CN114702011B - Preparation method of two-dimensional non-layered metal oxide porous nano-sheet - Google Patents

Preparation method of two-dimensional non-layered metal oxide porous nano-sheet Download PDF

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CN114702011B
CN114702011B CN202210264103.3A CN202210264103A CN114702011B CN 114702011 B CN114702011 B CN 114702011B CN 202210264103 A CN202210264103 A CN 202210264103A CN 114702011 B CN114702011 B CN 114702011B
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黄亮
刘凯思
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Huazhong University of Science and Technology
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Abstract

The invention discloses a preparation method of a two-dimensional non-layered metal oxide porous nano-sheet, and belongs to the technical field of nano-material preparation. Glucose, ammonium nitrate and metal salt are uniformly mixed, and then the mixture is calcined at a certain temperature, so that the corresponding two-dimensional metal oxide porous nano-sheet can be obtained. The method can be used for preparing various metal oxide porous nano-sheets with non-layered structures, wherein the metal oxide porous nano-sheets comprise rare earth metal oxides, transition metal oxides, III main group metal oxides, II main group metal oxides, high entropy metal oxides, various perovskite oxides and the like. The prepared large-size two-dimensional metal oxide porous nano-sheets have wide application prospects in catalysis, energy storage, sensing and other aspects.

Description

Preparation method of two-dimensional non-layered metal oxide porous nano-sheet
Technical Field
The invention belongs to the field of nano material preparation, and particularly relates to a preparation method of a two-dimensional non-layered metal oxide porous nano sheet, in particular to a method for preparing the two-dimensional metal oxide nano sheet in a large scale.
Background
The two-dimensional oxide has an atomic-scale thickness, and surface atoms thereof are almost completely exposed. Due to the size confinement effect, two-dimensional metal oxides have unique electronic structures and physicochemical properties compared to bulk metal oxides. Thus, the two-dimensional oxide has wide application in the fields of energy storage and conversion.
Various strategies have been developed to date to produce two-dimensional metal oxides, including vapor deposition and liquid phase processes. Vapor deposition methods include physical and chemical vapor deposition methods. The method is favorable for producing the oxide nano-sheet with high quality, large area and controllable thickness. However, this approach typically involves complex and demanding synthetic procedures. In addition, the method has low yield and cannot be used for mass production. In contrast, liquid phase processes (including liquid phase stripping processes as well as wet chemical processes), which are low cost and simple to operate, are considered to be one of the effective processes for producing two-dimensional oxides. However, the liquid phase stripping method is only suitable for strippingOxides having a layered structure, e.g. delta-MnO 2 And V 2 O 5 Etc. Whereas most oxides have a non-layered structure with atoms or molecules of the same strength in each dimension. Therefore, the liquid phase exfoliation method cannot universally produce two-dimensional metal oxides. Wet chemistry is not limited to the intrinsic structure of the synthetic material, but the process requires the introduction of surfactants or organics to promote the formation of two-dimensional morphology. And the surfactant or organic matters are difficult to remove in the subsequent process, so that the performance of the two-dimensional material is affected. Thus, achieving the preparation of a variety of two-dimensional metal oxides using a simple and versatile process remains a significant challenge.
Disclosure of Invention
In order to meet the above defects or improvement demands of the prior art, the invention provides a method for preparing two-dimensional metal oxide nano sheets in a large scale, glucose, ammonium nitrate and metal salt are uniformly mixed and then calcined, and the two-dimensional metal oxide porous nano sheets are formed by sintering. The method aims to realize large-scale industrialized preparation of various two-dimensional metal oxide nano-sheets, and solves the technical problems that the yield of the oxide nano-sheets is low and the large-scale preparation cannot be realized in the prior art.
According to a first aspect of the present invention, there is provided a method for preparing a two-dimensional non-layered metal oxide porous nanosheet, comprising the steps of:
(1) Uniformly mixing glucose, ammonium nitrate and metal salt, wherein the metal salt is rare earth metal salt, transition metal salt, III main group metal salt or II main group metal salt;
(2) Calcining the mixture obtained in the step (1) to make ammonium ions and glucose undergo Maillard reaction to form melanoidin polymer; the melanoidin polymer and nitrate ions undergo oxidation-reduction reaction, so that the melanoidin polymer is internally expanded and converted into carbon nano sheets; meanwhile, the metal ions are oxidized into metal oxide nano particles to be embedded into the carbon nano sheets; finally, the metal oxide nano particles take the carbon nano sheet as a template, the porous metal oxide nano sheet is formed by sintering, and the carbon nano sheet serving as the template is calcined and decomposed.
Preferably, the metal salt is at least one of nitrate, chloride and acetate.
Preferably, the metal salt is a single metal salt or a mixed metal salt.
Preferably, the rare earth metal salt is samarium nitrate, erbium nitrate, praseodymium nitrate, gadolinium nitrate, yttrium nitrate, ytterbium nitrate or neodymium nitrate; the transition metal salt is cobalt nitrate, nickel nitrate, chromium nitrate or zirconium nitrate; the III main group metal salt is aluminum nitrate, gallium nitrate or indium nitrate; the metal salt of the main group II is magnesium nitrate, calcium nitrate or strontium nitrate.
Preferably, the mass ratio of the glucose to the ammonium nitrate is 1 (1-10).
Preferably, the sum of the mass ratio of the glucose and the ammonium nitrate is 1 (1-50).
Preferably, the calcination temperature is 400-1100 ℃, and the calcination time is 10-240 min.
According to another aspect of the invention, there is provided a two-dimensional non-layered metal oxide porous nanoplatelet prepared by any of the methods.
Preferably, the thickness of the nanoplatelets is 1.5nm to 50nm.
In general, the above technical solutions conceived by the present invention, compared with the prior art, enable the following beneficial effects to be obtained:
(1) The invention adopts a solid-phase combustion method to uniformly mix glucose, ammonium nitrate and metal salt, and then calcines the mixture at a certain temperature to obtain the corresponding two-dimensional metal oxide porous nano-sheet. The method has low raw material cost and simple operation, and can be used for mass preparation and industrial production.
(2) The method successfully prepares a plurality of metal oxide two-dimensional porous nano-sheets with non-lamellar structures, wherein the metal oxide two-dimensional porous nano-sheets comprise rare earth metal oxides, transition metal oxides, III main group metal oxides, II main group metal oxides, high entropy metal oxides, a plurality of perovskite oxides and the like.
(3) The invention prepares the two-dimensional nano-sheet porous structure by a one-step method. The nano-sheets with the porous structure can effectively prevent the nano-sheets from being stacked and increase the specific surface area of the nano-sheets. In addition, the defect of the porous nanoplatelets has a large number of active sites.
(4) The invention can strictly control the aperture and thickness of the porous nano-sheet, and the aperture of the porous nano-sheet is reduced and the thickness is increased along with the increase of the precursor content.
Drawings
FIG. 1 is a schematic illustration of a method of mass-producing two-dimensional metal oxide nanoplatelets according to the present invention.
FIG. 2 is a two-dimensional Er prepared in example 1 2 O 3 SEM pictures of nanoplatelets.
FIG. 3 is a two-dimensional Er prepared in example 1 2 O 3 TEM image of nanoplatelets.
FIG. 4 is a two-dimensional Er obtained in example 1 2 O 3 XRD pattern of nanoplatelets.
FIG. 5 is a two-dimensional Er prepared in example 2 2 O 3 SEM pictures of nanoplatelets.
FIG. 6 is a two-dimensional Er prepared in example 2 2 O 3 TEM image of nanoplatelets.
FIG. 7 is a two-dimensional Er prepared in example 3 with 0.02g of precursor metal salt 2 O 3 TEM image of nanoplatelets.
FIG. 8 is a two-dimensional Er prepared in example 3 with 0.02g of precursor metal salt 2 O 3 Pore size distribution of nanoplatelets.
FIG. 9 is a two-dimensional Er prepared in example 3 with 0.1g of precursor metal salt 2 O 3 TEM image of nanoplatelets.
FIG. 10 is a two-dimensional Er prepared in example 3 with 0.1g of precursor metal salt 2 O 3 Pore size distribution of nanoplatelets.
FIG. 11 is a two-dimensional Er prepared in example 3 with 0.02g of precursor metal salt 2 O 3 AFM image of nanoplatelets.
FIG. 12 is a two-dimensional Er prepared in example 3 with 0.1g of precursor metal salt 2 O 3 AFM pictures of nanoplatelets.
FIG. 13 is a TEM image of the two-dimensional MgO nano-sheet prepared in example 4.
Fig. 14 is an XRD pattern of the two-dimensional MgO nanosheets prepared in example 4.
FIG. 15 shows two-dimensional Al prepared in example 5 2 O 3 TEM image of nanoplatelets.
FIG. 16 shows two-dimensional Al prepared in example 5 2 O 3 XRD pattern of nanoplatelets.
FIG. 17 shows two-dimensional La prepared in example 6 0.96 Mn 0.96 O 3 TEM image of nanoplatelets.
FIG. 18 shows two-dimensional La prepared in example 6 0.96 Mn 0.96 O 3 XRD pattern of nanoplatelets.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The method for preparing the two-dimensional metal oxide nano-sheets in large scale is provided in the embodiment: glucose, ammonium nitrate and corresponding metal salts are uniformly mixed, and then the mixture is calcined to obtain the large-size two-dimensional metal oxide porous nano-sheet.
(1) Glucose, ammonium nitrate and corresponding metal salts are uniformly mixed; the mixing mode of glucose, ammonium nitrate and corresponding metal salt comprises solid phase grinding, freeze drying after mixing the solutions, and evaporating the solvent after mixing the solutions to form uniform gel. The mass ratio of glucose to ammonium nitrate is 1:1 to 1:10; the mass ratio of the metal nitrate to the mixture of glucose and ammonium nitrate is 1:1 to 1:50; the types of metal salts include, but are not limited to: nitrate, chloride and acetate; the kinds of the metal salts include a single kind or plural kinds; the metal element species of the metal salts include, but are not limited to, mg, ca, sr, ba, sc, Y, ti, zr, V, nb, ta, cr, mo, W, mn, fe, ru, co, rh, ni, cu, ag, zn, cd, al, ga, in, ge, sn, pb, sb, bi, la, ce, pr, nd, sm, eu, gd, tb, dy, ho, er, tm, yb, lu.
(2) Directly calcining the mixture; the calcination temperature is 400-1100 ℃, and the calcination time is 10-240 min.
The process of forming the two-dimensional metal oxide nanoplatelets of the present invention undergoes the following three steps. First, the ammonium ion and glucose undergo a maillard reaction to form a viscous melanoidin polymer having sufficient oxygen-containing functional groups, such as carboxyl, hydroxyl and epoxy groups, to ensure adsorption of a wide variety of metal ions. Secondly, the viscous melanoidin polymer and nitrate ions undergo a severe oxidation-reduction reaction, and the inside of the polymer rapidly expands to form large-size carbon nano sheets. At the same time, the metal ions are oxidized to metal oxide particles embedded on the carbon nanoplatelets. Finally, in the subsequent calcination process, the oxide nano-particles take the large-size carbon nano-sheets as templates, and the metal oxide porous nano-sheets are formed by sintering, and the carbon nano-sheets are completely decomposed.
The method for mass-producing two-dimensional metal oxide nanoplatelets provided by the present invention is described below with reference to specific examples. FIG. 1 is a schematic illustration of a method of mass-producing two-dimensional metal oxide nanoplatelets according to the present invention.
Example 1
(1) 0.5g of ammonium nitrate and 0.4g of glucose and 0.015g of erbium chloride were sufficiently ground in a mortar, after which the ground paste was put into a crucible.
(2) The crucible was placed in a muffle furnace. The muffle furnace was heated to 900 ℃ at a rate of 10 ℃/min and held at 900 ℃ for 10 minutes. When the furnace temperature is reduced to room temperature, the crucible is taken out to obtain two-dimensional Er 2 O 3 Porous nanoplatelets.
Two-dimensional Er prepared in example 1 2 O 3 SEM pictures of nanoplatelets are shown in FIG. 2, from which it can be seen that Er is produced 2 O 3 Is a large-sized nano-sheet.
As shown in FIG. 3, a two-dimensional Er was obtained in example 1 2 O 3 TEM image of the nanoplatelets, from which it can be seen that the two-dimensional Er obtained 2 O 3 The nanometer sheet is composed of nanometer particlesThe granules are assembled.
As shown in FIG. 4, a two-dimensional Er was obtained in example 1 2 O 3 XRD pattern of nanoplatelets. As can be seen by XRD, er 2 O 3 Is pure phase, has no impurity peak and good crystallinity.
Example 2
(1) 0.5g of ammonium nitrate and 0.4g of glucose and 0.02g of erbium acetate pentahydrate were sufficiently ground in a mortar, and then the ground paste was put into a crucible.
(2) The crucible was placed in a muffle furnace. The muffle furnace was heated to 900 ℃ at a rate of 10 ℃/min and held at 900 ℃ for 10 minutes. When the furnace temperature is reduced to room temperature, the crucible is taken out to obtain Er 2 O 3 Two-dimensional porous nanoplatelets.
Two-dimensional Er prepared in example 2 2 O 3 SEM pictures of porous nanoplatelets are shown in FIG. 5, from which it can be seen that Er was prepared 2 O 3 Is a large-sized nano-sheet.
As shown in FIG. 6, a two-dimensional Er was obtained in example 2 2 O 3 TEM image of the nanoplatelets, from which it can be seen that the two-dimensional Er obtained 2 O 3 The porous nanoplatelets are assembled from nanoparticles.
Example 3
(1) 0.5g of ammonium nitrate and 0.4g of glucose and 0.02g of erbium nitrate pentahydrate were sufficiently ground in a mortar, and then the ground paste was put into a crucible.
(2) 0.5g of ammonium nitrate and 0.4g of glucose and 0.1g of erbium nitrate pentahydrate were sufficiently ground in a mortar, and then the ground paste was put into a crucible.
(3) The crucible was placed in a muffle furnace. The muffle furnace was heated to 900 ℃ at a rate of 10 ℃/min and held at 900 ℃ for 10 minutes. When the furnace temperature is reduced to room temperature, the crucible is taken out to obtain Er 2 O 3 A nano-sheet.
Example 3 Er prepared with 0.02g erbium nitrate pentahydrate 2 O 3 The TEM and pore size distribution of the porous nanoplatelets are shown in fig. 7 and 8. Er prepared with 0.1g erbium nitrate pentahydrate 2 O 3 Porous nanoThe TEM and pore size distribution of the rice flakes are shown in fig. 9 and 10. From the figure, it can be seen that Er is prepared 2 O 3 The nanoplatelet pore size decreases with increasing precursor content.
As shown in FIG. 11 and FIG. 12, the Er prepared in example 3 with different contents of metal salts 2 O 3 AFM pictures of porous nanoplates from which it can be seen that Er was produced 2 O 3 The nanoplatelet thickness increases with increasing precursor content.
Example 4
(1) 0.5g of ammonium nitrate, 0.4g of glucose and 0.02g of magnesium nitrate were sufficiently ground in a mortar, and then the ground paste was put into a crucible.
(2) The crucible was placed in a muffle furnace. The muffle furnace was heated to 500℃at a rate of 10℃per minute and held at 500℃for 20 minutes. When the furnace temperature is reduced to room temperature, the crucible is taken out, and the two-dimensional MgO porous nano-sheet is obtained.
As shown in fig. 13, which is a TEM photograph of the two-dimensional MgO nanoplatelets prepared in example 4, it can be seen from the figure that the two-dimensional MgO prepared is a large-sized flexible porous nanoplatelet.
As shown in fig. 14, the XRD pattern of the two-dimensional MgO nanosheets prepared in example 4. As can be seen by XRD, mgO is a pure phase, has no impurity peak, and has good crystallinity.
Example 5
(1) 0.5g of ammonium nitrate and 0.4g of glucose and 0.02g of aluminum nitrate pentahydrate were sufficiently ground in a mortar, and then the ground paste was put into a crucible.
(2) The crucible was placed in a muffle furnace. The muffle furnace was heated to 900 ℃ at a rate of 10 ℃/min and held at 900 ℃ for 10 minutes. When the furnace temperature is reduced to room temperature, the crucible is taken out to obtain two-dimensional Al 2 O 3 Porous nanoplatelets.
As shown in FIG. 15, two-dimensional Al prepared in example 5 2 O 3 TEM image of nanoplatelets, from which it can be seen that two-dimensional Al is produced 2 O 3 Is a large-size flexible porous nano-sheet.
As shown in FIG. 16, the method of example 5Prepared two-dimensional Al 2 O 3 XRD pattern of nanoplatelets. As can be seen by XRD, al 2 O 3 Is pure phase, has no impurity peak and good crystallinity.
Example 6
(1) 0.5g of ammonium nitrate and 0.4g of glucose, as well as 0.021565g of lanthanum nitrate hexahydrate, 0.0215g of manganese nitrate tetrahydrate were sufficiently ground in a mortar, and then the ground paste was put into a crucible.
(2) The crucible was placed in a muffle furnace. The muffle furnace was heated to 700℃ at a rate of 10℃/min and held at 700℃ for 20 minutes. When the furnace temperature is reduced to room temperature, the crucible is taken out to obtain two-dimensional La 0.96 Mn 0.96 O 3 Porous nanoplatelets.
As shown in FIG. 17, two-dimensional La was prepared in example 6 0.96 Mn 0.96 O 3 TEM image of the nanoplatelets, from which it can be seen that two-dimensional La is produced 0.96 Mn 0.96 O 3 Is a large-size flexible porous nano-sheet.
As shown in FIG. 18, two-dimensional La was prepared in example 6 0.96 Mn 0.96 O 3 XRD pattern of nanoplatelets. As can be seen by XRD, la 0.96 Mn 0.96 O 3 Is pure phase, has no impurity peak and good crystallinity.
The embodiment of the method for preparing the two-dimensional metal oxide nano sheets in large scale is simple, low in cost and capable of synthesizing various large-size two-dimensional metal oxide nano sheets in large scale.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.

Claims (7)

1. The preparation method of the two-dimensional non-layered metal oxide porous nano-sheet is characterized by comprising the following steps of:
(1) Uniformly mixing glucose, ammonium nitrate and metal salt in a solid phase, wherein the metal salt is rare earth metal salt, transition metal salt, III main group metal salt or II main group metal salt;
(2) Calcining the mixture obtained in the step (1) in a solid phase to enable ammonium ions and glucose to carry out Maillard reaction to form melanoidin polymer; the melanoidin polymer and nitrate ions undergo oxidation-reduction reaction, so that the melanoidin polymer is internally expanded and converted into carbon nano sheets; meanwhile, the metal ions are oxidized into metal oxide nano particles to be embedded into the carbon nano sheets; finally, the metal oxide nano particles take the carbon nano sheet as a template, the porous metal oxide nano sheet is formed by sintering, and the carbon nano sheet serving as the template is calcined and decomposed.
2. The method for preparing a two-dimensional non-layered metal oxide porous nanosheet of claim 1, wherein the metal salt is at least one of nitrate, chloride and acetate.
3. The method for preparing a two-dimensional non-layered metal oxide porous nanosheet according to claim 1, wherein the metal salt is a single metal salt or a mixed metal salt.
4. The method for preparing the two-dimensional non-layered metal oxide porous nanosheets according to claim 1, wherein the rare earth metal salt is samarium nitrate, erbium nitrate, praseodymium nitrate, gadolinium nitrate, yttrium nitrate, ytterbium nitrate or neodymium nitrate; the transition metal salt is cobalt nitrate, nickel nitrate, chromium nitrate or zirconium nitrate; the III main group metal salt is aluminum nitrate, gallium nitrate or indium nitrate; the metal salt of the main group II is magnesium nitrate, calcium nitrate or strontium nitrate.
5. The method for preparing the two-dimensional non-layered metal oxide porous nanosheets according to claim 1, wherein the mass ratio of glucose to ammonium nitrate is 1 (1-10).
6. The method for preparing the two-dimensional non-layered metal oxide porous nanosheets according to any one of claims 1 to 4, wherein the sum of the mass ratio of the metal salt to the mass of glucose and ammonium nitrate is 1 (1 to 50).
7. The method for preparing the two-dimensional non-layered metal oxide porous nanosheets according to claim 1, wherein the calcination temperature is 400-1100 ℃, and the calcination time is 10-240 min.
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101269973A (en) * 2008-05-08 2008-09-24 清华大学 Method for synthesizing nano-scale oxide ceramic powder body

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101269973A (en) * 2008-05-08 2008-09-24 清华大学 Method for synthesizing nano-scale oxide ceramic powder body

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