CN114853038B - Large-size two-dimensional amorphous metal oxide material and preparation method thereof - Google Patents

Large-size two-dimensional amorphous metal oxide material and preparation method thereof Download PDF

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CN114853038B
CN114853038B CN202210428539.1A CN202210428539A CN114853038B CN 114853038 B CN114853038 B CN 114853038B CN 202210428539 A CN202210428539 A CN 202210428539A CN 114853038 B CN114853038 B CN 114853038B
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CN114853038A (en
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刘磊
李锐杰
于树磊
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Peking University
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    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
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    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/30—Preparation of aluminium oxide or hydroxide by thermal decomposition or by hydrolysis or oxidation of aluminium compounds
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    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
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    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer

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Abstract

The invention discloses a large-size two-dimensional amorphous metal oxide material based on conventional metal inorganic salt and a general preparation method thereof. The invention takes conventional metal inorganic salt as raw material, deionized water and ammonia (NH) 3 ) One or two of the two-dimensional amorphous metal oxides are used as forming auxiliary agents, the growth process of the amorphous metal oxides is regulated through the strong foaming action generated by the intense gas release induced by the forming auxiliary agents in the calcination treatment, so that the amorphous metal oxides exhibit anisotropic growth, and finally the large-size two-dimensional amorphous metal oxides are prepared. The method comprises the following specific steps: firstly preparing conventional metal inorganic salt raw materials, and then using deionized water and ammonia (NH) 3 ) One or two of the two-dimensional amorphous metal oxide forming auxiliary agents are used as the large-size two-dimensional amorphous metal oxide forming auxiliary agents, the raw materials are placed into an alumina crucible after the forming auxiliary agents are selected, the alumina crucible is placed into a muffle furnace or a tube furnace for low-temperature calcination, and finally the obtained powdery product is collected, namely the large-size two-dimensional amorphous metal oxide. Compared with the traditional preparation method, the conventional metal inorganic salt is low in price and easy to obtain, the reaction condition is mild, the high-temperature and high-pressure reaction is not involved, the environmental pollution is small, and the method is suitable for industrial mass production. The prepared large-size amorphous metal oxide has the transverse size in the range of tens of micrometers to hundreds of micrometers, has the characteristics of thin layer and large size, and can be applied to the fields of energy storage, catalysis, mechanics, electronic industry (such as grid dielectric) and the like.

Description

Large-size two-dimensional amorphous metal oxide material and preparation method thereof
Technical Field
The invention belongs to the technical field of two-dimensional amorphous metal oxide synthesis, and particularly relates to large-size two-dimensional amorphous metal oxides of different types and a preparation method of the two-dimensional amorphous metal oxides, in particular to a large-size two-dimensional amorphous metal oxide material based on metal inorganic salts and a general preparation method thereof.
Background
The flaky amorphous metal oxide represents an important class of materials due to the special atomic arrangement of short-range order and long-range disorderAnd special two-dimensional planar structures (the main morphological features are smaller thickness to larger aspect ratio) which make them widely applicable in energy storage, catalysis, mechanics and electronics industries (such as gate dielectrics). For example, semiconductor amorphous metal oxides such as indium tin oxide (IGZO) as substitutes for crystalline silicon in thin film electronic devices and organic materials in light emitting diode displays have light transmittance, conductivity and good expandability, exhibiting excellent overall performance. Insulating amorphous metal oxides such as silicon dioxide (SiO) 2 ) And hafnium oxide (HfO) with high dielectric constant 2 ) Is a critical industrial dielectric in logic devices, used as gate insulator and memory devices. In the field of energy storage, the unique internal structure of the flaky amorphous metal oxides gives them a smaller volume expansion rate, a faster ion diffusion rate and more active sites, and presents great potential advantages for long-term electrochemical charge storage.
Although several wet chemical methods have been established to successfully produce thin films and agglomerated powders of metal oxides, for some strong acid weak base salts (FeCl 3 、Zr(NO 3 ) 4 、Cr(NO 3 ) 3 、Al(NO 3 ) 3 Etc.) are extremely prone to precipitate to form corresponding metal oxide nanoparticles, and it is difficult to form corresponding flaky amorphous metal oxides. Thus, the controlled synthesis of amorphous metal oxide size and shape remains a significant challenge due to the complex growth mechanism of amorphous nanomaterials.
Based on the method, the invention provides a large-size two-dimensional amorphous metal oxide material based on controllable synthesis of metal inorganic salt and a general preparation method thereof. The general preparation method of the large-size two-dimensional amorphous metal oxide is applicable to a plurality of systems including a monobasic compound, a dibasic compound and a tribasic compound, and can synthesize more than 10 types of large-size two-dimensional amorphous metal oxides. The method is simple to operate and does not involve complex operation flow; the process cost is low, the used raw materials are low in cost, the commercial process is available, and the processing process does not involve high-cost, high-energy consumption and high-pollution process flows; the method has expandability, and can realize the batch preparation of the large-size two-dimensional amorphous metal oxide by the capacity increase of the preparation equipment and the equal proportion amplification of the technological parameters.
Disclosure of Invention
The invention aims to overcome the preparation difficulty of two-dimensional amorphous metal oxide and provides a large-size two-dimensional amorphous metal oxide material capable of being controllably synthesized and a general preparation method thereof. The general preparation method disclosed by the invention takes the conventional metal inorganic salt as a preparation raw material, is mild in reaction condition, free of environmental pollution, low in preparation process cost and strong in expandability, and can be used for batch preparation of large-size two-dimensional amorphous metal oxides.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a process for preparing the two-dimensional amorphous metal oxide with large lamellar layer based on conventional metal inorganic salt features that deionized water and ammonia (NH) 3 ) One or two of the two-dimensional amorphous metal oxide forming auxiliary agents are used as large-sheet-layer two-dimensional amorphous metal oxide forming auxiliary agents.
Further, the preparation method of the large-scale two-dimensional amorphous metal oxide based on the conventional metal inorganic salt comprises the step of preparing a mixed material according to the mol ratio of metal atoms in the conventional metal inorganic salt to deionized water of 1:6-600.
Further, the preparation method of the large-lamellar two-dimensional amorphous metal oxide based on the conventional metal inorganic salt comprises the steps of NH in the low-temperature calcination process 3 And a step of setting the flux to 20sccm to 100 sccm.
Further, the preparation method of the large-lamellar two-dimensional amorphous metal oxide based on the conventional metal inorganic salt comprises the following steps of:
s1, preparing conventional metal inorganic salt raw materials;
s2, deionized water and ammonia (NH) 3 ) One or two of the two-dimensional amorphous metal oxide molding auxiliary agents with large size; wherein, when deionized water is used as the molding auxiliary agent, the deionized water is mixed with the metal inorganic salt and is gently stirred to obtain a uniform mixed material before low-temperature calcination, and then the uniform mixed material is fedCalcining; with NH 3 NH as a molding aid 3 As a gaseous forming auxiliary agent, the material is introduced into a reaction chamber during the calcination process of the metal inorganic salt raw material to assist the preparation of the large-size lamellar amorphous metal oxide;
s3, placing the raw materials into an alumina crucible, and placing the alumina crucible into a muffle furnace or a tube furnace for low-temperature calcination;
s4, after low-temperature calcination, collecting the obtained powdery product, namely the large-size two-dimensional amorphous metal oxide.
Preferably, in step S1, the conventional metal inorganic salts include, but are not limited to, one or more of aluminum nitrate, gallium nitrate, chromium nitrate, zirconium nitrate, indium nitrate, iron nitrate, copper nitrate, zinc nitrate, and hafnium oxychloride.
Preferably, in step S1, for the preparation of two-dimensional amorphous metal oxides of binary system and ternary system, it is necessary to mix different kinds of metal inorganic salt raw materials according to metal atom mole ratio.
Preferably, in the step S2, when deionized water is used as the molding auxiliary agent, the mixture is prepared according to a molar ratio of 1:6-600 between the metal atoms in the metal inorganic salt and the deionized water, and is uniformly mixed under the condition of mild stirring.
Preferably, in step S2, NH is used 3 When the metal inorganic salt is used as the molding auxiliary agent, the metal inorganic salt raw material or the mixture prepared by mixing the metal inorganic salt and deionized water is placed in a low-temperature calcining chamber, and NH of 20-100 sccm is continuously introduced in the whole calcining process 3 . Wherein NH is 3 The flux is directly proportional to the reaction chamber volume.
Preferably, in step S3, the muffle furnace or tube furnace is heated from room temperature to 250-800 ℃ at a heating rate of 5-20 ℃/min.
Preferably, in step S3, the muffle furnace or tube furnace is kept at the calcination temperature for 30-180 min.
Preferably, in step S4, the muffle furnace or the tube furnace is naturally cooled to room temperature after the low-temperature calcination is completed.
In the large-size two-dimensional amorphousIn the general preparation method of the metal oxide, common metal inorganic salt is taken as raw material, deionized water and NH are adopted 3 Or deionized water and NH 3 The synergy assists the formation of the large-size two-dimensional amorphous metal oxide. In the low-temperature calcination process, conventional metal inorganic salt is converted into amorphous material by utilizing the stability of amorphous substances at a specific temperature, and simultaneously, under the induction of a molding auxiliary agent, the large-size two-dimensional amorphous metal oxide is prepared.
When deionized water is used as a forming auxiliary agent, foaming action generated by boiling of the deionized water at a specific temperature induces anisotropic growth of conventional metal inorganic salt in the process of converting the conventional metal inorganic salt into amorphous metal oxide, so that large-size two-dimensional amorphous metal oxide with a large radius-thickness ratio is formed. In the calcination process at a specific temperature, the decomposition of the metal inorganic salt and the boiling of deionized water are almost synchronously carried out, and bubbles generated by the severe boiling of water encountered in the process of 'growing' the oxide lead to the preferential orientation of the amorphous metal oxide in the bubbling direction, so that the amorphous oxide foam with macroscopic to microscopic pores is finally generated. The basic multi-void three-dimensional network structure is formed in such foams by the interdigitation and stacking of large-sized sheets of amorphous oxide. The sheets are the large-size amorphous metal oxide, and have higher surface finish and larger length-diameter ratio, the thickness can reach several micrometers, and the transverse size can reach tens of micrometers to hundreds of micrometers.
Due to the foaming effect generated by the boiling of deionized water, the metal inorganic salt generates certain preferred orientation in the process of forming amorphous metal oxide after decomposition, and the finally prepared growth product is in a porous structure formed by amorphous metal oxide large sheets, and the large-size two-dimensional amorphous metal oxide is obtained after treatment. To further explain the key role and mechanism of deionized water as a formation inducer, a comparison was made with a control group that did not have sufficient deionized water additive. By comparison, it was found that if there is no foaming effect by intense boiling of water, the calcined end product appears as submicron ultrafine powder without any flakes, the amorphous metal oxide grows isotropically, strongly indicating that intense boiling of water and sufficient gas release has a critical effect on the formation of porous structures and large-sized two-dimensional flakes.
NH 3 Is very soluble in water and has very high solubility and a fraction of NH 3 And water to form ammonia monohydrate. With NH 3 As a shaping aid, the NH continuously introduced into the reaction chamber is in this case brought about by the gradual conversion of the water of crystallization contained in the customary metal inorganic salts into liquid water as the temperature increases during the calcination treatment 3 Is soluble in liquid water, part of which is NH 3 Reacts with water to form ammonia monohydrate. NH dissolved in water continuously rises along with the temperature of the reaction chamber 3 The ammonia monohydrate formed by the reaction is strongly decomposed by the intense release and produces a strong foaming action. Within a certain temperature range, NH 3 Is reacted to form ammonia monohydrate and NH 3 The vigorous precipitation of ammonia monohydrate and the repeated decomposition of ammonia monohydrate finally appear to produce a strong foaming action during the growth of the amorphous metal oxide. Under the induction of the foaming action, the conventional metal inorganic salt grows anisotropically in the process of being converted into amorphous metal oxide, so that the large-size two-dimensional amorphous metal oxide with a large diameter-thickness ratio is formed.
The invention has the beneficial effects that: aiming at the difficult problem of controllable synthesis of the size and shape of the amorphous metal oxide and the defects existing in the prior art, the low-cost, pollution-free and macro-scale preparation of the large-size two-dimensional amorphous metal oxide can be realized through the induction effect of the molding auxiliary agent and the simple low-temperature calcination process. In the general preparation method, high-pressure reaction conditions are not involved, the reaction process is rapid and efficient, more importantly, the macro regulation and control of the size and shape of the amorphous metal oxide can be realized on the basis of the prior art, the key problem of large-scale preparation of the amorphous metal oxide is solved, and an effective raw material preparation way is provided for realizing the wide application of the two-dimensional amorphous metal oxide in the energy storage, catalysis, mechanics and electronic industry. In addition, compared with the traditional method, the two-dimensional amorphous metal oxide prepared by the general preparation method has a unique hierarchical structure and has a transverse dimension on the order of tens to hundreds of micrometers, so that the two-dimensional amorphous metal oxide has a huge potential application space in the energy storage, catalysis and electronic industries.
Drawings
FIG. 1 is a flow chart of a general preparation method of the large-size two-dimensional amorphous metal oxide material;
FIG. 2 is a large-sized two-dimensional amorphous AlO prepared in example 1 x Scanning electron microscope pictures of (a);
FIG. 3 is a large-sized two-dimensional amorphous AlO prepared in example 1 x Is selected from the electron diffraction pictures;
FIG. 4 is a two-dimensional amorphous CrO of large size prepared in example 2 x Scanning electron microscope pictures of (a);
FIG. 5 is a two-dimensional amorphous CrO of large size prepared in example 2 x Is selected from the electron diffraction pictures;
FIG. 6 is a two-dimensional amorphous CrO of large size prepared in example 2 x Elemental analysis pictures of (a);
FIG. 7 is a large-size two-dimensional amorphous ZrO 3 prepared by example 3 x Scanning electron microscope pictures of (a);
FIG. 8 is a large-size two-dimensional amorphous ZrO 3 prepared by example 3 x Is selected from the electron diffraction pictures;
FIG. 9 is a large-size two-dimensional amorphous ZrO 3 prepared by example 3 x Elemental analysis pictures of (a);
FIG. 10 is a large-size two-dimensional amorphous AlZrO 2 prepared in example 4 x Scanning electron microscope pictures of (a);
FIG. 11 is a large-size two-dimensional amorphous AlZrO 2 prepared in example 4 x Is selected from the electron diffraction pictures;
FIG. 12 is a large-size two-dimensional amorphous AlZrO 2 prepared in example 4 x Elemental analysis pictures of (a);
FIG. 13 is a large-size two-dimensional amorphous GaInO prepared in example 5 x Scanning electron microscope pictures of (a);
FIG. 14 is a large-size two-dimensional amorphous GaInO prepared in example 5 x Is selected from the electron diffraction pictures;
FIG. 15 is a large-size two-dimensional amorphous GaInO prepared in example 5 x Elemental analysis pictures of (a);
FIG. 16 is a large-sized two-dimensional amorphous AlZrHfO prepared in example 6 x Scanning electron microscope pictures of (a);
FIG. 17 is a large-size two-dimensional amorphous AlZrHfO prepared in example 6 x Is selected from the electron diffraction pictures;
FIG. 18 is a large-size two-dimensional amorphous AlZrHfO prepared in example 6 x Elemental analysis pictures of (a);
Detailed Description
The invention will now be described in further detail with reference to the following examples, wherein the raw materials and equipment are commercially available from the disclosure unless otherwise specified.
Example 1: large-size two-dimensional amorphous AlO x And a preparation method thereof, comprising the following steps:
(one), preparing Al (NO) 3 ) 3 ·9H 2 O raw material;
secondly, deionized water is used as a large-sheet two-dimensional amorphous metal oxide forming auxiliary agent, and a control experiment without adding the deionized water forming auxiliary agent is set at the same time;
(III) according to Al (NO) 3 ) 3 ·9H 2 Preparing a mixed material by the mol ratio of metal atoms in O to deionized water being 1:60;
fourthly, placing the mixture into an alumina crucible after mild stirring uniformly, placing the alumina crucible into a muffle furnace for low-temperature calcination, raising the temperature in the muffle furnace from room temperature to 800 ℃ at a heating rate of 13 ℃/min, and preserving heat for 90min;
fifthly, naturally cooling the temperature in the muffle furnace to room temperature after calcination, and collecting the obtained powdery product, namely the large-size lamellar amorphous metal oxide;
sixthly, observing the prepared large-size two-dimensional amorphous AlO by adopting a scanning electron microscope x Is tested by adopting electron diffraction in selected areas to prepare large-size two-dimensional amorphous AlO x Amorphous character of (a);
(seventh), find after test, as shown in the figure2, comparative experiment in example 1 Large size two-dimensional amorphous AlO prepared without deionized water x Has obvious lamellar structure, and the transverse dimension exceeds 100 mu m; after deionized water is added as a molding auxiliary agent, the large-size two-dimensional amorphous AlO is prepared x There is substantially no apparent change in the microscopic morphology. This is mainly due to the raw material Al (NO) 3 ) 3 ·9H 2 The O contains more crystal water, and the foaming and boiling intensity in a high-temperature environment is enough to ensure that AlO x Forming a large sheet. After deionized water is added as a molding auxiliary agent, the foaming and boiling degree of the mixed material in a high-temperature environment is only enhanced to a certain extent, so that the prepared lamellar two-dimensional amorphous AlO x The morphological effect is not obvious. As shown in FIG. 3, the prepared large-size two-dimensional amorphous AlO x The selected area electron diffraction characterization result shows a diffraction ring shape, which shows that the two-dimensional amorphous AlO prepared by the process x Has obvious amorphous structure.
Example 2: a large-size two-dimensional amorphous CrOx and a preparation method thereof comprise the following steps:
(one), preparing zizane Cr (NO) 3 ) 3 ·9H 2 O raw material;
(II) deionized water and NH 3 As a large-sheet two-dimensional amorphous metal oxide molding auxiliary agent, a control test without adding the molding auxiliary agent is set at the same time;
(III) when deionized water is used as a molding aid, cr (NO) 3 ) 3 ·9H 2 Preparing a mixed material by the mol ratio of metal atoms in O to deionized water being 1:200;
(IV) deionized water and NH 3 When used as a molding aid, deionized water was used as a molding aid in accordance with Cr (NO 3 ) 3 ·9H 2 The mol ratio of metal atoms in O to deionized water is 1:50 for adding NH 3 The flux is related to the reaction chamber volume as follows:
Q＝(10～30)·V
wherein:
q represents NH 3 Flux, unitIs sccm;
v represents the volume of the reaction chamber in dm 3 Or L.
The volume of the reaction chamber adopted in the experiment is 3.04L, and corresponding NH can be determined by the above relation 3 Flux range. In the experiment, 40sccm of NH is continuously introduced in the low-temperature calcination process 3 ；
(V) after the mixture is mildly and uniformly stirred, placing the mixture into an alumina crucible, placing the alumina crucible into a muffle furnace or a tube furnace for low-temperature calcination, raising the temperature of the furnace body from room temperature to 250 ℃ at a heating rate of 10 ℃/min, and preserving heat for 100min;
naturally cooling the temperature in the muffle furnace to room temperature after low-temperature calcination, and collecting the obtained powdery product, namely the large-size lamellar amorphous metal oxide;
seventh, observing the prepared large-size two-dimensional amorphous CrO by adopting a scanning electron microscope x Is tested and prepared into large-size two-dimensional amorphous CrO by adopting selected area electron diffraction x The amorphous characteristic of (2) is calibrated by an energy spectrometer to obtain the large-size two-dimensional amorphous CrO x Element distribution of (2);
as shown in FIG. 4, the experiment of the control group in example 2 shows that the large-size two-dimensional amorphous CrO prepared without adding the molding auxiliary agent x The surface of the block is uneven, and no obvious lamellar structure exists; after deionized water is added as a molding auxiliary agent, the large-size two-dimensional amorphous CrO is prepared x Exhibiting a lamellar structure of large size, the lateral dimension exceeding 30 μm; deionized water and NH 3 When used as a molding auxiliary agent, the prepared large-size two-dimensional amorphous CrO x Exhibiting a lamellar structure of large size, the lateral dimension exceeding 30 μm; description of additional deionized Water or deionized Water and NH 3 Simultaneously, the two-dimensional amorphous CrO with larger size is successfully prepared by taking the two-dimensional amorphous CrO as a molding auxiliary agent x At the same time, the induction effect of deionized water as a molding auxiliary agent, deionized water and NH are obviously shown 3 Is a synergistic induction of (a) by (b). As shown in FIG. 5, the prepared large-size two-dimensional amorphous CrO x Selected area electron diffraction characterization junctionThe result shows a diffraction ring shape, which indicates the two-dimensional amorphous CrO prepared by the process x Has obvious amorphous structure. As shown in FIG. 6, the prepared two-dimensional amorphous CrO is subjected to energy spectrometer x Element analysis shows that Cr elements in the lamellar structure are uniformly distributed, which indicates that the uniformity of the material is good.
Example 3: a large-size two-dimensional amorphous ZrOx and a preparation method thereof comprise the following steps:
(one), prepare zizania Zr (NO) 3 ) 4 ·5H 2 O raw material;
(II) deionized water and NH respectively 3 As a large-sheet two-dimensional amorphous metal oxide molding auxiliary agent, a control test without adding the molding auxiliary agent is set at the same time;
(III) when deionized water is used as a molding aid, zr (NO) 3 ) 4 ·5H 2 Preparing a mixed material by the mol ratio of metal atoms in O to deionized water being 1:75; with NH 3 NH as molding aid 3 The flux is related to the reaction chamber volume as follows:
Q＝(10～30)·V
wherein:
q represents NH 3 Flux in sccm;
v represents the volume of the reaction chamber in dm 3 Or L.
The volume of the reaction chamber adopted in the experiment is 3.04L, and corresponding NH can be determined by the above relation 3 Flux range. In the experiment, 50sccm of NH is continuously introduced in the low-temperature calcination process 3 ；
Fourthly, in a control group experiment and an experiment using deionized water as a molding auxiliary agent, placing the mixture into an alumina crucible after being mildly and uniformly stirred, placing the alumina crucible into a muffle furnace for low-temperature calcination, increasing the temperature in the muffle furnace from room temperature to 250 ℃ at a heating rate of 8 ℃/min, and preserving heat for 120min; at NH of 3 In the experiment for forming an auxiliary agent, a metal inorganic salt raw material is placed in a quartz tube of a tube furnace, the temperature is increased to 250 ℃ from room temperature at a heating rate of 8 ℃/min, and the temperature is kept for 120min;
fifthly, naturally cooling the temperature in the muffle furnace to room temperature after low-temperature calcination, and collecting the obtained powdery product, namely the large-size lamellar amorphous metal oxide;
observing the microscopic morphology of the prepared large-size two-dimensional amorphous ZrOx by adopting a scanning electron microscope, and testing the amorphous characteristic of the prepared large-size two-dimensional amorphous ZrOx by adopting selective electron diffraction; calibrating the element distribution of the prepared large-size two-dimensional amorphous ZrOx by an energy spectrometer;
(seventh), as shown in FIG. 7, the control experiment in example 3 was conducted to prepare large-sized two-dimensional amorphous ZrO x Appearance of ultrafine powder without any flakes; adding deionized water as forming auxiliary agent to prepare large-size two-dimensional amorphous ZrO x The two-dimensional amorphous ZrO with larger size is obtained by representing a lamellar structure with larger size, and the transverse size is more than 60 mu m, which shows that the two-dimensional amorphous ZrO with larger size is successfully prepared by adding deionized water as a molding auxiliary agent x Meanwhile, the induction effect of deionized water as a molding auxiliary agent is also obviously shown; NH is introduced during the calcination process 3 After being used as a molding auxiliary agent, the prepared large-size two-dimensional amorphous ZrO x Also shows a lamellar structure of large size, with a lateral dimension exceeding 60 μm, indicating NH 3 The preparation of the large-size two-dimensional amorphous metal oxide is obviously induced by the preparation of the large-size two-dimensional amorphous metal oxide as a molding auxiliary agent. As shown in FIG. 8, the prepared large-size two-dimensional amorphous ZrO x The selected area electron diffraction characterization result shows diffraction ring shape, which shows that the two-dimensional amorphous ZrO prepared by the process x Has obvious amorphous structure. As shown in FIG. 9, the two-dimensional amorphous ZrO obtained by the preparation of the mass spectrometer x Elemental analysis shows that Zr elements in the lamellar structure are uniformly distributed, which indicates that the uniformity of the material is good.
To sum up, deionized water and NH 3 The amorphous metal oxide has a key effect on the formation of large-size amorphous metal oxides as a forming auxiliary agent.
The preparation of large-size two-dimensional amorphous metal oxides for binary and ternary systems is illustrated in the following three examples. Wherein the proportion of different metal inorganic salts in the multi-element system is needed to be noted.
Example 4: a large-size two-dimensional amorphous AlZrOx of a binary system and a preparation method thereof comprise the following steps:
(one), preparing Al (NO) 3 ) 3 ·9H 2 O and Zr (NO) 3 ) 4 ·5H 2 O raw material;
secondly, deionized water is used as a large-sheet two-dimensional amorphous metal oxide forming auxiliary agent of a binary system;
(III) according to Al (NO) 3 ) 3 ·9H 2 O and Zr (NO) 3 ) 4 ·5H 2 Mixing the two metal inorganic salts with the metal atom mol ratio of 1:1, wherein the mol ratio of the metal atoms in the two metal inorganic salts to deionized water is 1:100 in the preparation process of the mixed material;
fourthly, placing the mixture into an alumina crucible after mild stirring uniformly, placing the alumina crucible into a muffle furnace for low-temperature calcination, raising the temperature in the muffle furnace from room temperature to 350 ℃ at a heating rate of 13 ℃/min, and preserving heat for 130min;
fifthly, naturally cooling the temperature in the muffle furnace to room temperature after low-temperature calcination, and collecting the obtained powdery product, namely the large-size lamellar amorphous metal oxide;
observing the microscopic morphology of the prepared large-size two-dimensional amorphous AlZrOx by adopting a scanning electron microscope, testing the amorphous characteristic of the prepared large-size two-dimensional amorphous AlZrOx by adopting selective electron diffraction, and calibrating the element distribution of the prepared large-size two-dimensional amorphous AlZrOx by adopting an energy spectrometer;
(seventh), as shown in fig. 10, the two-dimensional amorphous AlZrOx with large size in the binary system prepared by adding deionized water as the molding auxiliary agent in example 4 shows a lamellar structure with large size, and the transverse size exceeds 50 μm; the method shows that the addition of deionized water as the molding auxiliary agent is also effective for preparing the large-size two-dimensional amorphous oxide of the binary system, and simultaneously highlights the induction effect of the deionized water as the molding auxiliary agent. As shown in fig. 11, the electron diffraction characterization result of the large-size two-dimensional amorphous AlZrOx selective area shows a diffraction ring shape, which indicates that the two-dimensional amorphous AlZrOx prepared by the process has an obvious amorphous structure. As shown in fig. 12, elemental analysis of the two-dimensional amorphous AlZrOx obtained by the preparation method by an energy spectrometer shows that the Al element and the Zr element in the lamellar structure are uniformly distributed, which indicates that the uniformity of the material is good.
Example 5: a large-size two-dimensional amorphous GaInOx of a binary system and a preparation method thereof comprise the following steps:
(one), preparing Ga (NO) 3 ) 3 ·H 2 O and In (NO) 3 ) 3 ·4H 2 O raw material;
secondly, deionized water is used as a large-sheet two-dimensional amorphous metal oxide forming auxiliary agent of a binary system;
(III) according to Ga (NO) 3 ) 3 ·H 2 O and In (NO) 3 ) 3 ·4H 2 Mixing the two metal inorganic salts with the metal atom mol ratio of 8:1, wherein the mol ratio of the metal atoms in the two metal inorganic salts to deionized water is 1:80 in the preparation process of the mixed material;
fourthly, placing the mixture into an alumina crucible after mild stirring uniformly, placing the alumina crucible into a muffle furnace for low-temperature calcination, raising the temperature in the muffle furnace from room temperature to 250 ℃ at a heating rate of 10 ℃/min, and preserving heat for 120min;
fifthly, naturally cooling the temperature in the muffle furnace to room temperature after low-temperature calcination, and collecting the obtained powdery product, namely the large-size lamellar amorphous metal oxide;
observing the microscopic morphology of the prepared large-size two-dimensional amorphous GaInOx by adopting a scanning electron microscope, testing the amorphous characteristic of the prepared large-size two-dimensional amorphous GaInOx by adopting selective electron diffraction, and calibrating the element distribution of the prepared large-size two-dimensional amorphous GaInOx by adopting an energy spectrometer;
(seventh), as shown in fig. 13, the two-dimensional amorphous GaInOx with large size of binary system prepared by adding deionized water as molding auxiliary agent in example 5 shows a lamellar structure with large size, and the transverse size exceeds 100 μm; the method has the advantages that the addition of deionized water as the molding auxiliary agent is effective for preparing the large-size two-dimensional amorphous oxide of the binary system, and meanwhile, the induction effect of the deionized water as the molding auxiliary agent is highlighted. As shown in fig. 14, the electron diffraction characterization result of the large-size two-dimensional amorphous GaInOx selective area shows a diffraction ring shape, which indicates that the two-dimensional amorphous GaInOx prepared by the process has an obvious amorphous structure. As shown In fig. 15, elemental analysis of the two-dimensional amorphous GaInOx obtained by the preparation method by an energy spectrometer shows that Ga element and In element In the lamellar structure are uniformly distributed, which indicates that the uniformity of the material is good.
Example 6: a large-size two-dimensional amorphous AlZrHfOx of a ternary system and a preparation method thereof comprise the following steps:
(one), preparing Al (NO) 3 ) 3 ·9H 2 O、Zr(NO 3 ) 4 ·5H 2 O and Cl 2 HfO·8H 2 O raw material;
secondly, deionized water is used as a large-sheet two-dimensional amorphous metal oxide forming auxiliary agent of a ternary system;
(III) according to Al (NO) 3 ) 3 ·9H 2 O、Zr(NO 3 ) 4 ·5H 2 O and Cl 2 HfO·8H 2 Mixing the three metal inorganic salts according to the metal atom molar ratio of 8:1:1, wherein the molar ratio of the metal atoms in the three metal inorganic salts to deionized water is 1:75 in the preparation process of the mixed material;
fourthly, placing the mixture into an alumina crucible after mild stirring uniformly, placing the alumina crucible into a muffle furnace for low-temperature calcination, raising the temperature in the muffle furnace from room temperature to 250 ℃ at a heating rate of 10 ℃/min, and preserving heat for 120min;
fifthly, naturally cooling the temperature in the muffle furnace to room temperature after low-temperature calcination, and collecting the obtained powdery product, namely the large-size lamellar amorphous metal oxide;
observing the microscopic morphology of the prepared large-size two-dimensional amorphous AlZrHfOx by adopting a scanning electron microscope, testing the amorphous characteristic of the prepared large-size two-dimensional amorphous AlZrHfOx by adopting selective electron diffraction, and calibrating the element distribution of the prepared large-size two-dimensional amorphous AlZrHfOx by adopting an energy spectrometer;
(seventh), as shown in fig. 16, the large-size two-dimensional amorphous alzrfrox of the ternary system prepared by adding deionized water as the molding auxiliary agent in example 6 shows a large-size lamellar structure, and the transverse size exceeds 50 μm; the method has the advantages that the deionized water is added as the molding auxiliary agent to be effective for preparing the large-size two-dimensional amorphous oxide of the ternary system, and meanwhile, the induction effect of the deionized water as the molding auxiliary agent is highlighted. As shown in fig. 17, the electron diffraction characterization result of the large-size two-dimensional amorphous AlZrHfOx selected region shows a diffraction ring shape, which indicates that the two-dimensional amorphous AlZrHfOx prepared by the process has an obvious amorphous structure. As shown in fig. 18, elemental analysis of the two-dimensional amorphous alzhfox obtained by the preparation method by an energy spectrometer shows that the Al element, zr element and Hf element in the lamellar structure are uniformly distributed, which indicates that the uniformity of the material is good.
When deionized water is used as a molding auxiliary agent, the above examples show that the amorphous metal oxide lamellar structure with the transverse dimension exceeding 50 μm can be obtained after the low-temperature calcination treatment of the mixed material prepared according to the molar ratio of the metal atoms in the metal inorganic salt to the deionized water of 1:50-100, and the process stability and the dimensional stability of the lamellar structure are good. When the adding amount of deionized water is too low, the foaming and boiling degree of the deionized water in a high-temperature environment is weak, so that the metal inorganic salt generates obvious preferred orientation in the process of forming amorphous metal oxide after decomposition, the amorphous metal oxide tends to isotropically grow, and the calcined final product shows an amorphous metal oxide lamellar structure with smaller transverse dimension. In the limit of no deionized water forming aid added, the metal inorganic salt after calcination appears as submicron ultrafine powder without any flakes. When the addition amount of deionized water is too high, excessive deionized water in the mixed material in the reaction chamber is largely evaporated in the heating process, and the foaming and boiling degree generated is strong enough, but the too strong foaming and boiling effect can not only increase the air hole residues in the calcined product, but also can cause the reduction of the transverse size of the sheet layer due to the influence of a large amount of bubbles in the amorphous metal oxide growth process. In addition, with energy conservation and cost conservation as standards, on the premise that a small amount of deionized water can play a role, the addition of excessive deionized water can also obtain the lamellar two-dimensional amorphous metal oxide with larger size, but is not beneficial to optimizing the cost control process flow. Therefore, when deionized water is used as the molding aid, a molar ratio of the metal atoms in the metal inorganic salt to deionized water of 1:50-100 can be used as the preferable ratio range.
Similarly, in NH 3 As can be seen from the above examples, when the volume of the reaction chamber is fixed at 3.04L as the molding aid, 50sccm of NH was continuously introduced into the reaction chamber during the low-temperature calcination of the metal-inorganic salt raw material 3 Finally, an amorphous metal oxide layered structure having a lateral dimension exceeding 50 μm can be obtained. When NH 3 When the flux is too low, NH is used in the calcination process 3 The foaming degree is weak, and the foaming degree is insufficient to ensure that the metal inorganic salt generates obvious preferred orientation in the process of forming amorphous metal oxide after decomposition, so that the flaky amorphous metal oxide with larger transverse dimension cannot be obtained. When NH 3 When the flux is too high, the NH is excessive 3 Cannot all contribute to the foaming during calcination, most of the NH 3 After being introduced into the reaction chamber, the gas is discharged from the tail gas, so that the foaming effect is not effectively enhanced, and most of gas cannot be utilized to cause waste. Thus, NH is used as 3 NH continuously introduced into the reaction chamber during calcining of the metal inorganic salt raw material when being the molding auxiliary agent 3 A flux of 40 to 60sccm may be used as the preferred ratio range. Namely NH 3 The preferred ratio ranges of flux to reaction chamber volume are as follows:
Q＝(13～20)·V
wherein:
q represents NH 3 Flux in sccm;
v represents the volume of the reaction chamber in dm 3 Or L.
In summary, the factors such as the promotion effect of the forming auxiliary agent on the growth of the large-size lamellar amorphous metal oxide, the process stability in the preparation process, the process cost and the like are comprehensively considered, and the preferred proportion ranges when deionized water and ammonia are respectively used as the forming auxiliary agent are further summarized through specific examples, so that the method has guiding significance on the stable synthesis of the large-size lamellar amorphous metal oxide.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (6)

1. The preparation method of the large-size two-dimensional amorphous metal oxide based on the conventional metal inorganic salt is characterized by comprising the following steps of:
s1, preparing conventional metal inorganic salt raw materials;
s2, deionized water and NH are used 3 One or two of the two-dimensional amorphous metal oxide forming auxiliary agents of the large sheet layer; when deionized water is used as a forming auxiliary agent, the deionized water is mixed with metal inorganic salt and stirred gently to obtain a uniform mixed material before low-temperature calcination, and then calcination is carried out; with NH 3 NH as a molding aid 3 As a gaseous forming auxiliary agent, the material is introduced into a reaction chamber during the calcination process of the metal inorganic salt raw material to assist the preparation of the large-size lamellar amorphous metal oxide;
when deionized water is used as a forming auxiliary agent, preparing a mixed material according to the mol ratio of metal atoms in the metal inorganic salt to the deionized water being 1:50-100; with NH 3 NH as a molding aid 3 The ratio of flux to reaction chamber volume ranges from:
Q＝(13～20)·V
wherein:
q represents NH 3 Flux in units ofsccm；
V represents the volume of the reaction chamber in dm 3 Or L;
s3, placing the raw materials into an alumina crucible, and placing the alumina crucible into a muffle furnace or a tube furnace for low-temperature calcination; the muffle furnace or the tube furnace increases the temperature from room temperature to 250-800 ℃ at a heating rate of 5-20 ℃/min; the heat preservation time of the muffle furnace or the tube furnace is 30-180 min at the calcining temperature;
s4, after low-temperature calcination, collecting the obtained powdery product, namely the large-size lamellar amorphous metal oxide, wherein the transverse size of the large-size lamellar amorphous metal oxide exceeds 30 mu m.
2. The method for preparing a large-sized two-dimensional amorphous metal oxide according to claim 1, wherein in step S1, the conventional metal inorganic salts include, but are not limited to, one or more of aluminum nitrate, gallium nitrate, chromium nitrate, zirconium nitrate, indium nitrate, ferric nitrate, copper nitrate, zinc nitrate, and hafnium oxychloride.
3. The method for preparing a large-size two-dimensional amorphous metal oxide according to claim 1, wherein the two-dimensional amorphous metal oxide comprising a binary system and a ternary system requires a step of mixing different kinds of metal inorganic salt raw materials according to a metal atom mole ratio.
4. The method for producing a large-size two-dimensional amorphous metal oxide according to claim 1, wherein in step S4, the muffle furnace or the tube furnace is naturally cooled to room temperature after the low-temperature calcination is completed.
5. The method for producing a large-size two-dimensional amorphous metal oxide according to any one of claims 1 to 4, wherein the method comprises NH during calcination 3 A step of measuring a flux of 20sccm to 100sccm, wherein NH 3 The flux is in a proportional relationship with the volume of the reaction chamber; the lateral dimension of the prepared large-lamellar two-dimensional amorphous metal oxide exceeds 30 mu m;
NH 3 the ratio of flux to reaction chamber volume ranges from:
Q＝(13～20)·V
wherein:
q represents NH 3 Flux in sccm;
v represents the volume of the reaction chamber in dm 3 Or L.
6. A large-size two-dimensional amorphous metal oxide material, wherein the large-size two-dimensional amorphous metal oxide is prepared by the preparation method of the large-size two-dimensional amorphous metal oxide according to any one of claims 1 to 5.
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