CN113086949B - Mechanical catalytic synthesis of H 2 O 2 Method (2) - Google Patents
Mechanical catalytic synthesis of H 2 O 2 Method (2) Download PDFInfo
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Abstract
The invention relates to a mechanical catalytic synthesis method of H 2 O 2 The method of (1), characterized in that the catalyst is dispersed in an ethanol-water mixed solution, kept in shade and then subjected toCatalytic synthesis of H under ultrasonic vibration condition 2 O 2 The catalyst contains tetragonal phase BaTiO with ferroelectricity 3 . Compared with the prior art, the invention has the advantages of capability of converting mechanical energy into chemical energy, low energy consumption, easy operation, no toxicity of catalytic materials, recyclability and the like.
Description
Technical Field
The invention relates to the technical field of catalysis, in particular to a method for synthesizing H by mechanical catalysis 2 O 2 The method of (1).
Background
H 2 O 2 As an important pharmaceutical chemical raw material, the photocatalyst is widely used in the fields of disinfection and sterilization, environmental pollution purification, biological medical treatment and the like, but H is synthesized by photocatalysis at present 2 O 2 Is generally not high and the conventional industrial production of H 2 O 2 High energy consumption and serious pollution.
Over the 90 s of the 20 th century, researchers in various countries around the world have developed a series of fundamental researches and application fundamental researches on clean energy conversion, environmental pollution control, biomedical materials and the like, particularly on hydrogen and oxygen production and H synthesis through photo (electro) catalytic hydrolysis 2 O 2 Great development and progress are made in the aspects of degrading organic matters, resisting (killing) bacteria of organisms and the like. However, the industrial development and application based on the photocatalytic technology has not made a substantial breakthrough, and the global energy problem and the environmental problem associated therewith are still very severe, and these problems need to be optimized and solved by using a new method, a new theory and a new technology so as to better realize the sustainable development of the human society.
The factors restricting the industrial development and application of the photocatalytic technology are various, and the prominent limitations are mainly that the electron-hole pairs of the photocatalytic material after being excited by light are seriously compounded, and the effective absorption and utilization rate of the photocatalytic material to sunlight is not high. Therefore, people are seeking to inhibit the recombination of photogenerated carriers, improve the quantum yield of the photocatalytic material in the visible light band and improve the photocatalytic performance, and are also seeking new energy efficient catalytic conversion approaches.
The piezoelectric semiconductor is used as a non-centrosymmetric material, and can induce and generate polarization field intensity under the action of external stress, so that mechanical energy is converted into electric energy, and the phenomenon is also called as piezoelectric effect. Recent research shows that the piezoelectric potential difference generated at two ends of a polarization meter interface by a depolarization built-in electric field generated by piezoelectric polarization field strength induction can also drive oxidation reductionThe reaction is carried out, so that hydrogen and oxygen are prepared by water decomposition, chemical synthesis, bacteria inactivation, degradation of organic pollutants and the like are realized. However, most piezoelectric materials do not have good electrical properties, and the mobility of carriers is low, so that the catalytic efficiency, activity and selectivity of the materials are greatly developed and limited, and particularly, the materials still have insufficient advantages compared with the traditional photocatalytic reaction efficiency. Therefore, a piezoelectric semiconductor material having excellent piezoelectric response property and high electrical conductivity was developed for H 2 O 2 The catalytic synthesis of (A) is very meaningful and necessary.
Disclosure of Invention
The invention aims to provide a method for synthesizing H by mechanical catalysis 2 O 2 The method has low energy consumption and easy operation, and the material can be recycled.
The purpose of the invention can be realized by the following technical scheme: mechanical catalytic synthesis of H 2 O 2 The method comprises dispersing the catalyst into ethanol-water mixed solution, shading and standing, and then catalytically synthesizing H under the ultrasonic vibration condition 2 O 2 The catalyst contains tetragonal phase BaTiO with ferroelectricity 3 . Tetragonal phase of BaTiO 3 The material is a piezoelectric material, has electromechanical coupling property, and can generate piezoelectric polarization effect under the condition of ultrasonic vibration to cause the redistribution of surface free charges to form surface free energy; when the surface free energy is large enough to reduce the dissolved oxygen in water into H 2 O 2 In contact with a reaction medium such as ethanol and aqueous solutions, H is induced 2 O 2 And (4) generating.
Furthermore, the catalyst also contains Nb and/or C quantum dots. The Nb and/or C quantum dot doping can improve the electric polarization strength of the material on one hand, and can enhance the conductivity of the surface of the material on the other hand, so that the effective utilization rate of the free charges on the surface of the material is synergistically improved.
Still further, the catalyst comprises BaTiO 3 :Nb、BaTiO 3 /C、BaTiO 3 Nb/C or BaTiO 3 Nb-C. The catalyst is preferably BaTiO 3 Nb/C, modified by ion doping, tetragonal phase BaTiO 3 The lattice of the nano piezoelectric material is distorted while the structure of the object phase is kept unchanged, so that the ion displacement orientation polarization is caused, and the BaTiO material 3 The inherent polarization intensity is greatly improved, and further the surface Gibbs free energy induced by piezoelectric polarization is enhanced. Wherein, the load of the C quantum dots accelerates the Nb doping of BaTiO 3 Mobility of surface free charge of the nano-piezoelectric material. The synergy of the two aspects leads to a large number of surface free electrons and dissolved O in solution 2 Reaction to form H 2 O 2 And a large number of surface cavities react with ethanol to form acetaldehyde. In the reaction system, ethanol as a hole trapping agent inhibits the recombination of surface electrons and holes, and improves the separation efficiency of the surface electrons and the holes.
Preferably, the BaTiO 3 In the/C, the total weight of the C quantum dots is BaTiO 3 0.6-1.8 wt.% of total weight;
the BaTiO 3 Nb/C or BaTiO 3 In Nb-C, the total weight of C quantum dots is BaTiO 3 0.6 to 1.8wt.% of the total weight of Nb. Excessive C quantum dot load can inhibit the transfer of surface free charges to a reaction medium, and too little C quantum dot load is not beneficial to improving the conductivity of the material to the maximum extent, so the load amount of the C quantum dots in the reaction system should be controlled to a reasonable value.
The catalyst is a piezoelectric material, can induce the surface interface of the material to generate a piezoelectric potential under the action of periodic mechanical external stress, further changes the charge distribution state of the surface interface of the material, and drives a reactant (such as water molecules or charged particles) in contact with the material to generate an oxidation-reduction reaction of getting and losing electrons, when the reaction thermodynamics and the reaction kinetics meet the requirement of H 2 O 2 At the conditions of thermodynamics and kinetics of the reaction formed, i.e. of the conversion of catalytic water into H 2 O 2 。
The preparation method of the catalyst comprises the following steps:
(1) Dissolving polyethylene glycol or sodium oleate in an ethanol-water mixed solution, and stirring to form a solvent A;
(2) Mixing tetrabutyl titanate solution or tetrabutyl titanate solution with NbCl 5 Adding the mixture into absolute ethyl alcohol, performing ultrasonic dispersion to form a light white suspension B, then dropwise adding the solution B into the solution A, stirring and reacting for 10-20 min, wherein the tetrabutyl titanate solution and NbCl 5 In the mixture of (A) tetrabutyl titanate and NbCl 5 The molar ratio of (A) to (B) is 8 to 11;
(3) Dissolving sodium hydroxide in the mixed solution of ethanol and water, dropwise adding the mixed solution into the mixed solution of the solution A and the solution B which are completely reacted, stirring for 25-35 min, and then adding BaCl 2 Stirring the crystals for 25-35 min, wherein the molar ratio of tetrabutyl titanate to barium chloride is 1;
(4) Transferring the reaction mixed solution obtained in the step (3) into a high-pressure reaction kettle to react for 10-14 h at 190-210 ℃, washing and drying the precipitate, calcining the dried powder for 1-3 h at 700-900 ℃ to obtain the product containing the tetragonal phase BaTiO 3 Nanorod, tetragonal phase BaTiO 3 Nano-spherical particle, nb doped tetragonal phase BaTiO 3 Nanorod or Nb doped tetragonal phase BaTiO 3 Catalyst in the form of nano-spherical particles.
The volume ratio of ethanol to water in the ethanol-water mixed solution is 1, and magnetic stirring is adopted in the stirring process. The washing and drying process of the precipitate comprises the steps of washing the precipitate for 3 to 5 times by deionized water and 0.1mol/L formic acid, and then drying the precipitate in an oven at 105 ℃ for 10 hours. Soluble removal of concomitant BaTiO using formic acid wash 3 Generated to form BaCO 3 And the like.
The polyethylene glycol has a relative molecular weight of 6000, is viscous when dissolved in water, and can control BaTiO 3 And (4) forming nanorod particles. Sodium oleate contains long-chain alkane, has emulsifying property, and can control BaTiO 3 And (4) generating nano spherical particles.
Further, the tetragonal phase BaTiO is added 3 Dispersing the nanorod particles and glucose into deionized water simultaneously, performing ultrasonic dispersion to form milky suspension, transferring the milky suspension into a high-pressure reaction kettle, reacting for 5-7 h at 170-190 ℃, washing and drying precipitates to obtain C quantum dot-loaded BaTiO 3 A powder catalytic material. The washing and drying process of the precipitate is washing with deionized water and ethanol solution 35 times, and then drying in a drying oven at 90 ℃ for 12 hours.
The Nb is doped with tetragonal phase BaTiO 3 Dispersing the nanorod particles and glucose in deionized water simultaneously, performing ultrasonic dispersion to form milky suspension, transferring the milky suspension into a high-pressure reaction kettle, reacting for 5-7 h at 170-190 ℃, washing and drying the precipitate to obtain BaTiO 3 Nb/C catalyst. The washing and drying process of the precipitate is to wash the precipitate for 3 to 5 times by using deionized water and ethanol solution and then dry the precipitate in a drying oven at the temperature of 90 ℃ for 12 hours.
The Nb is doped with tetragonal phase BaTiO 3 Dispersing the nano spherical particles and glucose in deionized water simultaneously, performing ultrasonic dispersion to form milky suspension, transferring the milky suspension into a high-pressure reaction kettle, reacting for 5-7 h at 170-190 ℃, washing and drying the precipitate to obtain BaTiO 3 Nb-C catalyst. The washing and drying process of the precipitate is to wash the precipitate for 3 to 5 times by using deionized water and ethanol solution and then dry the precipitate in a drying oven at the temperature of 90 ℃ for 12 hours. The organic matter such as sodium oleate remaining on the surface of the product can be removed by washing with ethanol.
Containing C-supported BaTiO 3 Marking the catalyst of Nb nano-rod particles as BaTiO 3 Nb/C, containing C-supported BaTiO 3 The catalyst of Nb nano spherical particles is marked as BaTiO 3 :Nb-C。
The shading dead time is 2-4 min, so that the solution and the powder are completely soaked, the ultrasonic vibration frequency is 35-45 kHz, and the power is 140-160W. In practical operation, the ultrasonic frequency and power should be coordinated and controlled within a reasonable interval, otherwise, too low mechanical vibration energy cannot initiate catalytic reaction, and too high mechanical vibration energy may damage the inherent composition structure of the material.
The volume ratio of ethanol to water in the ethanol-water solution is 0.25-0.45, the mass ratio of the catalytic material to the ethanol-water solution is 0.005-0.02. Volume ratio control of ethanol to water in ethanol-water solution for H 2 O 2 The rate of the synthesis reaction is greatly affected because ethanol, acting as an electron donor, will itself contribute to the synthesisTakes part in the oxidation reaction to generate acetaldehyde, and excessive or insufficient ethanol is not beneficial to H 2 O 2 A large number of syntheses.
Compared with the prior art, the invention has the following advantages:
1. the invention adopts tetragonal phase BaTiO with electromechanical coupling property 3 、BaTiO 3 The piezoelectric material such as Nb/C is used as catalyst, under the condition of ultrasonic vibration the piezoelectric polarization potential can be induced and produced, and the ethanol-water solution can be catalyzed to synthesize H 2 O 2 Mechanical energy is converted into chemical energy, the energy consumption is low, the operation is easy, and the catalytic material has no toxicity and can be recycled;
2. the invention modifies tetragonal phase BaTiO by Nb doping 3 The catalytic material has higher piezoelectric response performance due to ion displacement orientation polarization, which means that under the same mechanical external stress action, baTiO 3 Relatively pure BaTiO of Nb phase 3 Exhibit a higher voltage potential;
3. according to the invention, through the loading of the C quantum dots, on one hand, the whole conductivity of the material is improved, on the other hand, more chemical reaction active sites are provided, and the synergistic effect of the high-voltage potential and the excellent conductivity leads to BaTiO 3 Nb/C nano composite material shows obviously enhanced catalytic synthesis of H under the activation of mechanical stress 2 O 2 The reactivity of (a);
4. the invention applies the piezoelectric semiconductor material to the field of catalytic chemical synthesis, and the conversion of mechanical energy into chemical energy is feasible, which means that the piezoelectric semiconductor material with proper reaction thermodynamics and kinetics can not only capture and utilize the mechanical energy in the external environment to the maximum extent, but also drive the synthesis of H 2 O 2 The application range of the material in time and space dimensions is greatly expanded, and the use cost of the material is greatly reduced;
5. the invention supplements and expands the H of the current industry or laboratory 2 O 2 The synthesis process route enriches H 2 O 2 The composition range of the catalytic synthetic material, the related reaction conditions are not limited by space and time, the operability is strong, and the mass production is easy to reach the standard and popularize and use；
6. The invention improves the tetragonal phase BaTiO synergistically through ion doping and surface loading modification 3 The electric polarization strength and the surface conductance of the nano material enable the piezoelectric material to convert mechanical energy into chemical energy to the maximum extent, and the chemical energy is reflected in the catalytic reaction system, namely H synthesized by the material within 120min of the piezoelectric catalytic reaction 2 O 2 The concentration values were as high as 953. Mu.M, and the high concentration continued to increase with increasing reaction time.
Drawings
FIG. 1 shows the pure phase C, baTiO prepared 3 、BaTiO 3 :Nb、BaTiO 3 Powder XRD diffraction pattern of Nb/C;
FIG. 2 shows (a) BaTiO 3 XPS element total spectrum of Nb/C surface and (b) XPS spectrum of C1 s;
FIG. 3 shows (a) pure phase C and (b) BaTiO 3 SEM picture of Nb-C;
FIG. 4 shows BaTiO 3 SEM picture of Nb/C;
FIG. 5 shows BaTiO 3 TEM and high-power TEM images of Nb/C powder;
FIG. 6 shows pure phase C, baTiO 3 、BaTiO 3 :Nb、BaTiO 3 /C、BaTiO 3 Nb/C and BaTiO 3 Catalytic synthesis of H from Nb-C under the action of mechanical stress 2 O 2 The concentration of (c) is plotted against the reaction time.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The following examples are carried out on the premise of the technical scheme of the invention, and detailed embodiments and specific operation procedures are given, but the scope of the invention is not limited to the following examples.
Example 1
Nb-doped modified tetragonal phase BaTiO 3 (BaTiO 3 Nb) preparation method, which mainly comprises the following steps:
(1) 1.0g of polyethylene glycol (PEG, relative molecular weight 6000) was weighed and dissolved in 14ml of an ethanol-water mixed solution (volume ratio of ethanol to water is 1.
(2) Weighing 500. Mu.l tetrabutyl titanate solution according to NbCl 5 The molar ratio of the NbCl to tetrabutyl titanate is 1-11, and the calculated amount of NbCl is weighed 5 And adding the mixture into 10ml of absolute ethyl alcohol, and carrying out ultrasonic treatment for 3min to form a light white suspension B. Then, the solution B was added dropwise to the solution A, and magnetically stirred for 15min.
(3) 1.4g of sodium hydroxide was weighed and dissolved in 12ml of an ethanol-water mixed solution (the volume ratio of ethanol to water is 1) 5 The molar ratio of the BaCl to the tetrabutyl titanate is 1 2 The crystals were stirred for 30min.
(4) And (3) transferring the reaction mixed solution (3) to a high-pressure reaction kettle, reacting for 10-14 h at 200 ℃, after the reaction is finished and the reaction kettle is cooled to room temperature, washing the reaction precipitate for 3-5 times by using deionized water and 0.1mol/L formic acid, and then drying in an oven at 105 ℃ for 10h.
(5) Calcining the dry powder in a muffle furnace at 800 ℃ for 2 hours in the air atmosphere at the temperature programming rate of 5 DEG/min, and cooling the powder to room temperature to obtain Nb-doped tetragonal phase BaTiO with good crystallinity 3 (BaTiO 3 Nb) nanoparticles.
Example 2
Nb-doped modified tetragonal phase BaTiO loaded by C quantum dots 3 Preparation method of nanorod piezoelectric composite material (BaTiO) 3 Nb/C), which mainly comprises the following steps:
(1) BaTiO prepared according to C and example 1 3 Weighing calculated amounts of glucose and BaTiO with Nb of 0.6-1.8 wt% 3 Nb powder is dispersed in 30ml deionized water solution and is treated by ultrasonic treatment for 15min to form milky suspension.
(2) And transferring the milky white suspension to a sealed high-pressure reaction kettle, and placing the kettle in an oven at 180 ℃ for reaction for 6 hours.
(3) After the reaction kettle is cooled to room temperature, taking out the reaction mixture, washing the reaction mixture for 3 to 5 times by using deionized water and ethanol solution, and then drying the reaction mixture in a drying oven at the temperature of 90 ℃ for 12 hours to obtain the BaTi loaded with the C quantum dotsO 3 Nb nanorod piezoelectric composite material powder.
Example 3
A preparation method of pure phase C mainly comprises the following steps:
(1) Firstly, 0.75g of glucose is weighed and dissolved in 30ml of deionized water, then the glucose is transferred to a high-pressure reaction kettle and reacts for 4 to 8 hours at the temperature of between 160 and 200 ℃.
(2) And after the reaction kettle is cooled to room temperature, taking out the reaction mixture, washing the reaction mixture for 3 to 5 times by using deionized water and ethanol solution, and then placing the reaction mixture in a drying oven at the temperature of 90 ℃ for drying treatment for 12 hours to obtain pure-phase nano C particles.
Example 4
Tetragonal phase BaTiO 3 The preparation method mainly comprises the following steps:
(1) 1.0g of polyethylene glycol (PEG, relative molecular weight 6000) was weighed and dissolved in 14ml of an ethanol-water mixed solution (volume ratio of ethanol to water is 1.
(2) Weighing 500 μ l tetrabutyl titanate solution, adding into 10ml anhydrous ethanol, and performing ultrasonic treatment for 3min to obtain light white suspension B. Then, the solution B was added dropwise to the solution A, and magnetically stirred for 15min.
(3) Weighing 1.4g of sodium hydroxide, dissolving the sodium hydroxide in 12ml of ethanol-water mixed solution (the volume ratio of ethanol to water is 1) 2 The crystals were stirred for 30min.
(4) And (3) transferring the reaction mixed solution (3) to a high-pressure reaction kettle, reacting for 10-14 h at 200 ℃, after the reaction is finished and the reaction kettle is cooled to room temperature, washing the reaction precipitate for 3-5 times by using deionized water and 0.1mol/L formic acid, and then drying in an oven at 105 ℃ for 10h.
(5) Calcining the dry powder in a muffle furnace at 800 ℃ for 2 hours in the air atmosphere at the programmed heating rate of 5 DEG/min, and cooling the powder to room temperature to obtain tetragonal phase BaTiO 3 And (3) nanoparticles.
Example 5
C quantum dot load squarePhase BaTiO 3 Composite material (BaTiO) 3 The preparation method of the/C) mainly comprises the following steps:
(1) According to C and BaTiO 3 The calculated amount of glucose and BaTiO is weighed up in the weight percentage of 0.6 to 1.8 wt% 3 And dispersing the powder in 30ml of deionized water solution, and performing ultrasonic treatment for 15min to form milky suspension.
(2) And transferring the milky white suspension to a sealed high-pressure reaction kettle, and placing the kettle in an oven at 180 ℃ for reaction for 6 hours.
(3) Cooling the reaction kettle to room temperature, taking out the reaction mixture, washing the reaction mixture for 3 to 5 times by using deionized water and ethanol solution, and then drying the reaction mixture in a drying oven at the temperature of 90 ℃ for 12 hours to obtain the BaTiO loaded with the C quantum dots 3 And (3) powder.
Example 6
C quantum dot loaded tetragonal phase BaTiO 3 Nanoparticle piezoelectric composite material (BaTiO) 3 The preparation method of Nb-C) mainly comprises the following steps:
(1) Weighing 1.0g of sodium oleate, dissolving in 14ml of ethanol-water mixed solution (volume ratio of ethanol to water is 1).
(2) Weighing 500. Mu.l of n-tetrabutyl titanate solution according to NbCl 5 The molar ratio of the NbCl to tetrabutyl titanate is 1 5 Adding into 10ml absolute ethanol, and performing ultrasonic treatment for 3min to obtain light white suspension B. Then, the solution B was added dropwise to the solution A, and magnetically stirred for 15min.
(3) 1.4g of sodium hydroxide was weighed and dissolved in 12ml of an ethanol-water mixed solution (volume ratio of ethanol to water is 1) 2 The crystals were stirred for 30min.
(4) And (3) transferring the reaction mixed solution (3) to a high-pressure reaction kettle, reacting for 10-14 h at 200 ℃, after the reaction is finished and the reaction kettle is cooled to room temperature, washing the reaction precipitate for 3-5 times by using deionized water and 0.1mol/L formic acid, and then drying in an oven at 105 ℃ for 10h.
(5) Calcining the dried powder in a muffle furnace at 800 ℃ in an air atmosphereTreating for 2h, wherein the temperature programming rate is 5 DEG/min, and obtaining Nb-doped tetragonal phase BaTiO after the powder is cooled to room temperature 3 A nano-spherical particle.
(6) By mixing C with BaTiO 3 Weighing calculated amounts of glucose and BaTiO with Nb of 0.6-1.8 wt% 3 And dispersing the powder in 30ml of deionized water solution, and performing ultrasonic treatment for 15min to form milky suspension.
(7) And transferring the milky white suspension to a sealed high-pressure reaction kettle, and placing the kettle in an oven at 180 ℃ for reaction for 6 hours.
(8) Cooling the reaction kettle to room temperature, taking out the reaction mixture, washing the reaction mixture for 3 to 5 times by using deionized water and ethanol solution, and then drying the reaction mixture in a drying box at the temperature of 90 ℃ for 12 hours to obtain the C quantum dot supported Nb doped BaTiO 3 And (3) powder.
Example 7
Mechanochemical method catalysis H 2 O 2 The synthetic performance test mainly comprises the following operation steps:
(1) 30mg of the synthesized catalyst powder is weighed and dispersed in a 200ml glass beaker filled with 60ml of 2mol/L ethanol-water mixed solution, and the solution and the powder are completely soaked by shading and standing for 3 min.
(2) And (3) suspending and fixing the beaker containing the dispersion liquid in an ultrasonic instrument water tank with ultrasonic vibration frequency of 40kHz and power of 150W, and controlling the water temperature and the liquid level height of the water tank at a room temperature state and a constant height position by virtue of flowing water. The whole reaction device is placed in a dark room to remove the interference of light.
(3) Taking out 300-500 mul of reaction liquid at intervals of 30min under the drive of mechanical energy, and calibrating the generated H by an iodine titration method 2 O 2 And (4) concentration.
FIG. 1 shows the pure C, baTiO prepared 3 、BaTiO 3 Nb and BaTiO 3 Powder XRD diffraction pattern of Nb/C. It can be seen from the graph that the diffraction peak of the (120) crystal plane of pure C at the diffraction angle of 22.7 ℃ corresponds to the diffraction peak of standard C (PDF No. 50-0926), indicating that pure C is prepared to have a hexagonal phase structure. Prepared BaTiO 3 Characteristic diffraction peak and tetragonal phase structure BaTiO 3 (PDF No. 050626) corresponding to the aboveMing the BaTiO 3 Has ferroelectricity, and spontaneous polarization field intensity exists in crystals of the ferroelectricity. Nb doped modified BaTiO 3 With the prepared pure BaTiO 3 Diffraction peaks were consistent and at 31.5 ° diffraction angle the diffraction peak was relatively pure BaTiO 3 A slight red shift occurs, which indicates that BaTiO 3 Nb in the presence of BaTiO in a tetragonal phase 3 The structure simultaneously generates lattice distortion, and the change of the lattice spacing can affect the polarization field strength. BaTiO 2 3 Characteristic diffraction peak position of Nb/C and BaTiO 3 Nb is consistent, which shows that C is loaded on BaTiO 3 The crystal structure of Nb has no influence, and in addition, no C diffraction peak is observed, which is associated with an excessively small C content. However, from BaTiO 3 XPS spectrum of Nb/C (FIG. 2) was easily found in BaTiO 3 The presence of Nb and C elements in Nb/C verifies that Nb doping is incorporated into BaTiO 3 Lattice, and C is supported on BaTiO 3 Nb surface.
FIG. 3 shows the pure C and BaTiO compounds thus prepared 3 SEM picture of Nb-C. FIG. 4 shows BaTiO 3 SEM image of Nb/C. As can be seen, C is prepared as spherical particles having an average particle size of 300nm, baTiO 3 Nb/C is mainly composed of rod-shaped BaTiO 3 Nb and spherical C quantum dots (particle size of 10 nm), baTiO 3 Nb-C is mainly formed by piling two-phase fine nanorod particles. The grain size of pure C is obviously larger than that of BaTiO 3 Nb/C and BaTiO 3 The particle size of C in Nb-C, which is closely related to the concentration of the glucose reaction solution.
FIG. 5 shows BaTiO 3 Nb/C in (a) TEM and (b) high-power TEM images. As can be seen from the TEM image, baTiO 3 The morphology of Nb/C is mainly formed by BaTiO 3 The Nb particles have a rod-like structure, the particle size length distribution is in the range of 200 to 500nm, and the composition of the C quantum dots is hardly observed. From the high power TEM image, two kinds of lattice fringes belonging to BaTiO can be seen 3 Nb and graphitized C, wherein the size of the C quantum dots is about 2nm.
FIG. 6 shows that the prepared material is catalyzed to synthesize H under the action of mechanical stress 2 O 2 The concentration of (c) is plotted against the reaction time. Apparently, in the same reaction time, baTiO 3 Nb/C shows the largest synthesis H 2 O 2 Of (2) BaTiO 3 The second is that the lattice distortion caused by Nb doping can induce higher piezoelectric polarization field, and the C load improves the conductivity of the material, thereby leading the BaTiO to be more conductive 3 Nb/C has excellent mechanical catalysis synthesis H 2 O 2 The performance of (c).
The invention passes through BaTiO 3 Nb/C nano-piezoelectric composite material for converting mechanical energy into chemical energy of high value-added product, i.e. ethanol-water solution is catalytically converted into H under the drive of mechanical stress 2 O 2 Opens up a new way of environmental mechanical energy in the field of catalytic chemical synthesis application, and expands the current H 2 O 2 A synthetic process method, key material composition and a preparation technology thereof.
The embodiments described above are intended to facilitate a person of ordinary skill in the art in understanding and using the invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make modifications and alterations without departing from the scope of the present invention.
Claims (6)
1. Mechanical catalytic synthesis of H 2 O 2 The method is characterized in that the catalyst is dispersed into ethanol-water mixed solution, lightproof and static stagnation are carried out, and then H is synthesized by catalysis under the condition of ultrasonic vibration 2 O 2 The catalyst contains tetragonal phase BaTiO with ferroelectricity 3 ；
The catalyst also contains Nb and/or C quantum dots;
the catalyst comprises BaTiO 3 :Nb、BaTiO 3 /C、BaTiO 3 Nb/C or BaTiO 3 :Nb-C；
The BaTiO 3 In the/C, the total weight of the C quantum dots is BaTiO 3 0.6 to 1.8wt.% of the total weight;
the BaTiO 3 Nb/C or BaTiO 3 In Nb-C, the total weight of C quantum dots is BaTiO 3 0.6 to 1.8wt.% of the total weight of Nb;
the preparation method of the catalyst comprises the following steps:
(1) Dissolving polyethylene glycol or sodium oleate in an ethanol-water mixed solution, and stirring to form a solvent A;
(2) Mixing tetrabutyl titanate solution with NbCl 5 Adding the mixture into absolute ethyl alcohol, performing ultrasonic dispersion to form a light white suspension B, then dropwise adding the solution B into the solution A, stirring and reacting for 10-20min, wherein the tetrabutyl titanate solution and NbCl 5 In the mixture of (A) tetrabutyl titanate and NbCl 5 The molar ratio of (a) is 8 to 11;
(3) Dissolving sodium hydroxide in an ethanol-water mixed solution, dropwise adding the mixed solution into a mixed solution of the solution A and the solution B which are completely reacted, stirring for 25 to 35min, and then adding BaCl 2 Stirring the crystal for 25 to 35min, wherein the molar ratio of the tetrabutyl titanate to the barium chloride is 1;
(4) Transferring the reaction mixed solution obtained in the step (3) into a high-pressure reaction kettle, reacting at 190-210 ℃ for 10-14h, washing and drying the precipitate, and calcining the dried powder at 700-900 ℃ for 1-3h to obtain the Nb-doped tetragonal-phase BaTiO 3 Nanorod or Nb doped tetragonal phase BaTiO 3 Catalyst in the form of nano-spherical particles.
2. Mechanocatalytic synthesis of H according to claim 1 2 O 2 The method is characterized in that the tetragonal phase BaTiO is mixed with 3 Dispersing the nanorod particles and glucose in deionized water simultaneously, performing ultrasonic dispersion to form a milky white suspension, transferring the milky white suspension into a high-pressure reaction kettle, reacting for 5 to 7 hours at the temperature of 170 to 190 ℃, washing and drying the precipitate to obtain the C quantum dot supported BaTiO 3 A powder catalytic material.
3. Mechanocatalytic synthesis of H according to claim 1 2 O 2 Characterized in that said Nb is doped with tetragonal phase BaTiO 3 Nanorod particles anddispersing glucose in deionized water simultaneously, performing ultrasonic dispersion to form a milky white suspension, transferring the milky white suspension into a high-pressure reaction kettle, reacting for 5 to 7 hours at the temperature of 170 to 190 ℃, washing and drying the precipitate to obtain BaTiO 3 Nb/C catalyst.
4. Mechanocatalytic synthesis of H according to claim 1 2 O 2 Characterized in that said Nb is doped with a tetragonal phase of BaTiO 3 Dispersing the nano spherical particles and glucose in deionized water simultaneously, performing ultrasonic dispersion to form milky suspension, transferring the milky suspension into a high-pressure reaction kettle, reacting for 5 to 7 hours at the temperature of 170 to 190 ℃, washing and drying the precipitate to obtain BaTiO 3 Nb-C catalyst.
5. Mechanocatalytic synthesis of H according to claim 1 2 O 2 The method is characterized in that the shading static lag time is 2-4 min, so that the solution and the powder are completely soaked and the absorption and desorption balance is achieved, and the ultrasonic vibration frequency is 35-45 kHz and the power is 140-160W.
6. Mechanocatalytic synthesis of H according to claim 1 2 O 2 The method is characterized in that the volume ratio of ethanol to water in the ethanol-water solution is 0.25 to 0.45, the mass ratio of the catalytic material to the ethanol-water solution is 0.005 to 0.02, and the catalytic process is carried out at room temperature in a dark place.
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| CN105000626A (en) * | 2015-06-26 | 2015-10-28 | 中山大学 | Method for reinforcing piezoelectric effect to improve organic pollutant degradation efficiency and application thereof |
| CN105329938A (en) * | 2015-10-29 | 2016-02-17 | 东华大学 | Oil-water interface method for preparing BaTiO3 nanoparticles |
| CN112209431A (en) * | 2020-09-28 | 2021-01-12 | 新昌中国计量大学企业创新研究院有限公司 | Functionalized BaTiO3Preparation method and application of nano material |
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| JPH08217421A (en) * | 1994-12-12 | 1996-08-27 | Sansui Kagaku Kk | Production unit for aqueous hydrogen peroxide |
| CN105000626A (en) * | 2015-06-26 | 2015-10-28 | 中山大学 | Method for reinforcing piezoelectric effect to improve organic pollutant degradation efficiency and application thereof |
| CN105329938A (en) * | 2015-10-29 | 2016-02-17 | 东华大学 | Oil-water interface method for preparing BaTiO3 nanoparticles |
| CN112209431A (en) * | 2020-09-28 | 2021-01-12 | 新昌中国计量大学企业创新研究院有限公司 | Functionalized BaTiO3Preparation method and application of nano material |
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