CN108793231B - Method for synthesizing spindle-shaped zinc germanate nanoparticles by molten salt method - Google Patents
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Abstract
The invention relates to the technical field of nano materials, in particular to a method for synthesizing spindle-shaped zinc germanate nano particles by a molten salt method, which comprises the following steps: (1) uniformly mixing divalent zinc ion salt, germanium oxide, KCl and LiCl according to the mass ratio of 2: 1: 50 x: 20x, wherein x is more than 0.4 and less than 1.8; (2) putting the obtained mixture into a muffle furnace, heating and roasting, and naturally cooling; (3) soaking the product after reaction in deionized water to remove salt, and performing suction filtration to obtain an off-white solid; (4) and taking the obtained off-white solid out of a centrifuge tube, centrifugally washing the off-white solid for a plurality of times by using deionized water, and drying the off-white solid in vacuum to obtain the product, namely the spindle-shaped zinc germanate nano-particles. The method disclosed by the invention is environment-friendly, short in time, low in energy consumption, few in reaction steps, simple and convenient in process, simple in equipment, easy to obtain raw materials, excellent in product performance and strong in controllability.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a method for synthesizing spindle-shaped zinc germanate nano particles.
Background
The zinc germanate material has a forbidden band width of 4.4eV, is a direct semiconductor, and has valence and conduction band potentials of 3.88eV and-0.62 eV, respectively, calculated from the Mulliken electronegativity (relative to a standard hydrogen electrode). The valence band is mainly formed by hybridization of O2 p, Zn 3d and Ge4p orbitals, and the conduction band is mainly formed by hybridization of Ge 4s, Ge4p, Zn 4s and Zn 3d orbitals. The large-amplitude overlap of the valence band orbits enables electrons on the valence band to have high mobility, and the recombination of photoproduction electrons and holes is inhibited, so that the catalytic performance of zinc germanate is improved. The zinc germanate is used as a photocatalyst, is mainly used for decomposing water, treating various refractory organic benzenes and aromatic pollutants and various organic dyes which are difficult to degrade and reducing carbon dioxide, and has good catalytic performances of decomposing water to prepare hydrogen and oxygen and reducing carbon dioxide into methane, carbon monoxide and the like.
The germanate nano material not only has good luminescence performance and excellent photocatalyst, but also can be used as a negative electrode material of a lithium ion battery. The germanium metal has higher theoretical specific capacity (1600 mA.h.g)-1) The ideal lithium ion diffusion coefficient is considered to be one of the ideal materials to replace the conventional graphite. However, the synthesis cost of the germanium metal nano material is high, the preparation is difficult, and the practical process of the germanium metal nano material is seriously hindered. Zinc germanate as the semiconductor compound has a molecular weight of 1443ma.h.g-1The theoretical lithium intercalation capacity of the zinc germanate is 90.19 percent of germanium, but the mass fraction of the germanium in the zinc germanate is only 27.15 percent, so that the material cost can be effectively reducedTo provide the possibility of large-scale application. Zn element has lithium storage activity and low price, and can ensure higher specific capacity while reducing material cost. The zinc germanate nano material is used for the lithium ion battery cathode material and shows very stable cycle and rate performance.
Develops Zn which is environment-friendly, has good size controllability, uniform appearance and good dispersity and is easy to synthesize in large quantity2GeO4Nano material is favorable to raising Zn content2GeO4The photoelectric property of the nano material explores the application of the nano material in energy and environment.
Disclosure of Invention
The invention aims to provide a method for synthesizing fusiform zinc germanate nanoparticles by a molten salt growth method, so as to solve the problem of Zn in the prior art2GeO4The synthesis process has the problems of high cost, poor performance, poor size controllability of the prepared product, non-uniform appearance, poor dispersibility and the like.
In order to achieve the purpose, the invention provides the following technical scheme:
a method for synthesizing spindle-shaped zinc germanate nanoparticles by a molten salt method comprises the following steps:
(1) uniformly mixing divalent zinc ion salt, germanium oxide, KCl and LiCl according to the mass ratio of 2: 1: 50 x: 20x, wherein x is more than 0.4 and less than 1.8;
(2) putting the obtained mixture into a muffle furnace, heating and roasting, and naturally cooling;
(3) soaking the product after reaction in deionized water to remove salt, and performing suction filtration to obtain an off-white solid;
(4) and taking the obtained off-white solid out of a centrifuge tube, centrifugally washing the off-white solid for a plurality of times by using deionized water, and drying the off-white solid in vacuum to obtain the product, namely the spindle-shaped zinc germanate nano-particles.
The method for synthesizing the spindle-shaped zinc germanate nanoparticles by the molten salt method is characterized in that divalent zinc ion salt is one or more of zinc nitrate, zinc oxide, zinc acetate, zinc oxalate or zinc carbonate.
The method for synthesizing the fusiform zinc germanate nanoparticles by the molten salt method is characterized in that in the step (1), the uniform mixing is grinding and mixing in an agate mortar.
The method for synthesizing the fusiform zinc germanate nanoparticles by the molten salt method comprises the step (2) of collecting an obtained mixture in an alumina crucible and then putting the alumina crucible into a muffle furnace.
The method for synthesizing the fusiform zinc germanate nanoparticles by the molten salt method comprises the step (2), wherein the heating rate is 5 ℃/min, and the temperature is increased to 540-880 ℃.
The method for synthesizing the fusiform zinc germanate nano-particles by the molten salt method comprises the step (2) of roasting for 3-8 hours.
The method for synthesizing the fusiform zinc germanate nano-particles by the molten salt method, disclosed by the invention, wherein in the step (4), the vacuum drying temperature is 40-80 ℃.
The method for synthesizing the fusiform zinc germanate nanoparticles by the molten salt method is characterized in that in the step (4), the fusiform zinc germanate nanoparticles are 1-2 mu m in length, 300-800 nm in diameter and are fusiform.
Compared with the prior art, the invention has the beneficial effects that: the method comprises the steps of uniformly mixing divalent zinc ion salt, germanium oxide, KCl and LiCl according to a certain mass ratio, roasting at high temperature, soaking in distilled water to remove salt, performing suction filtration, washing and drying to obtain the product which is the monodisperse fusiform zinc germanate nano-particles. The synthetic method with low use cost and simple process for preparing Zn with good chemical stability2GeO4Nano material effectively expands Zn2GeO4And (3) application of nano materials. The method disclosed by the invention is environment-friendly, short in time, low in energy consumption, few in reaction steps, simple and convenient in process, simple in equipment, easy to obtain raw materials, excellent in product performance, strong in controllability and wide in market prospect in the aspects of light, electricity, catalysis and the like.
Drawings
FIG. 1 is an X-ray diffraction pattern of a spindle-shaped zinc germanate nanomaterial prepared in example 2 of the present invention;
fig. 2 is a scanning electron microscope image of the spindle-shaped zinc germanate nanoparticles prepared in example 2 of the present invention;
FIG. 3 is a scanning electron microscope image of spindle-shaped zinc germanate nanoparticles prepared in example 4 of the present invention;
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A method for synthesizing spindle-shaped zinc germanate nanoparticles by a molten salt method comprises the following steps:
(1) grinding divalent zinc ion salt, germanium oxide, KCl and LiCl by using an agate mortar according to the mass ratio of 2: 1: 50 x: 20x, wherein x is more than 0.4 and less than 1.8, and uniformly mixing to obtain a solid mixture;
(2) collecting the mixture obtained in the step 1 in an alumina crucible, then putting the alumina crucible in a muffle furnace, heating to 540-880 ℃ at the speed of 5 ℃/min, roasting for 3-8 hours, and naturally cooling;
(3) soaking the product obtained after the reaction in the step 2 in deionized water to remove salt, and performing suction filtration to obtain an off-white solid;
(4) and (3) taking the off-white solid obtained in the step (3) out to a centrifugal tube, centrifugally washing the off-white solid for a plurality of times by using deionized water, and drying the off-white solid in vacuum at the temperature of between 40 and 80 ℃ to obtain the spindle-shaped particles with the length of 1 to 2 mu m and the diameter of 300 to 800 nm.
If the reaction temperature in the step 2 is lower than 540 ℃ or the reaction time is lower than 3 hours, the solid mixture cannot completely react, a pure-phase compound cannot be generated, and the spindle-shaped zinc germanate nanoparticles cannot be obtained; if the reaction temperature in step 2 is higher than 880 ℃, the solid mixture will be converted into larger and non-uniform particles of zinc germanate.
Example 2
Adding Zn (CH)3COO)2And oxidizing the mixtureGrinding germanium, KCl and LiCl by using an agate mortar according to the mass ratio of 2: 1: 50: 20, and uniformly mixing to obtain a solid mixture; collecting the obtained mixture in an alumina crucible, putting the alumina crucible into a muffle furnace, heating to 540 ℃ at the speed of 5 ℃/min, roasting for 4 hours, and naturally cooling; soaking the product after reaction in deionized water to remove salt, and performing suction filtration to obtain an off-white solid; and taking the obtained off-white solid out of a centrifugal tube, centrifugally washing the off-white solid for a plurality of times by using deionized water, and drying the off-white solid in vacuum at the temperature of 60 ℃ to obtain the off-white zinc germanate powder.
XRD tests show that the product is a pure-phase zinc germanate compound (shown in figure 1), and scanning electron microscope tests show that the synthesized spindle-shaped zinc germanate nano-particles are good in dispersity, 1-2 mu m in length and 300-600 nm in diameter. Compared with other preparation methods, the method has the advantages of low cost, simple synthesis process, uniform appearance and good dispersibility.
Example 3
Grinding ZnO, germanium oxide, KCl and LiCl in a mass ratio of 2: 1: 50: 20 by using an agate mortar, and uniformly mixing to obtain a solid mixture; collecting the obtained mixture in an alumina crucible, putting the alumina crucible into a muffle furnace, heating to 680 ℃ at the speed of 5 ℃/min, roasting for 4 hours, and naturally cooling; soaking the product after reaction in deionized water to remove salt, and performing suction filtration to obtain an off-white solid; and taking the obtained off-white solid out of a centrifugal tube, centrifugally washing the off-white solid for a plurality of times by using deionized water, and drying the off-white solid in vacuum at 60 ℃ to obtain the off-white zinc germanate powder.
Example 4
Adding Zn (CH)3COO)2Germanium oxide, KCl and LiCl, according to the mass ratio of 2: 1: 25: 10, grinding by using an agate mortar, and uniformly mixing to obtain a solid mixture; collecting the obtained mixture in an alumina crucible, putting the alumina crucible into a muffle furnace, heating to 600 ℃ at the speed of 5 ℃/min, roasting for 6 hours, and naturally cooling; soaking the product after reaction in deionized water to remove salt, and performing suction filtration to obtain an off-white solid; taking the obtained offwhite solid out of a centrifuge tube, centrifugally washing the offwhite solid for a plurality of times by using deionized water, and drying the offwhite solid in vacuum at the temperature of 60 ℃ to obtain the offwhite germanic acidZinc powder. Scanning electron microscope detection shows that (figure 3), the synthesized spindle-shaped zinc germanate nanoparticles have good dispersibility, the length of 1-2 mu m and the diameter of 500-800 nm.
Example 5
Adding Zn (CH)3COO)2Germanium oxide, KCl and LiCl, according to the mass ratio of 2: 1: 75: 30, grinding by using an agate mortar, and uniformly mixing to obtain a solid mixture; collecting the obtained mixture in an alumina crucible, putting the alumina crucible into a muffle furnace, heating to 580 ℃ at the speed of 5 ℃/min, roasting for 5 hours, and naturally cooling; soaking the product after reaction in deionized water to remove salt, and performing suction filtration to obtain an off-white solid; and taking the obtained off-white solid out of a centrifugal tube, centrifugally washing the off-white solid for a plurality of times by using deionized water, and drying the off-white solid in vacuum at 60 ℃ to obtain the off-white zinc germanate powder.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (6)
1. A method for synthesizing spindle-shaped zinc germanate nanoparticles by a molten salt method is characterized by comprising the following steps:
(1) uniformly mixing divalent zinc ion salt, germanium oxide, KCl and LiCl according to the mass ratio of 2: 1: 50 x: 20x, wherein x is more than 0.4 and less than 1.8;
(2) putting the obtained mixture into a muffle furnace, heating and roasting, and naturally cooling; wherein the heating rate is 5 ℃/min, and the temperature is increased to 540-880 ℃; roasting for 3-8 hours;
(3) soaking the product after reaction in deionized water to remove salt, and performing suction filtration to obtain an off-white solid;
(4) and taking the obtained off-white solid out of a centrifuge tube, centrifugally washing the off-white solid for a plurality of times by using deionized water, and drying the off-white solid in vacuum to obtain the product, namely the spindle-shaped zinc germanate nano-particles.
2. The method for synthesizing fusiform zinc germanate nanoparticles by the molten salt method according to claim 1, wherein the method comprises the following steps: the divalent zinc ion salt is one or more of zinc nitrate, zinc acetate, zinc oxalate or zinc carbonate.
3. The method for synthesizing fusiform zinc germanate nanoparticles by the molten salt method according to claim 1, wherein the method comprises the following steps: in the step (1), the uniform mixing is grinding and mixing in an agate mortar.
4. The method for synthesizing fusiform zinc germanate nanoparticles by the molten salt method according to claim 1, wherein the method comprises the following steps: in the step (2), the obtained mixture is collected in an alumina crucible and then put into a muffle furnace.
5. The method for synthesizing fusiform zinc germanate nanoparticles by the molten salt method according to claim 1, wherein the method comprises the following steps: in the step (4), the temperature of the vacuum drying is 40-80 ℃.
6. The method for synthesizing fusiform zinc germanate nanoparticles by the molten salt method according to claim 1, wherein the method comprises the following steps: in the step (4), the length of the spindle-shaped zinc germanate nano-particles is 1-2 μm, the diameter is 300-800 nm, and the spindle-shaped zinc germanate nano-particles are spindle-shaped.
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