood that all combinations of the foregoing concepts and additional concepts described in greater detail below can be considered as part of the inventive subject matter of this disclosure unless such concepts are mutually inconsistent.
The foregoing and other aspects, embodiments and features of the present teachings can be more fully understood from the following description taken in conjunction with the accompanying drawings. Additional aspects of the present invention, such as features and/or advantages of exemplary embodiments, will be apparent from the description which follows, or may be learned by practice of the specific embodiments according to the teachings of the present invention.
Drawings
The drawings are not intended to be drawn to scale. In the drawings, each identical or nearly identical component that is illustrated in various figures may be represented by a like numeral. For purposes of clarity, not every component may be labeled in every drawing. Embodiments of various aspects of the present invention will now be described, by way of example, with reference to the accompanying drawings, in which:
FIG. 1 is a TEM image of spinel-type manganese titanate nanoparticles prepared at a calcination temperature of 450 ℃ according to the present invention;
FIG. 2 is a TEM image of perovskite-type manganese titanate nanoparticles prepared at a calcination temperature of 650 ℃ according to the present invention;
FIG. 3 is a TEM image of manganese titanate nanoparticles prepared at a calcination temperature of 350 ℃ according to the present invention;
FIG. 4 is a TEM image of manganese titanate nanoparticles prepared at a calcination temperature of 550 ℃ according to the present invention;
FIG. 5 is an XRD spectrum of manganese titanate nanoparticles prepared at various calcination temperatures in accordance with the present invention;
FIG. 6 shows that the manganese titanate nanoparticles prepared at various calcination temperatures according to the present invention selectively catalyze NH 3 And (4) an efficiency map.
Detailed Description
In order to better understand the technical content of the present invention, specific embodiments are described below with reference to the accompanying drawings.
In this disclosure, aspects of the present invention are described with reference to the accompanying drawings, in which a number of illustrative embodiments are shown. Embodiments of the present disclosure are not intended to be limited to all aspects of the invention. It should be appreciated that the various concepts and embodiments described above, as well as those described in greater detail below, may be implemented in any of numerous ways, as the disclosed concepts and embodiments are not limited to any one implementation. In addition, some aspects of the present disclosure may be used alone, or in any suitable combination with other aspects of the present disclosure.
Based on the fact that different methods are needed to be adopted to prepare manganese titanate nanoparticles with different crystal forms in the prior art, the reaction steps are various, and spinel-type MnTi can not be obtained simultaneously by adopting a single method 2 O 4 Nanoparticles and perovskite-type MnTiO 3 A nanoparticle; the invention aims to provide a method for simultaneously preparing spinel type and perovskite type manganese titanate nanoparticles and application thereof, and the method has the advantages of few reaction steps and environmental friendliness.
The invention discloses a method for simultaneously preparing spinel-type and perovskite-type manganese titanate nanoparticles, which comprises the following steps: s1, adding MnO 2 Dispersing the nano-sheet in ethanol to obtain MnO 2 A nanosheet suspension; s2 MnO Conditioning S1 under stirring 2 The pH of the nanosheet suspension is alkaline; s3, dropwise adding ethanol solution of tetrabutyl titanate into alkaline MnO of S2 2 In the nano-sheet suspension, stirring is continued until tetrabutyl titanate is in MnO 2 Fully reacting the surface of the nanosheet; s4, filtering the reaction solution of S3, taking a solid product, alternately centrifuging and washing the solid product by using ethanol and deionized water respectively, and drying the washed solid product to obtain a titanium-manganese compound nanosheet; and S5, calcining the titanium-manganese compound nanosheet obtained in the step S4 in an argon environment at different temperatures to respectively obtain spinel type manganese titanate nanoparticles and perovskite type manganese titanate nanoparticles.
The design principle of the reaction steps is that tetrabutyl titanate is utilized in a sol-gel system of pure ethanol in MnO 2 Selectively hydrolyzing the surface of the nano sheet to generate amorphous titanium oxide, and then regulatingAnd (3) calcining, heating in an argon atmosphere to promote titanium oxide and manganese dioxide to perform solid-phase reaction to obtain spinel type manganese titanate and perovskite type manganese titanate, namely directly obtaining manganese titanate nanoparticles with different crystal forms by combining a sol-gel method and a solid-phase reaction method.
The method and application of the present invention for preparing spinel-type and perovskite-type manganese titanate nanoparticles are further described in detail with reference to the examples shown in the drawings.
Example 1
Preparation of spinel-type MnTi 2 O 4 Nanoparticles
MnO is crushed by ultrasonic 2 The nanoplatelets are uniformly dispersed in a pure ethanol solvent to form stable MnO 2 The concentration of the nano-sheet suspension is 2mg/mL, the ultrasonic power is 700w, and the ultrasonic treatment is carried out for 30 min; taking MnO 2 40mL of nanosheet suspension is added into MnO under the stirring condition of a magnetic stirrer 2 Adding 0.1mL of ammonia water into the nanosheet suspension to adjust MnO 2 The pH value of the nanosheet suspension is alkaline; adding 10mL of ethanol into another drying beaker, adding 0.5mL of tetrabutyl titanate (TBOT) into the drying beaker under the stirring condition to prepare an ethanol solution of tetrabutyl titanate with the concentration of 50mL/L, and dropwise adding ethanol solution of TBOT with the concentration of 50mL/L into alkaline MnO 2 Nanosheet suspension, stirred overnight to TBOT in MnO 2 Fully reacting the surface of the nanosheet; filtering the reaction liquid after the reaction, taking a solid product, then respectively using de-ethanol and ionized water to centrifugally wash for three times, and drying, wherein the drying condition is drying at 80 ℃ for 12 hours to obtain a titanium-manganese composite nanosheet; placing the dried titanium-manganese composite nanosheet in a flowing argon tube type furnace, setting the calcining temperature to be 450 ℃, setting the programmed heating rate to be 10 ℃/min, and calcining for 2h to obtain spinel-type MnTi with low crystallinity 2 O 4 The transmission electron microscope image of the nano-particles and the product is shown in figure 1, and the crystal form image of the product is shown in figure 5.
In the invention, ammonia water is selected to adjust MnO 2 The pH of the nano-sheet suspension liquid makes the nano-sheet suspension liquid alkaline, and the aim is that the alkaline environment is favorable for slowing down the subsequent addition of tetrabutyl titanate in MnO 2 Hydrolysis rate of nanosheet surfaceWhen tetrabutyl titanate is hydrolyzed too quickly, the amorphous titanium oxide formed cannot be uniformly attached to MnO 2 The nano sheets and the titanium oxide are stacked mutually, so that the purity of the manganese titanate nano particles in the final product is influenced. Similarly, tetrabutyl titanate is firstly dissolved in ethanol, and the tetrabutyl titanate is prevented from being hydrolyzed directly in air during taking.
Example 2
Preparation of perovskite-type MnTiO 3 Nanoparticles
The difference between the embodiment 2 and the embodiment 1 is that the dried titanium-manganese composite nanosheet is placed in a flowing argon tube type furnace, the calcining temperature is set to be 650 ℃, the temperature programming rate is 10 ℃/min, and the calcining time is 2h, so that perovskite type MnTiO with high crystallinity is obtained 3 The transmission electron micrograph of the nanoparticles, the product, is shown in figure 2.
Example 3
The difference between the example 3 and the example 1 is that the dried titanium-manganese composite nanosheet is placed in a flowing argon tube type furnace, the calcining temperature is set to be 350 ℃, the temperature programming rate is 10 ℃/min, and calcining is carried out for 2h, so that spinel type manganese titanate nanoparticles with poor crystallinity are obtained, and a transmission electron microscope image of the product is shown as fig. 3.
Example 4
Example 4 is different from example 1 in that the dried titanium-manganese composite nanosheets are placed in a flowing argon tube type furnace, the calcining temperature is set to be 350 ℃, the temperature programming rate is 10 ℃/min, and calcining is carried out for 2h, so that spinel-type and perovskite-type mixed manganese titanate nanoparticles are obtained, and a transmission electron microscope image of the product is shown in fig. 4.
As shown in connection with fig. 5, at a calcination temperature of 350 ℃, the titanium manganese composite nanoplates begin to produce spinel-type MnTi with very poor crystallinity 2 O 4 (ii) a Obtaining spinel-type MnTi with low crystallinity at the calcination temperature of 450 DEG C 2 O 4 A nanoparticle; as the calcination temperature was increased to 550 ℃, a small portion of the final product began to convert to MnTiO with a perovskite structure of higher crystallinity 3 (ii) a When the calcining temperature is increased to 650 ℃, the final product is MnTiO of perovskite type with high crystallinity 3 And (3) nanoparticles.
The invention also discloses the application of the manganese titanate nano-particles prepared by the preparation method in Selective Catalytic Reduction (SCR) of NH 3 The final product manganese titanate nano-particles are used as a catalyst to selectively catalyze and reduce NH 3 The specific procedure is shown in the following examples. The data for NO at each reaction temperature in example 5 are the concentration data of NO in ppm measured at the current temperature by sampling.
Example 5
Respectively taking 50mg of the manganese titanate nanoparticles obtained in the embodiments 1 to 4 as catalysts, tabletting any one part of the catalysts by a tabletting machine at 20MPa, and then sieving the tabletted particles with a sieve of 50-60 meshes to obtain small solid particles, and filling the obtained particles into a fixed bed quartz reactor for SCR test; before testing, purging is carried out for 40min to enable the fixed bed quartz reactor to reach a stable state, then heating is started, when the temperature of the reactor reaches 80 ℃, 120 ℃, 160 ℃, 200 ℃, 240 ℃ and is stabilized for 10min, samples are respectively taken, and analysis and detection are carried out on the samples. In the embodiment, the change of the concentration of NO catalyzed in the simulated flue gas is detected to represent that the catalyst catalyzes and reduces NH 3 The gas concentration of NO in the sample was measured on-line by a smoke analyzer, and the specific results are shown in table 1 and fig. 6.
The manganese titanate nano-particles obtained at different temperatures are used as a catalyst to perform selective catalytic reduction on NH3, and the result shows that spinel MnTi with low crystallinity 2 O 4 Nanoparticles to NH at low temperature, i.e. reaction temperature below 240 ℃ 3 The SCR of (1) has excellent performance, and the NO conversion efficiency reaches 96% when the reaction temperature is increased to 240 ℃. Compared with spinel MnTi 2 O 4 Nanoparticles, perovskite-type MnTiO 3 The conversion rate of the nanoparticles to NO is relatively low when the reaction temperature is lower than 160 ℃, and the conversion rate of NO gradually increases when the reaction temperature exceeds 160 ℃.
TABLE 1 Selective catalytic reduction of NH by manganese titanate nanoparticles prepared at different calcination temperatures 3 Efficiency meter
The spinel-type MnTi prepared from ethanol solutions of TBOT with different concentrations is further researched in the application document of the invention 2 O 4 Nanoparticle Selective Catalytic (SCR) reduction of NH 3 The specific results of (3) are shown in Table 2.
TABLE 2 Selective catalytic reduction of NH by manganese titanate nanoparticles prepared with different reactant concentrations 3 Efficiency meter
Combining Table 2, different concentrations of ethanol solutions of TBOT versus spinel-type MnTi 2 O 4 Nanoparticle catalytic reduction of NH 3 The influence of (2) is small, wherein when the concentration of the TBOT ethanol solution is 50mL/L, the NO conversion efficiency is highest. When the concentration of ethanol solution of TBOT is less than 50mL/L, the amount of substance of TBOT is small and MnO may not be reduced 2 The surface of the nano sheet is completely covered. When the concentration of the TBOT ethanol solution is higher than 50mL/L, the purity of the phase is affected due to the excessive amount of TBOT substances, and excessive TiO exists 2 Fail to contact MnO 2 The nanosheets react, thereby affecting the catalytic effect of the manganese titanate nanoparticles.
Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, the protection scope of the present invention should be determined by the appended claims.
Claims (3)
1. A method for simultaneously preparing spinel-type and perovskite-type manganese titanate nanoparticles is characterized by comprising the following steps:
s1, adding MnO 2 Dispersing the nano-sheet in ethanol to obtain MnO 2 A nanosheet suspension; wherein the ethanol is a pure ethanol solvent;
s2, MnO Conditioning S1 under stirring 2 The pH of the nanosheet suspension is alkaline;
s3, dropwise adding ethanol solution of tetrabutyl titanate with the concentration of 10-100 mL/L into alkaline MnO of S2 2 In the nano-sheet suspension, stirring is continued until tetrabutyl titanate is in MnO 2 Fully reacting the surface of the nanosheet;
s4, filtering the reaction solution of S3, taking a solid product, alternately centrifuging and washing the solid product by using ethanol and deionized water respectively, and drying the washed solid product to obtain a titanium-manganese compound nanosheet; wherein the titanium manganese compound nano sheet is MnO with amorphous titanium oxide on the surface 2 Nanosheets;
s5, calcining the manganese titanate compound nanosheets obtained in the step S4 in an argon environment at different temperatures to respectively obtain spinel type manganese titanate nanoparticles and perovskite type manganese titanate nanoparticles;
wherein the reaction process of S5 is MnO 2 The nano-sheet and amorphous titanium oxide on the surface of the nano-sheet are subjected to solid phase reaction to prepare MnTi 2 O 4 Or MnTiO 3 A nanoparticle; and in the calcination process in S5, the calcination temperature is set, the heating rate is 10 ℃/min, the constant-temperature calcination is carried out for 2h at the set calcination temperature, the calcination temperature for preparing the spinel type manganese titanate nanoparticles is set to be 450 ℃, and the calcination temperature for preparing the perovskite type manganese titanate nanoparticles is set to be 650 ℃.
2. The method for simultaneously preparing spinel and perovskite manganese titanate nanoparticles of claim 1, wherein the step of S2 is conducted to MnO 2 Adding ammonia water into nanosheet suspension to adjust MnO 2 The nanosheet suspension is alkaline.
3. The method for simultaneously preparing spinel and perovskite manganese titanate nanoparticles according to claim 1, wherein MnO is subjected to ultrasonic pulverization in S1 2 The nanosheets are uniformly dispersed in ethanol.
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