CN107758676B - Method for preparing double-layer hollow nano manganese silicate based on bell-shaped structure template - Google Patents

Method for preparing double-layer hollow nano manganese silicate based on bell-shaped structure template Download PDF

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CN107758676B
CN107758676B CN201711134136.1A CN201711134136A CN107758676B CN 107758676 B CN107758676 B CN 107758676B CN 201711134136 A CN201711134136 A CN 201711134136A CN 107758676 B CN107758676 B CN 107758676B
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刘惠玉
王伟伟
孙晓
潘雪婷
申鹤云
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Beijing University of Chemical Technology
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Abstract

The invention discloses a method for preparing double-layer hollow nano manganese silicate based on a template with a bell-shaped structure. The ZIF-8 nano composite particles coated by the mesoporous silica with the unique bell-shaped core-shell structure are used as a template, and ammonium ions (NH) are utilized by utilizing the characteristic that the pore structure of the mesoporous silica and the ZIF-8 imidazolate framework are easy to decompose under the acid-base condition4 +) Hydrolysis to control the hydroxyl ion (OH) of the system‑) The release rate and the total concentration. With high specific surface area (445.3 m) capable of forming stable configuration2/g) double-layer hollow nano-manganese silicate nanoparticles. The double-layer hollow Mn (SiO) prepared by the invention4) The nano particles have good dispersibility, uniform appearance and size, simple synthesis method and process, economy and saving and high repeatability. And the prepared nano-particles show good biodegradability in a simulated body fluid. Has wide application prospect in the fields of electronics, energy, environment, life and the like.

Description

Method for preparing double-layer hollow nano manganese silicate based on bell-shaped structure template
The technical field is as follows:
the invention relates to a preparation method and a process of double-layer hollow manganese silicate nanoparticles, in particular to ZIF-8 (hereinafter referred to as ZIF-8@ mSiO for short) coated by mesoporous silica with a unique bell-shaped core-shell structure2) The nano composite particles are used as a template, and ammonium ions (NH) are introduced under the temperature condition of 10-35 ℃ or 50-180 ℃ by utilizing the characteristic that mesoporous silicon dioxide pore channel structure and ZIF-8 imidazole ester framework are easy to decompose under the acid-base condition4 +) Hydrolysis to control the hydroxyl ion (OH) of the system-) The release rate and the total concentration. First OH-The outer Si-O bond of the shell is converted to Silicate Ions (SiO) at the surface of the template3 2-) And part of the silicon carbide enters the pore canal and reaches the inside of the shell, so that the Si-O bond at the inner layer is converted into SiO3 2-(ii) a ByZIF-8 buffer in the core, OH-ZIF-8 is gradually decomposed, so that the inner surface and the outer surface of the template have enough space and manganese ions (Mn) in the system2 +) The reaction is carried out for 4-48 hours, and finally the stable configuration double-layer hollow Mn (SiO) can be formed4) And (3) nanoparticles.
Background art:
manganese silicate has the main chemical formula of MnSiO3It is mainly present in manganese ore in nature and is abundant in reserves. Due to the unique layered molecular structure and the higher specific surface area, the method has good research value in the fields of energy, catalysis, environment and the like. However, the process for separating natural manganese silicate from manganese ore is complicated and has low purity, which limits its wide application in various fields. Therefore, the artificial synthesis of the simple manganese silicate with higher purity, good structure and higher specific surface area has strong research significance.
With the development of nano science and technology, nano materials show excellent performance in various fields. In order to prepare manganese silicate nanomaterials having a high specific surface area, various methods for preparing manganese silicate nanoparticles having different structures (including solid, core-shell, and hollow structures) and compositions (including manganese-containing silicates having different valence states and different metal element compositions) have been reported. Such as template-precipitation, self-assembly, chemical deposition, hydrothermal, sol-gel, etc.
The manganese silicate nanoparticles with hollow structures have high specific surface area and good thermal stability, and show great application potential in vicinal domains of lithium ion batteries, environmental catalysis, adsorption separation, drug delivery and the like. For example, the Song defense team of the chemical institute of Chinese academy of 2012 (J.Mater. chem.,2012,22, 17222-17226), using carbon nanotubes as templates, self-assembled to grow silica on the surface, and calcined at high temperature to form silica particles with a higher specific surface area (649 m)2The porous silicon dioxide nano-tube of/g) is prepared into the manganese silicate nano-tube under hydrothermal conditions, and the manganese silicate nano-tube has excellent performance in the aspects of environmental pollutant adsorption removal and catalytic degradation. 2014 Zenghuachun et al utilize solid silica spheres asThe template is prepared by converting the formed silicic acid into manganese silicate under the high-temperature hydrothermal condition, and has higher specific surface area (316.1 m)2The hollow-structure manganese silicate nanoparticles (ACS Nano, 2014,8(6), 6407-6416) of/g) show higher catalytic degradation capability on organic dyes. Recently, Schjialin team (J.Am.chem.Soc.2016,138,9881-9894), prepared under hydrothermal conditions using mesoporous silica nanoparticles as templates, yielded a silica nanoparticles with a high specific surface area (222.0 m)2The hollow manganese silicate nanoparticle of/g) shows better biodegradability and tumor targeting diagnosis characteristics in a drug delivery system. The hollow nano particles have good monodispersity in aqueous solution and are not easy to agglomerate, so the hollow nano particles are widely concerned. In order to synthesize hollow manganese silicate nanoparticles having a higher specific surface area, more and more researchers are turning to design and control of the structure of the manganese silicate nanoparticles. However, there are few reports on the preparation method of the double-layered hollow manganese silicate nanoparticle, and thus, there are many challenges in synthesizing the double-layered hollow manganese silicate nanoparticle.
The invention content is as follows:
aiming at the current problems, the invention provides a method for preparing double-layer hollow nano manganese silicate (hereinafter referred to as Mn (SiO) for short) based on a template with a bell-shaped structure4) ) of (c). ZIF-8@ mSiO using unique bell-shaped core-shell structure2The nano composite particles are used as a template, the characteristic that mesoporous silicon dioxide in the nano composite particles is easy to decompose under acid-base conditions and the basic chemical hydrolysis equilibrium theory is utilized under the low-temperature or high-temperature conditions by utilizing the characteristic that the mesoporous silicon dioxide and the ZIF-8 imidazole ester framework are easy to decompose under the acid-base conditions4 +Hydrolysis to control the OH of the system-The release rate and the total concentration. First OH-The outer Si-O bond of the shell is converted to form SiO on the surface of the template3 2-And part of the silicon carbide enters the pore canal and reaches the inside of the shell, so that the Si-O bond at the inner layer is converted into SiO3 2-(ii) a OH due to ZIF-8 buffering action of the core-ZIF-8 is gradually decomposed, so that the inner surface and the outer surface of the template have enough space and Mn in the system2+The reaction is carried out for a period of time, and finally the shape of the product is formedDouble-layer hollow Mn (SiO) with stable configuration4) And (3) nanoparticles.
The technical scheme of the invention is as follows:
a method for preparing double-layer hollow nano manganese silicate based on a template with a bell-shaped structure comprises the following specific steps:
ZIF-8 (hereinafter referred to as ZIF-8@ mSiO) coated with prepared dumbbell-shaped mesoporous silica with core-shell structure2) Dispersing the nano composite particle template into deionized water to form a stable sol dispersion system with the mass concentration of 0.2-2%; dissolving manganese metal salt in deionized water, and adding ammonium chloride crystal (NH)4Cl) for regulating the system ammonium ion (NH)4 +) The rate of hydrolysis of (a). Followed by manganese ion (Mn)2+) Adding 38% ammonia (NH) into the solution3·H2O) and added to the above ZIF-8@ mSiO2In a sol system; after being stirred evenly, NH is added at the temperature of 10-35 ℃ or 50-180 DEG C4 +Hydrolysis to control the hydroxyl ion (OH) of the system-) The release rate and the total concentration of the compound can finally form a stable configuration double-layer hollow Mn (SiO) after continuous reaction for 4-48 hours4) And (3) nanoparticles. And centrifuging and washing the product with deionized water for three times, and drying in vacuum to obtain the sample.
Wherein, the bell-shaped core-shell structure ZIF-8@ mSiO2The preparation method of the template comprises the following steps: performing fractional adsorption and dispersion treatment on the prepared ZIF-8 by methanol and deionized water in a volume ratio of 1:9, and adjusting the system to be alkalescent (the pH value is 8-10) by using a sodium hydroxide (NaOH) solution under stirring; weighing 50 wt% of surfactant of fixed feeding amount of reactant ZIF-8, adding the surfactant into the system, and stirring for reaction for 0.5-1 hour; adding tetrabutyl silicate (TEOS) into the solution, continuously stirring for 0.1-2 hours, standing for 0.5-48 hours, centrifuging, washing and vacuum drying to obtain the final core-shell structure ZIF-8@ mSiO2A nanocomposite template.
The bell-shaped core-shell structure ZIF-8@ mSiO2The mass ratio of the template to the deionized water is as follows: 1: 500-10: 500.
The metal manganese salt mainly comprises manganese chloride, manganese acetate and manganese sulfate.
The mass ratio of the metal manganese salt, the ammonium chloride, the ammonia water and the deionized water is as follows: 0.5:15:105: 5000-3: 60:105: 5000.
In the synthesis method of the present invention, the reaction equation of the basic principle is as follows:
Figure BDA0001470079420000031
Figure BDA0001470079420000032
Mn2++SiO3 2-+O2(g)+OH-→Mn(SiO4)(s)+H2O(l) (3)
compared with the prior art, the invention has the following remarkable advantages: under low or high temperature conditions by NH4 +Hydrolysis to control the OH of the system-The release rate and total concentration of (equation 1), OH first-The outer Si-O bond of the shell is converted to form SiO on the surface of the template3 2-(equation 2), and a part of the Si-O bond enters the pores and reaches the inside of the shell, so that the Si-O bond in the inner layer is converted into SiO3 2-(ii) a OH due to ZIF-8 buffering action of the core-ZIF-8 is gradually decomposed, so that the inner surface and the outer surface of the template have enough space and Mn in the system2+The reaction is carried out for a period of time, and finally, a stable configuration with higher specific surface area (445.3 m) is formed2Double-layer hollow Mn (SiO)/g4) Nanoparticles (equation 3). The surface of the nano composite template with the bell-shaped structure provides enough Si-O bonds, the template can be etched under the buffering action of the inner core ZIF-8, and finally a stable double-layer hollow structure can be kept without collapse or decomposition of the template. The prepared double-layer hollow manganese silicate nano-particle has higher specific surface area than the existing hollow nano-particle, and can show better application value in related fields.
Hair brushBright synthetic double-layer hollow Mn (SiO)4) The nano particles have uniform appearance and size, good dispersibility, simple synthesis method and process, high repeatability, economy, low toxicity and environmental friendliness, and the multi-valence state can cause higher reaction activity and generate more types of compounds, thereby having wide application prospect in the fields of electronics, energy, environment, life and the like.
Description of the drawings:
FIG. 1 is a view showing the double-layered hollow Mn (SiO) prepared in FIG. 14) TEM images of nanoparticles.
The specific implementation mode is as follows:
the present invention will be described in more detail with reference to the following examples and the accompanying drawings.
Dumbbell-shaped core-shell structure ZIF-8@ mSiO2Preparation of nanocomposites
Dispersing prepared 50mg ZIF-8 into 20mL of methanol, after adsorption saturation, dispersing into 80mL of water, adding 0.2mL of 1mol/L NaOH solution while stirring, weighing 0.2g CTAB, adding into the system, stirring for 5min, dropwise adding 1.2mL TEOS, continuously stirring for 5min, standing for 5min, centrifuging, washing, and vacuum drying at 40 ℃ to obtain the bell-shaped core-shell structure ZIF-8@ mSiO2And (3) nano materials.
Example 1
50mg of the prepared dumbbell-shaped core-shell structure ZIF-8@ mSiO2Dispersing the nano composite particle template into 25mL of deionized water to form a stable sol dispersion system with the mass concentration of 0.2%; 0.5mmol of manganese chloride was dissolved in 90mL of deionized water and 15mmol of NH was added4And (4) Cl. Then 0.8mL NH was added to the manganese ion solution3·H2O, adding the formed manganese ion complex to the above ZIF-8@ mSiO2In a sol system; and after uniformly stirring, reacting at 10 ℃ for 4 hours to finally form stable and monodisperse double-layer hollow manganese silicate nanoparticles, centrifuging the product, washing the product with deionized water for three times, and drying the product in vacuum at 40 ℃ to obtain the sample.
Example 2
50mg of the prepared dumbbell-shaped core-shell structure ZIF-8@ mSiO2Dispersing the nano composite particle template into 25mL of deionized water to form a stable solutionA sol dispersion system with a certain mass concentration of 0.2%; 0.5mmol of manganese acetate was dissolved in 90mL of deionized water and 15mmol of NH was added4And (4) Cl. Then 0.8mL NH was added to the manganese ion solution3·H2O, adding the formed manganese ion complex to the above ZIF-8@ mSiO2In a sol system; and after uniformly stirring, reacting at 10 ℃ for 4 hours to finally form stable and monodisperse double-layer hollow manganese silicate nanoparticles, centrifuging the product, washing the product with deionized water for three times, and drying the product in vacuum at 40 ℃ to obtain the sample.
Example 3
50mg of the prepared dumbbell-shaped core-shell structure ZIF-8@ mSiO2Dispersing the nano composite particle template into 25mL of deionized water to form a stable sol dispersion system with the mass concentration of 0.2%; 0.5mmol of manganese sulfate was dissolved in 90mL of deionized water, and 15mmol of NH was added4And (4) Cl. Then 0.8mL NH was added to the manganese ion solution3·H2O, adding the formed manganese ion complex to the above ZIF-8@ mSiO2In a sol system; and after uniformly stirring, reacting at 10 ℃ for 4 hours to finally form stable and monodisperse double-layer hollow manganese silicate nanoparticles, centrifuging the product, washing the product with deionized water for three times, and drying the product in vacuum at 40 ℃ to obtain the sample.
Example 4
50mg of the prepared dumbbell-shaped core-shell structure ZIF-8@ mSiO2Dispersing the nano composite particle template into 25mL of deionized water to form a stable sol dispersion system with the mass concentration of 0.2%; 3mmol of manganese chloride was dissolved in 90mL of deionized water and 60mmol of NH was added4And (4) Cl. Then 0.8mL NH was added to the manganese ion solution3·H2O, adding the formed manganese ion complex to the above ZIF-8@ mSiO2In a sol system; and after uniformly stirring, reacting at 10 ℃ for 4 hours to finally form stable and monodisperse double-layer hollow manganese silicate nanoparticles, centrifuging the product, washing the product with deionized water for three times, and drying the product in vacuum at 40 ℃ to obtain the sample.
Example 5
50mg of the prepared dumbbell-shaped core-shell structure ZIF-8@ mSiO2The nanocomposite particle template was dispersed to 25Forming a stable sol dispersion system with the mass concentration of 0.2% in mL deionized water; 3mmol of manganese acetate were dissolved in 90mL of deionized water and 60mmol of NH were added4And (4) Cl. Then 0.8mL NH was added to the manganese ion solution3·H2O, adding the formed manganese ion complex to the above ZIF-8@ mSiO2In a sol system; and after uniformly stirring, reacting at 10 ℃ for 4 hours to finally form stable and monodisperse double-layer hollow manganese silicate nanoparticles, centrifuging the product, washing the product with deionized water for three times, and drying the product in vacuum at 40 ℃ to obtain the sample.
Example 6
50mg of the prepared dumbbell-shaped core-shell structure ZIF-8@ mSiO2Dispersing the nano composite particle template into 25mL of deionized water to form a stable sol dispersion system with the mass concentration of 0.2%; 3mmol of manganese sulfate was dissolved in 90mL of deionized water, and 60mmol of NH was added4And (4) Cl. Then 0.8mL NH was added to the manganese ion solution3·H2O, adding the formed manganese ion complex to the above ZIF-8@ mSiO2In a sol system; and after uniformly stirring, reacting at 10 ℃ for 4 hours to finally form stable and monodisperse double-layer hollow manganese silicate nanoparticles, centrifuging the product, washing the product with deionized water for three times, and drying the product in vacuum at 40 ℃ to obtain the sample.
Example 7
500mg of the prepared wobbled-bell-shaped core-shell structure ZIF-8@ mSiO2Dispersing the nano composite particle template into 25mL of deionized water to form a stable sol dispersion system with the mass concentration of 2%; 0.5mmol of manganese chloride was dissolved in 90mL of deionized water and 15mmol of NH was added4And (4) Cl. Then 0.8mL NH was added to the manganese ion solution3·H2O, adding the formed manganese ion complex to the above ZIF-8@ mSiO2In a sol system; and after uniformly stirring, reacting at 10 ℃ for 4 hours to finally form stable and monodisperse double-layer hollow manganese silicate nanoparticles, centrifuging the product, washing the product with deionized water for three times, and drying the product in vacuum at 40 ℃ to obtain the sample.
Example 8
500mg of the prepared wobbled-bell-shaped core-shell structure ZIF-8@ mSiO2NanocompositeDispersing the material particle template into 25mL of deionized water to form a stable sol dispersion system with the mass concentration of 2%; 0.5mmol of manganese acetate was dissolved in 90mL of deionized water and 15mmol of NH was added4And (4) Cl. Then 0.8mL NH was added to the manganese ion solution3·H2O, adding the formed manganese ion complex to the above ZIF-8@ mSiO2In a sol system; and after uniformly stirring, reacting at 10 ℃ for 4 hours to finally form stable and monodisperse double-layer hollow manganese silicate nanoparticles, centrifuging the product, washing the product with deionized water for three times, and drying the product in vacuum at 40 ℃ to obtain the sample.
Example 9
500mg of the prepared wobbled-bell-shaped core-shell structure ZIF-8@ mSiO2Dispersing the nano composite particle template into 25mL of deionized water to form a stable sol dispersion system with the mass concentration of 2%; 0.5mmol of manganese sulfate was dissolved in 90mL of deionized water, and 15mmol of NH was added4And (4) Cl. Then 0.8mL NH was added to the manganese ion solution3·H2O, adding the formed manganese ion complex to the above ZIF-8@ mSiO2In a sol system; and after uniformly stirring, reacting at 10 ℃ for 4 hours to finally form stable and monodisperse double-layer hollow manganese silicate nanoparticles, centrifuging the product, washing the product with deionized water for three times, and drying the product in vacuum at 40 ℃ to obtain the sample.
Example 10
500mg of the prepared wobbled-bell-shaped core-shell structure ZIF-8@ mSiO2Dispersing the nano composite particle template into 25mL of deionized water to form a stable sol dispersion system with the mass concentration of 2%; 3mmol of manganese chloride was dissolved in 90mL of deionized water and 60mmol of NH was added4And (4) Cl. Then 0.8mL NH was added to the manganese ion solution3·H2O, adding the formed manganese ion complex to the above ZIF-8@ mSiO2In a sol system; and after uniformly stirring, reacting at 10 ℃ for 4 hours to finally form stable and monodisperse double-layer hollow manganese silicate nanoparticles, centrifuging the product, washing the product with deionized water for three times, and drying the product in vacuum at 40 ℃ to obtain the sample.
Example 11
500mg of prepared dumbbell-shaped core-shell structure ZIF-8@mSiO2Dispersing the nano composite particle template into 25mL of deionized water to form a stable sol dispersion system with the mass concentration of 2%; 3mmol of manganese acetate were dissolved in 90mL of deionized water and 60mmol of NH were added4And (4) Cl. Then 0.8mL NH was added to the manganese ion solution3·H2O, adding the formed manganese ion complex to the above ZIF-8@ mSiO2In a sol system; and after uniformly stirring, reacting at 10 ℃ for 4 hours to finally form stable and monodisperse double-layer hollow manganese silicate nanoparticles, centrifuging the product, washing the product with deionized water for three times, and drying the product in vacuum at 40 ℃ to obtain the sample.
Example 12
500mg of the prepared wobbled-bell-shaped core-shell structure ZIF-8@ mSiO2Dispersing the nano composite particle template into 25mL of deionized water to form a stable sol dispersion system with the mass concentration of 2%; 3mmol of manganese sulfate was dissolved in 90mL of deionized water, and 60mmol of NH was added4And (4) Cl. Then 0.8mL NH was added to the manganese ion solution3·H2O, adding the formed manganese ion complex to the above ZIF-8@ mSiO2In a sol system; and after uniformly stirring, reacting at 10 ℃ for 4 hours to finally form stable and monodisperse double-layer hollow manganese silicate nanoparticles, centrifuging the product, washing the product with deionized water for three times, and drying the product in vacuum at 40 ℃ to obtain the sample.
Example 13
50mg of the prepared dumbbell-shaped core-shell structure ZIF-8@ mSiO2Dispersing the nano composite particle template into 25mL of deionized water to form a stable sol dispersion system with the mass concentration of 0.2%; 0.5mmol of manganese chloride was dissolved in 90mL of deionized water and 15mmol of NH was added4And (4) Cl. Then 0.8mL NH was added to the manganese ion solution3·H2O, adding the formed manganese ion complex to the above ZIF-8@ mSiO2In a sol system; and after uniformly stirring, reacting at 35 ℃ for 4 hours to finally form stable and monodisperse double-layer hollow manganese silicate nanoparticles, centrifuging the product, washing the product with deionized water for three times, and drying the product in vacuum at 40 ℃ to obtain the sample.
Example 14
50mg of the preparedDumbbell-shaped core-shell structure ZIF-8@ mSiO2Dispersing the nano composite particle template into 25mL of deionized water to form a stable sol dispersion system with the mass concentration of 0.2%; 3mmol of manganese chloride was dissolved in 90mL of deionized water and 60mmol of NH was added4And (4) Cl. Then 0.8mL NH was added to the manganese ion solution3·H2O, adding the formed manganese ion complex to the above ZIF-8@ mSiO2In a sol system; and after uniformly stirring, reacting at 35 ℃ for 4 hours to finally form stable and monodisperse double-layer hollow manganese silicate nanoparticles, centrifuging the product, washing the product with deionized water for three times, and drying the product in vacuum at 40 ℃ to obtain the sample.
Example 15
50mg of the prepared dumbbell-shaped core-shell structure ZIF-8@ mSiO2Dispersing the nano composite particle template into 25mL of deionized water to form a stable sol dispersion system with the mass concentration of 0.2%; 0.5mmol of manganese chloride was dissolved in 90mL of deionized water and 15mmol of NH was added4And (4) Cl. Then 0.8mL NH was added to the manganese ion solution3·H2O, adding the formed manganese ion complex to the above ZIF-8@ mSiO2In a sol system; and after uniformly stirring, reacting at 50 ℃ for 4 hours to finally form stable and monodisperse double-layer hollow manganese silicate nanoparticles, centrifuging the product, washing the product with deionized water for three times, and drying the product in vacuum at 40 ℃ to obtain the sample.
Example 16
50mg of the prepared dumbbell-shaped core-shell structure ZIF-8@ mSiO2Dispersing the nano composite particle template into 25mL of deionized water to form a stable sol dispersion system with the mass concentration of 0.2%; 3mmol of manganese chloride was dissolved in 90mL of deionized water and 60mmol of NH was added4And (4) Cl. Then 0.8mL NH was added to the manganese ion solution3·H2O, adding the formed manganese ion complex to the above ZIF-8@ mSiO2In a sol system; and after uniformly stirring, reacting at 50 ℃ for 4 hours to finally form stable and monodisperse double-layer hollow manganese silicate nanoparticles, centrifuging the product, washing the product with deionized water for three times, and drying the product in vacuum at 40 ℃ to obtain the sample.
Example 17
50mg of the prepared dumbbell-shaped core-shell structure ZIF-8@ mSiO2Dispersing the nano composite particle template into 25mL of deionized water to form a stable sol dispersion system with the mass concentration of 0.2%; 0.5mmol of manganese chloride was dissolved in 90mL of deionized water and 15mmol of NH was added4And (4) Cl. Then 0.8mL NH was added to the manganese ion solution3·H2O, adding the formed manganese ion complex to the above ZIF-8@ mSiO2In a sol system; and after uniformly stirring, reacting at 180 ℃ for 4 hours to finally form stable and monodisperse double-layer hollow manganese silicate nanoparticles, centrifuging the product, washing the product with deionized water for three times, and drying the product in vacuum at 40 ℃ to obtain the sample.
Example 18
50mg of the prepared dumbbell-shaped core-shell structure ZIF-8@ mSiO2Dispersing the nano composite particle template into 25mL of deionized water to form a stable sol dispersion system with the mass concentration of 0.2%; 3mmol of manganese chloride was dissolved in 90mL of deionized water and 60mmol of NH was added4And (4) Cl. Then 0.8mL NH was added to the manganese ion solution3·H2O, adding the formed manganese ion complex to the above ZIF-8@ mSiO2In a sol system; and after uniformly stirring, reacting at 180 ℃ for 4 hours to finally form stable and monodisperse double-layer hollow manganese silicate nanoparticles, centrifuging the product, washing the product with deionized water for three times, and drying the product in vacuum at 40 ℃ to obtain the sample.
Example 19
500mg of the prepared wobbled-bell-shaped core-shell structure ZIF-8@ mSiO2Dispersing the nano composite particle template into 25mL of deionized water to form a stable sol dispersion system with the mass concentration of 2%; 0.5mmol of manganese chloride was dissolved in 90mL of deionized water and 15mmol of NH was added4And (4) Cl. Then 0.8mL NH was added to the manganese ion solution3·H2O, adding the formed manganese ion complex to the above ZIF-8@ mSiO2In a sol system; and after uniformly stirring, reacting at 35 ℃ for 4 hours to finally form stable and monodisperse double-layer hollow manganese silicate nanoparticles, centrifuging the product, washing the product with deionized water for three times, and drying the product in vacuum at 40 ℃ to obtain the sample.
Example 20
500mg of the prepared wobbled-bell-shaped core-shell structure ZIF-8@ mSiO2Dispersing the nano composite particle template into 25mL of deionized water to form a stable sol dispersion system with the mass concentration of 2%; 3mmol of manganese chloride was dissolved in 90mL of deionized water and 60mmol of NH was added4And (4) Cl. Then 0.8mL NH was added to the manganese ion solution3·H2O, adding the formed manganese ion complex to the above ZIF-8@ mSiO2In a sol system; and after uniformly stirring, reacting at 35 ℃ for 4 hours to finally form stable and monodisperse double-layer hollow manganese silicate nanoparticles, centrifuging the product, washing the product with deionized water for three times, and drying the product in vacuum at 40 ℃ to obtain the sample.
Example 21
500mg of the prepared wobbled-bell-shaped core-shell structure ZIF-8@ mSiO2Dispersing the nano composite particle template into 25mL of deionized water to form a stable sol dispersion system with the mass concentration of 2%; 0.5mmol of manganese chloride was dissolved in 90mL of deionized water and 15mmol of NH was added4And (4) Cl. Then 0.8mL NH was added to the manganese ion solution3·H2O, adding the formed manganese ion complex to the above ZIF-8@ mSiO2In a sol system; and after uniformly stirring, reacting at 50 ℃ for 4 hours to finally form stable and monodisperse double-layer hollow manganese silicate nanoparticles, centrifuging the product, washing the product with deionized water for three times, and drying the product in vacuum at 40 ℃ to obtain the sample.
Example 22
500mg of the prepared wobbled-bell-shaped core-shell structure ZIF-8@ mSiO2Dispersing the nano composite particle template into 25mL of deionized water to form a stable sol dispersion system with the mass concentration of 2%; 3mmol of manganese chloride was dissolved in 90mL of deionized water and 60mmol of NH was added4And (4) Cl. Then 0.8mL NH was added to the manganese ion solution3·H2O, adding the formed manganese ion complex to the above ZIF-8@ mSiO2In a sol system; and after uniformly stirring, reacting at 50 ℃ for 4 hours to finally form stable and monodisperse double-layer hollow manganese silicate nanoparticles, centrifuging the product, washing the product with deionized water for three times, and drying the product in vacuum at 40 ℃ to obtain the sample.
Example 23
500mg of the prepared wobbled-bell-shaped core-shell structure ZIF-8@ mSiO2Dispersing the nano composite particle template into 25mL of deionized water to form a stable sol dispersion system with the mass concentration of 2%; 0.5mmol of manganese chloride was dissolved in 90mL of deionized water and 15mmol of NH was added4And (4) Cl. Then 0.8mL NH was added to the manganese ion solution3·H2O, adding the formed manganese ion complex to the above ZIF-8@ mSiO2In a sol system; and after uniformly stirring, reacting at 180 ℃ for 4 hours to finally form stable and monodisperse double-layer hollow manganese silicate nanoparticles, centrifuging the product, washing the product with deionized water for three times, and drying the product in vacuum at 40 ℃ to obtain the sample.
Example 24
500mg of the prepared wobbled-bell-shaped core-shell structure ZIF-8@ mSiO2Dispersing the nano composite particle template into 25mL of deionized water to form a stable sol dispersion system with the mass concentration of 2%; 3mmol of manganese chloride was dissolved in 90mL of deionized water and 60mmol of NH was added4And (4) Cl. Then 0.8mL NH was added to the manganese ion solution3·H2O, adding the formed manganese ion complex to the above ZIF-8@ mSiO2In a sol system; and after uniformly stirring, reacting for 4 hours at 150 ℃ to finally form stable and monodisperse double-layer hollow manganese silicate nanoparticles, centrifuging the product, washing the product with deionized water for three times, and drying the product in vacuum at 40 ℃ to obtain the sample.
Example 25
25mg of the prepared dumbbell-shaped core-shell structure ZIF-8@ mSiO2Dispersing the nano composite particle template into 10mL of deionized water to form a stable sol dispersion system with the mass concentration of 0.8%; 0.2mmol of manganese acetate was dissolved in 10mL of deionized water and 6mmol of NH was added4And (4) Cl. Then 0.6mL NH was added to the manganese ion solution3·H2O, adding the formed manganese ion complex to the above ZIF-8@ mSiO2In a sol system; stirring, reacting at 10 deg.C for 4 hr to obtain stable monodisperse double-layer hollow manganese silicate nanoparticles, centrifuging, washing with deionized water for three times, and vacuum drying at 40 deg.CThe sample was dried and the TEM image of the sample was shown in FIG. 1.
The specific surface area of the material is about 445.3m as characterized by the test2(ii)/g; the aperture is about 3nm, and the prepared nano-particles show good biodegradability in a simulated body fluid and can be degraded by about 50% in 4-6 hours.
Example 26
50mg of the prepared dumbbell-shaped core-shell structure ZIF-8@ mSiO2Dispersing the nano composite particle template into 25mL of deionized water to form a stable sol dispersion system with the mass concentration of 0.2%; 0.5mmol of manganese acetate was dissolved in 90mL of deionized water and 15mmol of NH was added4And (4) Cl. Then 0.8mL NH was added to the manganese ion solution3·H2O, adding the formed manganese ion complex to the above ZIF-8@ mSiO2In a sol system; and after uniformly stirring, reacting for 48 hours at 10 ℃ to finally form stable and monodisperse double-layer hollow manganese silicate nanoparticles, centrifuging the product, washing the product with deionized water for three times, and drying the product in vacuum at 40 ℃ to obtain the sample.
Example 27
50mg of the prepared dumbbell-shaped core-shell structure ZIF-8@ mSiO2Dispersing the nano composite particle template into 25mL of deionized water to form a stable sol dispersion system with the mass concentration of 0.2%; 3mmol of manganese acetate were dissolved in 90mL of deionized water and 60mmol of NH were added4And (4) Cl. Then 0.8mL NH was added to the manganese ion solution3·H2O, adding the formed manganese ion complex to the above ZIF-8@ mSiO2In a sol system; and after uniformly stirring, reacting for 48 hours at 10 ℃ to finally form stable and monodisperse double-layer hollow manganese silicate nanoparticles, centrifuging the product, washing the product with deionized water for three times, and drying the product in vacuum at 40 ℃ to obtain the sample.
Example 28
50mg of the prepared dumbbell-shaped core-shell structure ZIF-8@ mSiO2Dispersing the nano composite particle template into 25mL of deionized water to form a stable sol dispersion system with the mass concentration of 0.2%; 0.5mmol of manganese acetate was dissolved in 90mL of deionized water and 15mmol of NH was added4And (4) Cl. Followed byTo the manganese ion solution was added 0.8mL NH3·H2O, adding the formed manganese ion complex to the above ZIF-8@ mSiO2In a sol system; and after uniformly stirring, reacting for 48 hours at 35 ℃ to finally form stable and monodisperse double-layer hollow manganese silicate nanoparticles, centrifuging the product, washing the product with deionized water for three times, and drying the product in vacuum at 40 ℃ to obtain the sample.
Example 29
50mg of the prepared dumbbell-shaped core-shell structure ZIF-8@ mSiO2Dispersing the nano composite particle template into 25mL of deionized water to form a stable sol dispersion system with the mass concentration of 0.2%; 3mmol of manganese acetate were dissolved in 90mL of deionized water and 60mmol of NH were added4And (4) Cl. Then 0.8mL NH was added to the manganese ion solution3·H2O, adding the formed manganese ion complex to the above ZIF-8@ mSiO2In a sol system; and after uniformly stirring, reacting for 48 hours at 35 ℃ to finally form stable and monodisperse double-layer hollow manganese silicate nanoparticles, centrifuging the product, washing the product with deionized water for three times, and drying the product in vacuum at 40 ℃ to obtain the sample.
Example 30
50mg of the prepared dumbbell-shaped core-shell structure ZIF-8@ mSiO2Dispersing the nano composite particle template into 25mL of deionized water to form a stable sol dispersion system with the mass concentration of 0.2%; 0.5mmol of manganese acetate was dissolved in 90mL of deionized water and 15mmol of NH was added4And (4) Cl. Then 0.8mL NH was added to the manganese ion solution3·H2O, adding the formed manganese ion complex to the above ZIF-8@ mSiO2In a sol system; and after uniformly stirring, reacting for 48 hours at 50 ℃ to finally form stable and monodisperse double-layer hollow manganese silicate nanoparticles, centrifuging the product, washing the product with deionized water for three times, and drying the product in vacuum at 40 ℃ to obtain the sample.
Example 31
50mg of the prepared dumbbell-shaped core-shell structure ZIF-8@ mSiO2Dispersing the nano composite particle template into 25mL of deionized water to form a stable sol dispersion system with the mass concentration of 0.2%; 3mmol manganese acetate was dissolved in 90mL deionized water and added60mmol NH4And (4) Cl. Then 0.8mL NH was added to the manganese ion solution3·H2O, adding the formed manganese ion complex to the above ZIF-8@ mSiO2In a sol system; and after uniformly stirring, reacting for 48 hours at 50 ℃ to finally form stable and monodisperse double-layer hollow manganese silicate nanoparticles, centrifuging the product, washing the product with deionized water for three times, and drying the product in vacuum at 40 ℃ to obtain the sample.
Example 32
50mg of the prepared dumbbell-shaped core-shell structure ZIF-8@ mSiO2Dispersing the nano composite particle template into 25mL of deionized water to form a stable sol dispersion system with the mass concentration of 0.2%; 0.5mmol of manganese acetate was dissolved in 90mL of deionized water and 15mmol of NH was added4And (4) Cl. Then 0.8mL NH was added to the manganese ion solution3·H2O, adding the formed manganese ion complex to the above ZIF-8@ mSiO2In a sol system; and after uniformly stirring, reacting for 48 hours at 180 ℃ to finally form stable and monodisperse double-layer hollow manganese silicate nanoparticles, centrifuging the product, washing the product with deionized water for three times, and drying the product in vacuum at 40 ℃ to obtain the sample.
Example 33
50mg of the prepared dumbbell-shaped core-shell structure ZIF-8@ mSiO2Dispersing the nano composite particle template into 25mL of deionized water to form a stable sol dispersion system with the mass concentration of 0.2%; 3mmol of manganese acetate were dissolved in 90mL of deionized water and 60mmol of NH were added4And (4) Cl. Then 0.8mL NH was added to the manganese ion solution3·H2O, adding the formed manganese ion complex to the above ZIF-8@ mSiO2In a sol system; and after uniformly stirring, reacting for 48 hours at 180 ℃ to finally form stable and monodisperse double-layer hollow manganese silicate nanoparticles, centrifuging the product, washing the product with deionized water for three times, and drying the product in vacuum at 40 ℃ to obtain the sample.
Example 34
500mg of the prepared wobbled-bell-shaped core-shell structure ZIF-8@ mSiO2Dispersing the nano composite particle template into 25mL of deionized water to form a stable sol dispersion system with the mass concentration of 2%; 0.5mmol of manganese acetate was dissolvedIn 90mL of deionized water, and 15mmol of NH was added4And (4) Cl. Then 0.8mL NH was added to the manganese ion solution3·H2O, adding the formed manganese ion complex to the above ZIF-8@ mSiO2In a sol system; and after uniformly stirring, reacting for 48 hours at 10 ℃ to finally form stable and monodisperse double-layer hollow manganese silicate nanoparticles, centrifuging the product, washing the product with deionized water for three times, and drying the product in vacuum at 40 ℃ to obtain the sample.
Example 35
500mg of the prepared wobbled-bell-shaped core-shell structure ZIF-8@ mSiO2Dispersing the nano composite particle template into 25mL of deionized water to form a stable sol dispersion system with the mass concentration of 2%; 3mmol of manganese acetate were dissolved in 90mL of deionized water and 60mmol of NH were added4And (4) Cl. Then 0.8mL NH was added to the manganese ion solution3·H2O, adding the formed manganese ion complex to the above ZIF-8@ mSiO2In a sol system; and after uniformly stirring, reacting for 48 hours at 10 ℃ to finally form stable and monodisperse double-layer hollow manganese silicate nanoparticles, centrifuging the product, washing the product with deionized water for three times, and drying the product in vacuum at 40 ℃ to obtain the sample.
Example 36
500mg of the prepared wobbled-bell-shaped core-shell structure ZIF-8@ mSiO2Dispersing the nano composite particle template into 25mL of deionized water to form a stable sol dispersion system with the mass concentration of 2%; 0.5mmol of manganese acetate was dissolved in 90mL of deionized water and 15mmol of NH was added4And (4) Cl. Then 0.8mL NH was added to the manganese ion solution3·H2O, adding the formed manganese ion complex to the above ZIF-8@ mSiO2In a sol system; and after uniformly stirring, reacting for 48 hours at 35 ℃ to finally form stable and monodisperse double-layer hollow manganese silicate nanoparticles, centrifuging the product, washing the product with deionized water for three times, and drying the product in vacuum at 40 ℃ to obtain the sample.
Example 37
500mg of the prepared wobbled-bell-shaped core-shell structure ZIF-8@ mSiO2Dispersing the nano composite particle template into 25mL of deionized water to form stable sol dispersion with the mass concentration of 2%Is a step of; 3mmol of manganese acetate were dissolved in 90mL of deionized water and 60mmol of NH were added4And (4) Cl. Then 0.8mL NH was added to the manganese ion solution3·H2O, adding the formed manganese ion complex to the above ZIF-8@ mSiO2In a sol system; and after uniformly stirring, reacting for 48 hours at 35 ℃ to finally form stable and monodisperse double-layer hollow manganese silicate nanoparticles, centrifuging the product, washing the product with deionized water for three times, and drying the product in vacuum at 40 ℃ to obtain the sample.
Example 38
500mg of the prepared wobbled-bell-shaped core-shell structure ZIF-8@ mSiO2Dispersing the nano composite particle template into 25mL of deionized water to form a stable sol dispersion system with the mass concentration of 2%; 0.5mmol of manganese acetate was dissolved in 90mL of deionized water and 15mmol of NH was added4And (4) Cl. Then 0.8mL NH was added to the manganese ion solution3·H2O, adding the formed manganese ion complex to the above ZIF-8@ mSiO2In a sol system; and after uniformly stirring, reacting for 48 hours at 50 ℃ to finally form stable and monodisperse double-layer hollow manganese silicate nanoparticles, centrifuging the product, washing the product with deionized water for three times, and drying the product in vacuum at 40 ℃ to obtain the sample.
Example 39
500mg of the prepared wobbled-bell-shaped core-shell structure ZIF-8@ mSiO2Dispersing the nano composite particle template into 25mL of deionized water to form a stable sol dispersion system with the mass concentration of 2%; 3mmol of manganese acetate were dissolved in 90mL of deionized water and 60mmol of NH were added4And (4) Cl. Then 0.8mL NH was added to the manganese ion solution3·H2O, adding the formed manganese ion complex to the above ZIF-8@ mSiO2In a sol system; and after uniformly stirring, reacting for 48 hours at 50 ℃ to finally form stable and monodisperse double-layer hollow manganese silicate nanoparticles, centrifuging the product, washing the product with deionized water for three times, and drying the product in vacuum at 40 ℃ to obtain the sample.
Example 40
500mg of the prepared wobbled-bell-shaped core-shell structure ZIF-8@ mSiO2The nano-composite particle template is dispersed into 25mL of deionized water to form stable mass concentrationA sol dispersion with a degree of 2%; 0.5mmol of manganese acetate was dissolved in 90mL of deionized water and 15mmol of NH was added4And (4) Cl. Then 0.8mL NH was added to the manganese ion solution3·H2O, adding the formed manganese ion complex to the above ZIF-8@ mSiO2In a sol system; and after uniformly stirring, reacting for 48 hours at 180 ℃ to finally form stable and monodisperse double-layer hollow manganese silicate nanoparticles, centrifuging the product, washing the product with deionized water for three times, and drying the product in vacuum at 40 ℃ to obtain the sample.
EXAMPLE 41
500mg of the prepared wobbled-bell-shaped core-shell structure ZIF-8@ mSiO2Dispersing the nano composite particle template into 25mL of deionized water to form a stable sol dispersion system with the mass concentration of 2%; 3mmol of manganese acetate were dissolved in 90mL of deionized water and 60mmol of NH were added4And (4) Cl. Then 0.8mL NH was added to the manganese ion solution3·H2O, adding the formed manganese ion complex to the above ZIF-8@ mSiO2In a sol system; and after uniformly stirring, reacting for 48 hours at 180 ℃ to finally form stable and monodisperse double-layer hollow manganese silicate nanoparticles, centrifuging the product, washing the product with deionized water for three times, and drying the product in vacuum at 40 ℃ to obtain the sample.

Claims (4)

1. A method for preparing double-layer hollow nano manganese silicate based on a template with a bell-shaped structure is characterized in that the prepared ZIF-8 nano composite particle template coated by mesoporous silica with the bell-shaped core-shell structure is dispersed in deionized water, and ZIF-8 coated by the mesoporous silica with the bell-shaped core-shell structure is hereinafter referred to as ZIF-8@ mSiO2Forming a sol dispersion system with a mass concentration of 0.2 to 2%; dissolving metal manganese salt in deionized water, and adding ammonium chloride crystals;
then, 38% ammonia water was added to the manganese ion solution to form a manganese ion complex, and the manganese ion complex was added to the above ZIF-8@ mSiO2In a sol system; the mass ratio of the metal manganese salt, the ammonium chloride, the ammonia water and the deionized water is as follows: 0.5:15:105: 5000-3: 60:105: 5000; after being stirred uniformly, the mixture is heated to 10 to 35 ℃ or 50 to 180 DEG CThen, after the reaction is continued for 4-48 hours, the double-layer hollow Mn (SiO) with stable configuration can be finally formed4) A nanoparticle; and centrifuging the product, washing the product with deionized water, and drying the product in vacuum to obtain a sample.
2. The method according to claim 1, wherein said barbell ring core-shell structure ZIF-8@ mSiO2The preparation method of the template comprises the following steps: performing step-by-step adsorption and dispersion treatment on the prepared ZIF-8 by using methanol and deionized water in a volume ratio of 1:9, and adjusting the pH value of the system to 8-10 by using a sodium hydroxide solution under stirring; weighing 50 wt% of surfactant of fixed feeding amount of reactant ZIF-8, adding the surfactant into the system, and stirring for reaction for 0.5-1 hour; slowly adding tetrabutyl silicate into the solution, continuously stirring for 0.1-2 hours, standing for 0.5-48 hours, centrifuging, washing, and drying in vacuum to obtain the final core-shell structure ZIF-8@ mSiO2A nanocomposite template.
3. The method according to claim 1, wherein said barbell ring core-shell structure ZIF-8@ mSiO2The mass ratio of the template to the deionized water is as follows: 1: 500-10: 500.
4. The method of claim 1, wherein the manganese metal salt comprises manganese chloride, manganese acetate, or manganese sulfate.
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