CN112758945A - Barium silicate microsphere and preparation method and application thereof - Google Patents

Barium silicate microsphere and preparation method and application thereof Download PDF

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CN112758945A
CN112758945A CN201911063962.0A CN201911063962A CN112758945A CN 112758945 A CN112758945 A CN 112758945A CN 201911063962 A CN201911063962 A CN 201911063962A CN 112758945 A CN112758945 A CN 112758945A
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silicate
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朱万诚
孙盼盼
许林
姜学珍
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Qufu Normal University
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    • C01B33/00—Silicon; Compounds thereof
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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    • C—CHEMISTRY; METALLURGY
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Abstract

The invention provides a barium silicate microsphere and a preparation method and application thereof. The preparation method of the barium silicate microspheres comprises the following steps: and carrying out hydrothermal reaction on soluble barium salt and soluble silicate in a closed reactor to obtain the barium silicate microspheres. The invention also provides application of the barium silicate microspheres in sewage treatment or luminescent materials. According to the preparation method of the barium silicate microspheres, provided by the invention, soluble barium salt and soluble silicate are respectively used as a barium source and a silicon source, and hydrothermal reaction is carried out under static conditions or dynamic conditions to obtain barium silicate (Ba) which is pure in composition, high in crystallinity, has a multi-stage pore structure and is uniform in appearance5Si8O21) Microspheres, and can be obtained by adjusting the reaction conditionsThe preparation method has the advantages of cheap and easily-obtained raw materials, mild conditions, low energy consumption, simple operation process, strong controllability and the like, and is suitable for large-scale industrial popularization.

Description

Barium silicate microsphere and preparation method and application thereof
Technical Field
The invention relates to the field of inorganic chemical materials, in particular to barium silicate microspheres and a preparation method and application thereof.
Background
With the advancement of global industrialization and the increase of population, the problem of water pollution has become one of the problems to be solved urgently for all people. Industries such as food, textile, leather, plastic, synthetic rubber and the like generate a large amount of industrial wastewater every day, and the treatment of wastewater containing carcinogenic organic dyes is more concerned by researchers. The porous material which has no pollution to the environment and is rapid and efficient is used as the adsorbent, and the method is one of the methods for effectively treating water pollution.
In recent years, three-dimensional porous materials have been widely used in the fields of catalysis, adsorption and the like due to their advantages of rich pore structure, high specific surface area, large pore volume and the like. The silicate material has wide sources and is environment-friendly, and the basic structural units (silicon-oxygen tetrahedrons) are connected in the forms of chain, sheet, ring, three-dimensional skeleton and the like, so that the silicate material has the advantages of variable composition, excellent physical and chemical properties and the like. Based on the method, the controllable synthesis of the three-dimensional hierarchical porous silicate material and the application of the material in sewage treatment have important practical significance.
Among many silicate materials, barium silicate is widely used for doped luminescence, and relevant documents and patents are reported for the synthesis thereof. For example, Wang Pengjiu et al in BaCO3、SiO2And Eu2O3/Dy2O3Uses boric acid and ammonium chloride as auxiliary materials to synthesize a photoluminescence phosphor Ba by a high-temperature solid phase method5Si8O21:Eu2+,Dy3+(Inorganic Chemistry, 2015); lu Zhengwu et al with Ba (NO)3)2Synthesizing Ba with vermicular structure by using ethylenediamine and TEOS as raw materials3Si6O13And for fluorescent doping (Ceramics International, 2012); high-temperature solid-phase synthesis of long-afterglow luminescent material Ba by Chinese zodiac (CN1194292A)5Si8O21:Eu2+,Dy3+(ii) a Long afterglow luminescent material Ba synthesized by Lichengyu and the like (CN104774609) by high temperature solid phase method(1-x-y)SiO3:xEu2+,yR3+(R is a rare earth ion); zhao Zhang Ying et al (CN101962538A) high-temp. solid-phase synthesis of ultraviolet fluorescent powder Ba of lead-excited barium silicate3Si2O7Pb; high-temperature solid-phase synthesis of high-brightness barium silicate-based blue-green fluorescent powder Ba by using Rocheline and the like (CN101760191A)1-xCax)2Si3O8:yEu,zCe。
In the synthesis of the barium silicate material, high temperature (500 ℃ -.
Disclosure of Invention
Therefore, the invention aims to overcome the defects of high energy consumption, complex synthesis steps and environmental pollution of the preparation method of the barium silicate microspheres in the prior art, and provides the barium silicate microspheres and the preparation method and application thereof.
In a first aspect, the present invention provides a method for preparing barium silicate microspheres, comprising:
and carrying out hydrothermal reaction on soluble barium salt and soluble silicate in a closed reactor to obtain the barium silicate microspheres.
Further, the preparation method of the barium silicate microspheres comprises the following steps:
(1) respectively dissolving soluble barium salt and soluble silicate in deionized water to obtain a barium salt solution and a silicate solution;
(2) under the condition of stirring, dropwise adding the barium salt solution into the silicate solution to obtain a suspension;
(3) transferring the suspension into a closed reactor to carry out hydrothermal reaction to obtain a hydrothermal product;
(4) and washing and drying the hydrothermal product to obtain the barium silicate microspheres.
Further, the soluble barium salt comprises at least one of barium chloride or barium nitrate; the soluble silicate comprises at least one of sodium silicate or potassium silicate.
Further, the concentration of barium ions in the barium salt solution is 0.042-0.333 mol/L, the concentration of silicate ions in the silicate solution is 0.125-1.000 mol/L, and the molar ratio of the barium ions to the silicate ions is (0.5-1.0): 1.0.
further, in the step (1), stirring is carried out when the soluble silicate and the soluble barium salt are dissolved, wherein the stirring speed is 250-500 r/min, and the stirring time is 5-25 min; in the step (2), the stirring speed during dripping is 250-500 r/min, stirring is continued after dripping, the stirring temperature is 18-35 ℃, the stirring speed is 250-500 r/min, and the stirring time is 10 min.
Further, in the step (2), the dropping rate is 10-40 drops/min.
Further, in the step (3), the hydrothermal reaction conditions are: heating to 100-210 ℃ at the speed of 5-10 ℃/min, and reacting for 6.0-24.0 h, wherein the hydrothermal reaction is static hydrothermal reaction or dynamic hydrothermal reaction, and the rotation frequency of the reactor is 0-30 Hz.
Further, in the step (4), washing the hydrothermal product with deionized water for 2-3 times, washing with ethanol for 1-2 times, performing suction filtration, and drying the solid obtained by suction filtration at 60-100 ℃ for 6.0-24.0 hours.
In a second aspect, the invention provides a barium silicate microsphere obtained by the preparation method.
In a third aspect, the invention provides the barium silicate microspheres obtained by the preparation method, or the application of the barium silicate microspheres in sewage treatment or luminescent materials.
Further, the barium silicate microspheres are placed in sewage containing organic dye for adsorption treatment.
The technical scheme of the invention has the following advantages:
1. the preparation method of the barium silicate microspheres provided by the invention utilizes soluble barium salt and soluble silicate as a barium source and a silicon source respectively, and carries out water treatment under static condition or dynamic conditionThe barium silicate (Ba) with pure composition, high crystallinity, multi-level pore structure and uniform appearance is obtained by thermal reaction5Si8O21) The preparation method has the advantages of cheap and easily-obtained raw materials, mild conditions, low energy consumption, simple operation process, strong controllability and the like, and is suitable for large-scale industrial popularization.
2. The barium silicate microspheres provided by the invention are expected to be widely applied to the fields of dye-containing wastewater treatment, doped luminescence and the like, and particularly, when the barium silicate microspheres are used for sewage treatment, the barium silicate microspheres assembled by the nano rods are placed in simulated wastewater containing organic dye Congo red for adsorption treatment, and a good adsorption effect is shown, so that the method for sewage treatment is low in cost, simple and effective.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the embodiments or the technical solutions in the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a Ba assembly of nanorods prepared in example 15Si8O21XRD spectrum of microsphere;
FIG. 2 shows the assembly of Ba nanorods according to example 15Si8O21TEM photograph of the microspheres;
FIG. 3 shows a Ba nanosheet assembly prepared in example 25Si8O21XRD spectrum of microsphere;
FIG. 4 shows a Ba nanosheet assembly prepared in example 25Si8O21SEM photograph of microspheres;
FIG. 5 shows the assembly of nanoparticles Ba obtained in example 35Si8O21SEM photograph of microspheres;
FIG. 6 shows an embodimentBa nanorod assembly prepared in example 15Si8O21The adsorption performance curve of the microspheres to Congo red;
FIG. 7 shows a nano-sheet assembly Ba prepared in example 25Si8O21The adsorption performance curve of the microspheres to Congo red.
Detailed Description
The following examples are provided for the purpose of better understanding of the present invention, are not intended to limit the scope of the present invention, and are not intended to limit the scope of the present invention, any product that is similar or equivalent to the present invention, which can be obtained by combining the present invention with other features of the prior art, while the present invention is taught by the present invention.
Reagent and instrument sources
Sodium silicate nonahydrate (mao chemical reagents works, Tianjin); barium chloride dihydrate (shinyun science and technology development ltd); x-ray powder diffractometer (MiniFlex 600); cold field emission scanning electron microscope (JSM 6700F); high resolution transmission electron microscope (JEM 2100 PLUS); homogeneous reactors (JXF-0-200).
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
Barium silicate (Ba)5Si8O21) The preparation method of the microsphere comprises the following steps:
(1) 5mmol of BaCl2And 10mmol Na2SiO3Respectively adding the solid into 30mL and 20mL of deionized water, and magnetically stirring (300r/min) for 20min to obtain colorless clear solutions A and B;
(2) dropwise adding the solution B into the solution A at a speed of 10 drops/min under magnetic stirring at 300r/min, and continuously stirring for 10min at 20 ℃ to obtain a white suspension C;
(3) transferring the suspension C into a polytetrafluoroethylene inner container, sealing, heating to 120 ℃ at a heating rate of 5 ℃/min under the condition that the rotation frequency of a homogeneous reactor (JXF-0-200) is 10Hz, reacting at a constant temperature for 6.0h, and naturally cooling to room temperature to obtain a hydrothermal product;
(4) washing the hydrothermal product with deionized water for 3 times, washing with anhydrous ethanol for 1 time, filtering with Buchner funnel, and drying at 70 deg.C for 12.0 hr to obtain barium silicate (Ba)5Si8O21) And (3) microspheres.
Barium silicate (Ba) prepared in this example was recorded by an X-ray powder diffractometer (MiniFlex600)5Si8O21) The XRD pattern of the microsphere is shown in FIG. 1, and the XRD peak position and XRD standard card number JCPDS No.35-0766 (Ba)5Si8O21) The compositions are completely consistent, which indicates that the product composition is relatively pure.
Barium silicate (Ba) prepared in this example was photographed by a high-resolution transmission electron microscope (JEM 2100PLUS)5Si8O21) TEM of the microspheres, as shown in FIG. 2, barium silicate (Ba) can be seen5Si8O21) The surface of the microsphere is assembled by nano rods, the grain diameter is 0.6-1.3 mu m, and the distribution is uniform.
Example 2
Barium silicate (Ba)5Si8O21) The preparation method of the microsphere comprises the following steps:
(1) 2.5mmol of BaCl2And 5mmol Na2SiO3Respectively adding the solid into 30mL and 20mL of deionized water, and magnetically stirring (250r/min) for 25min to obtain colorless clear solutions A and B;
(2) dropwise adding the solution B into the solution A at a speed of 20 drops/min under magnetic stirring at 250r/min, and continuously stirring for 10min at 18 ℃ to obtain a white suspension C;
(3) transferring the suspension C into a polytetrafluoroethylene inner container, sealing, heating to 200 ℃ at a heating rate of 8 ℃/min under the condition that the rotation frequency of a homogeneous reactor (JXF-0-200) is 10Hz, reacting at a constant temperature for 6.0h, and naturally cooling to room temperature to obtain a hydrothermal product;
(4) washing the hydrothermal product with deionized water for 2 times, washing with anhydrous ethanol for 2 times, filtering with Buchner funnel, and drying at 60 deg.C for 24.0 hr to obtain silicic acidBarium (Ba)5Si8O21) And (3) microspheres.
Barium silicate (Ba) prepared in this example was recorded by an X-ray powder diffractometer (MiniFlex600)5Si8O21) The XRD pattern of the microsphere, as shown in FIG. 3, can be seen from the XRD peak position and XRD standard card number JCPDS No.35-0766 (Ba)5Si8O21) The product composition is relatively pure.
Barium silicate (Ba) prepared in this example was photographed by a cold field emission scanning electron microscope (JSM 6700F)5Si8O21) SEM of the microspheres, as shown in FIG. 4, barium silicate (Ba) can be seen5Si8O21) The surface of the microsphere is assembled by nano sheets, the grain diameter is 3.4-5.7 mu m, and the distribution is uniform.
Example 3
Barium silicate (Ba)5Si8O21) The preparation method of the microsphere comprises the following steps:
(1) 2.5mmol of BaCl2And 5mmol Na2SiO3Respectively adding the solid into 30mL and 20mL of deionized water, and magnetically stirring (500r/min) for 5min to obtain colorless clear solutions A and B;
(2) dropwise adding the solution B into the solution A at a speed of 10 drops/min under magnetic stirring at 500r/min, and continuously stirring for 10min at 35 ℃ to obtain a white suspension C;
(3) transferring the suspension C into a polytetrafluoroethylene inner container, sealing, heating to 150 ℃ at a heating rate of 5 ℃/min in a standing state, reacting at a constant temperature for 12.0h, and naturally cooling to room temperature to obtain a hydrothermal product;
(4) washing the hydrothermal product with deionized water for 3 times, washing with anhydrous ethanol for 2 times, filtering with Buchner funnel, and drying at 100 deg.C for 6.0h to obtain barium silicate (Ba)5Si8O21) And (3) microspheres.
Barium silicate (Ba) prepared in this example was photographed by a cold field emission scanning electron microscope (JSM 6700F)5Si8O21) SEM of the microspheres, as shown in FIG. 5, barium silicate (Ba) can be seen5Si8O21) The surface of the microsphere is assembled by nano particlesThe particle size is 5.2-14.6 μm, and the distribution is relatively uniform.
Example 4
Barium silicate (Ba)5Si8O21) The preparation method of the microsphere comprises the following steps:
(1) 2.5mmol of BaCl2And 5mmol Na2SiO3Respectively adding the solid into 30mL and 20mL of deionized water, and magnetically stirring (400r/min) for 10min to obtain colorless clear solutions A and B;
(2) dropwise adding the solution B into the solution A at a speed of 40 drops/min under magnetic stirring at 400r/min, and continuously stirring for 10min at 30 ℃ to obtain a white suspension C;
(3) transferring the suspension C into a polytetrafluoroethylene inner container, sealing, heating to 210 ℃ at a heating rate of 8 ℃/min in a standing state, reacting at a constant temperature for 12.0h, and naturally cooling to room temperature to obtain a hydrothermal product;
(4) washing the hydrothermal product with deionized water for 2 times, washing with anhydrous ethanol for 1 time, filtering with Buchner funnel, and drying at 80 deg.C for 10.0h to obtain barium silicate (Ba)5Si8O21) And (3) microspheres.
Barium silicate (Ba) prepared in this example5Si8O21) The microsphere is assembled by nano sheets, the particle size is 4.3-12.5 mu m, and the distribution is uniform.
Example 5
Barium silicate (Ba)5Si8O21) The preparation method of the microsphere comprises the following steps:
(1) 5mmol of BaCl2And 5mmol Na2SiO3Respectively adding the solid into 30mL and 20mL of deionized water, and magnetically stirring (350r/min) for 15min to obtain colorless clear solutions A and B;
(2) dropwise adding the solution B into the solution A at the speed of 30 drops/min under the magnetic stirring of 350r/min, and continuously stirring for 10min at the temperature of 30 ℃ to obtain a white suspension C;
(3) transferring the suspension C into a polytetrafluoroethylene inner container, sealing, heating to 120 ℃ at a heating rate of 5 ℃/min in a standing state, reacting at a constant temperature for 12.0h, and naturally cooling to room temperature to obtain a hydrothermal product;
(4) washing the hydrothermal product with deionized water for 3 times, washing with anhydrous ethanol for 1 time, filtering with Buchner funnel, and drying at 60 deg.C for 18.0h to obtain barium silicate (Ba)5Si8O21) And (3) microspheres.
Barium silicate (Ba) prepared in this example5Si8O21) The microsphere is assembled by nano particles, the particle size is 5.1-17.0 mu m, and the distribution is relatively uniform.
Example 6
Barium silicate (Ba)5Si8O21) The preparation method of the microsphere comprises the following steps:
(1) 5mmol of BaCl2And 10mmol Na2SiO3Respectively adding the solid into 30mL and 20mL of deionized water, and magnetically stirring (300r/min) for 15min to obtain colorless clear solutions A and B;
(2) dropwise adding the solution B into the solution A at a speed of 20 drops/min under magnetic stirring at 300r/min, and continuously stirring for 10min at 28 ℃ to obtain a white suspension C;
(3) transferring the suspension C into a polytetrafluoroethylene inner container, sealing, heating to 180 ℃ at a heating rate of 10 ℃/min under the condition that the rotation frequency of a homogeneous reactor (JXF-0-200) is 10Hz, reacting at a constant temperature for 6.0h, and naturally cooling to room temperature to obtain a hydrothermal product;
(4) washing the hydrothermal product with deionized water for 3 times, washing with anhydrous ethanol for 1 time, filtering with Buchner funnel, and drying at 60 deg.C for 18.0h to obtain barium silicate (Ba)5Si8O21) And (3) microspheres.
Barium silicate (Ba) prepared in this example5Si8O21) The microsphere is assembled by nano sheets, the particle size is 1.5-4.1 mu m, and the distribution is uniform.
Example 7
Barium silicate (Ba)5Si8O21) The preparation method of the microsphere comprises the following steps:
(1) 5mmol of BaCl2And 10mmol Na2SiO3Respectively adding the solid into 30mL and 20mL of deionized water, and magnetically stirring (300r/min) for 15min to obtain colorless clear solutions A and B;
(2) dropwise adding the solution B into the solution A at the speed of 30 drops/min under the magnetic stirring of 300r/min, and continuously stirring for 10min at the temperature of 28 ℃ to obtain a white suspension C;
(3) transferring the suspension C into a polytetrafluoroethylene inner container, sealing, heating to 120 ℃ at a heating rate of 5 ℃/min under the condition that the rotation frequency of a homogeneous reactor (JXF-0-200) is 5Hz, reacting at a constant temperature for 6.0h, and naturally cooling to room temperature to obtain a hydrothermal product;
(4) washing the hydrothermal product with deionized water for 2 times, washing with anhydrous ethanol for 2 times, filtering with Buchner funnel, and drying at 70 deg.C for 10.0h to obtain barium silicate (Ba)5Si8O21) And (3) microspheres.
Barium silicate (Ba) prepared in this example5Si8O21) The microsphere is assembled by nano rods, the grain diameter is 1.0-2.3 mu m, and the distribution is uniform.
Example 8
Barium silicate (Ba)5Si8O21) The preparation method of the microsphere comprises the following steps:
(1) 10mmol of BaCl2And 20mmol Na2SiO3Respectively adding the solid into 30mL and 20mL of deionized water, and magnetically stirring (500r/min) for 20min to obtain colorless clear solutions A and B;
(2) dropwise adding the solution B into the solution A at a speed of 10 drops/min under magnetic stirring at 500r/min, and continuously stirring for 10min at 25 ℃ to obtain a white suspension C;
(3) transferring the suspension C into a polytetrafluoroethylene inner container, sealing, heating to 120 ℃ at a heating rate of 5 ℃/min under the condition that the rotation frequency of a homogeneous reactor (JXF-0-200) is 10Hz, reacting at a constant temperature for 6.0h, and naturally cooling to room temperature to obtain a hydrothermal product;
(4) washing the hydrothermal product with deionized water for 3 times, washing with anhydrous ethanol for 2 times, filtering with Buchner funnel, and drying at 70 deg.C for 12.0 hr to obtain barium silicate (Ba)5Si8O21) And (3) microspheres.
Barium silicate (Ba) prepared in this example5Si8O21) The microsphere is assembled by nano rods, has the grain diameter of 0.6-1.8 mu m and is distributed more uniformly.
Example 9
Barium silicate (Ba)5Si8O21) The preparation method of the microsphere comprises the following steps:
(1) 5mmol of BaCl2And 10mmol Na2SiO3Respectively adding the solid into 30mL and 20mL of deionized water, and magnetically stirring (300r/min) for 18min to obtain colorless clear solutions A and B;
(2) dropwise adding the solution B into the solution A at the speed of 40 drops/min under magnetic stirring at the speed of 30-500 r/min, and continuously stirring for 10min at the temperature of 24 ℃ to obtain a white suspension C;
(3) transferring the suspension C into a polytetrafluoroethylene inner container, sealing, heating to 120 ℃ at a heating rate of 7 ℃/min under the condition that the rotation frequency of a homogeneous reactor (JXF-0-200) is 10Hz, reacting at a constant temperature for 12.0h, and naturally cooling to room temperature to obtain a hydrothermal product;
(4) washing the hydrothermal product with deionized water for 2 times, washing with anhydrous ethanol for 1 time, filtering with Buchner funnel, and drying at 80 deg.C for 12.0 hr to obtain barium silicate (Ba)5Si8O21) And (3) microspheres.
Barium silicate (Ba) prepared in this example5Si8O21) The microsphere is assembled by nano rods, the grain size is 0.9-1.7 mu m, and the distribution is relatively uniform.
Example 10
Barium silicate (Ba)5Si8O21) The preparation method of the microsphere comprises the following steps:
(1) 1.25mmol of Ba (NO)3)2And 2.50mmol K2SiO3Respectively adding the solid into 30mL and 20mL of deionized water, and mechanically stirring (300r/min) for 15min to obtain colorless clear solutions A and B;
(2) dropwise adding the solution B into the solution A at a speed of 20 drops/min under mechanical stirring at 300r/min, and continuously stirring for 10min at 23 ℃ to obtain a white suspension C;
(3) transferring the suspension C into a polytetrafluoroethylene inner container, sealing, heating to 210 ℃ at a heating rate of 8 ℃/min under the condition that the rotation frequency of a homogeneous reactor (JXF-0-200) is 20Hz, reacting at a constant temperature for 12.0h, and naturally cooling to room temperature to obtain a hydrothermal product;
(4) washing the hydrothermal product with deionized water for 3 times, washing with anhydrous ethanol for 1 time, filtering with Buchner funnel, and drying at 60 deg.C for 18.0h to obtain barium silicate (Ba)5Si8O21) And (3) microspheres.
Barium silicate (Ba) prepared in this example5Si8O21) The microsphere is assembled by nano sheets, the particle size is 1.1-3.8 mu m, and the distribution is uniform.
Example 11
Barium silicate (Ba)5Si8O21) The preparation method of the microsphere comprises the following steps:
(1) adding 10mmol of Ba (NO)3)2And 20mmol K2SiO3Respectively adding the solid into 30mL and 20mL of deionized water, and magnetically stirring (350r/min) for 15min to obtain colorless clear solutions A and B;
(2) dropwise adding the solution B into the solution A at the speed of 30 drops/min under the magnetic stirring of 350r/min, and continuously stirring for 10min at the temperature of 25 ℃ to obtain a white suspension C;
(3) transferring the suspension C into a polytetrafluoroethylene inner container, sealing, heating to 100 ℃ at a heating rate of 5 ℃/min under the condition that the rotation frequency of a homogeneous reactor (JXF-0-200) is 30Hz, reacting at a constant temperature for 24.0h, and naturally cooling to room temperature to obtain a hydrothermal product;
(4) washing the hydrothermal product with deionized water for 3 times, washing with anhydrous ethanol for 1 time, filtering with Buchner funnel, and drying at 70 deg.C for 15.0h to obtain barium silicate (Ba)5Si8O21) And (3) microspheres.
Barium silicate (Ba) prepared in this example5Si8O21) The microsphere is assembled by nano rods, has the grain diameter of 0.6-2.3 mu m and is distributed more uniformly.
Examples of the experiments
First, experiment purpose
Examination of barium silicate (Ba) prepared in examples 1 and 25Si8O21) The adsorption effect of the microspheres on the organic dye congo red.
Second, Experimental methods
(1) The preparation concentration is 20.0-700.0mg L-1Respectively measuring 50mL of Congo red solution by using a measuring cylinder, and placing the solution in a 100mL conical flask;
(2) 20mg of barium silicate (Ba) obtained in example 1 or example 2 were weighed out5Si8O21) Putting the microspheres into a conical flask containing a Congo red solution;
(3) putting the conical flask in the step (2) into a constant-temperature water bath oscillator, setting the temperature at 30 ℃, setting the oscillation frequency at 150r/min and oscillating;
(4) after oscillating for 5.0h, the barium silicate (Ba) adsorbed with Congo red is filtered out by a disposable water filter head5Si8O21) Carrying out microsphere measurement on the absorbance of the obtained solution by using a UV-756 type ultraviolet spectrophotometer; the concentration c at equilibrium is then obtained from the prepared working curvee(mg·L-1) By its mass, volume and initial concentration c0(mg·L-1) Calculating the corresponding adsorption quantity qe(mg·g-1)。
(5) Based on the data (equilibrium concentration and adsorption amount) measured at different concentrations, barium silicate (Ba) prepared in examples 1 and 2 was obtained5Si8O21) Adsorption isotherms of congo red adsorbed by the microspheres are shown in fig. 6 and 7, respectively.
Third, experimental results
The maximum adsorption amount of the nanorod-assembled barium silicate microspheres prepared in example 1 to Congo red is 1238.7mg g-1The maximum adsorption amount of the nanosheet-assembled barium silicate microspheres prepared in example 2 to Congo red is 499.8mg g-1The adsorption effect is higher than that of mesoporous alpha-FeOOH nano-rod (160.0mg g)-1，ACS Sustainable Chemistry&Engineering 2017) and flower-like MgO-GO microspheres (204.1mg g-1Applied Surface Science 2018), etc.; the effect of nano-sheet assembled barium silicate microspheres prepared in example 2 is also higher than that of hierarchical porous ZnO microspheres (334.0mg g)-1Journal of Colloid and Interface Science 2017) and NiCo2O4Hollow microspheres (336.0mg g)-1Journal of Alloys and Compound 2018), etc.; nanorod-assembled barium silicate microspheres prepared in example 1The adsorption effect on Congo red is also obviously higher than that of flower-shaped NiO microspheres (534.8mg g)-1，Journal of Colloid and Interface Science 2017)、Fe(OH)3@Cellulose PHFs(689.7mg g-1，ACS Sustainable Chemistry&Engineering 2017), sandwich-like graphene-based composite material (892.8mg g)-1，Colloid Surface A 2016)。
In addition, the above experiment was performed on the nanoparticle-assembled barium silicate microspheres prepared in example 3, and the maximum adsorption amount of Congo red was 258.4mg g-1Also, a good adsorption effect is exhibited.
Based on this, barium silicate (Ba) prepared by the present invention5Si8O21) The microsphere is assembled by nano rods, nano particles and nano sheets respectively, and shows good adsorption effect when used as an adsorbent.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims (10)

1. A preparation method of barium silicate microspheres is characterized by comprising the following steps:
and carrying out hydrothermal reaction on soluble barium salt and soluble silicate in a closed reactor to obtain the barium silicate microspheres.
2. The method for preparing barium silicate microspheres according to claim 1, comprising:
(1) respectively dissolving soluble barium salt and soluble silicate in deionized water to obtain a barium salt solution and a silicate solution;
(2) under the condition of stirring, dropwise adding the barium salt solution into the silicate solution to obtain a suspension;
(3) transferring the suspension into a closed reactor to carry out hydrothermal reaction to obtain a hydrothermal product;
(4) and washing and drying the hydrothermal product to obtain the barium silicate microspheres.
3. The method for preparing barium silicate microspheres according to claim 1 or 2, wherein the soluble barium salt comprises at least one of barium chloride or barium nitrate; the soluble silicate comprises at least one of sodium silicate or potassium silicate.
4. The method for preparing barium silicate microspheres according to claim 2 or 3, wherein the concentration of barium ions in the barium salt solution is 0.042-0.333 mol/L, the concentration of silicate ions in the silicate solution is 0.125-1.000 mol/L, and the molar ratio of barium ions to silicate ions is (0.5-1.0): 1.0.
5. the method for preparing barium silicate microspheres according to any one of claims 2 to 4, wherein in the step (2), the dropping rate is 10 to 40 drops/min.
6. The method for preparing barium silicate microspheres according to any one of claims 2 to 5, wherein in the step (3), the hydrothermal reaction conditions are as follows: heating to 100-210 ℃ at the speed of 5-10 ℃/min, and reacting for 6.0-24.0 h, wherein the hydrothermal reaction is static hydrothermal reaction or dynamic hydrothermal reaction, and the rotation frequency of the reactor is 0-30 Hz.
7. The hydrothermal preparation method of barium silicate microspheres according to any one of claims 2 to 6, characterized in that in the step (4), the hydrothermal product is sequentially washed with deionized water for 2 to 3 times, washed with ethanol for 1 to 2 times, filtered, and the filtered solid is dried at 60 to 100 ℃ for 6.0 to 24.0 hours.
8. A barium silicate microsphere, which is characterized by being obtained by the preparation method of any one of claims 1 to 7.
9. The barium silicate microspheres obtained by the preparation method of any one of claims 1 to 7, or the application of the barium silicate microspheres of claim 8 in sewage treatment or luminescent materials.
10. The use according to claim 9, wherein the barium silicate microspheres are subjected to adsorption treatment in sewage containing organic dye.
CN201911063962.0A 2019-11-04 2019-11-04 Barium silicate microsphere and preparation method and application thereof Pending CN112758945A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103482703A (en) * 2013-10-10 2014-01-01 哈尔滨工业大学 Preparation method of barium molybdate micro-nano powder having controllable morphology and particle size
CN109019618A (en) * 2018-08-15 2018-12-18 曲阜师范大学 A kind of preparation method of cupric silicate hollow microsphere

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103482703A (en) * 2013-10-10 2014-01-01 哈尔滨工业大学 Preparation method of barium molybdate micro-nano powder having controllable morphology and particle size
CN109019618A (en) * 2018-08-15 2018-12-18 曲阜师范大学 A kind of preparation method of cupric silicate hollow microsphere

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