CN114351239B - Preparation method of porous metal compound array film - Google Patents
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Abstract
The invention relates to the fields of photoelectric conversion, storage and catalysis, in particular to a preparation method of a porous metal compound array film. Taking a metal matrix or a matrix with a metal coating deposited on the surface as a precursor, suspending the precursor above a mixed solution of water containing ammonium bifluoride and ethylene glycol, sealing the mixed solution in a reaction kettle for hydrothermal treatment, taking out a sample after cooling to room temperature, cleaning with deionized water, and drying to obtain an ammonium-metal oxyfluoride single crystal array film supported by the matrix; or further heat-treating under different atmospheres, and then topologically converting the ammonium-metal oxyfluoride single crystal array film into a porous metal compound array film. The invention realizes the simple preparation of the porous metal compound array film and the effective adjustment of the microscopic morphology thereof, and provides effective materials and method basis for the photoelectric conversion, storage and catalysis fields based on the development of the porous compound functional film.
Description
Technical Field
The invention relates to the fields of photoelectric conversion, storage and catalysis, in particular to a preparation method of a porous metal compound array film.
Background
The porous material has rich pores and large specific surface area, and has important application prospects in the fields of catalysis, separation, energy conversion, storage and the like. The porous monocrystal-like structure has longer charge diffusion length due to grain oriented stacking, and has greater application potential in (photo) electrocatalytic and storage field production. Taking titanium dioxide as an example, the titanium dioxide as a photocatalytic material has the advantages of high efficiency, stability, low cost, good biocompatibility and the like, and is a material with great competition among a plurality of photocatalytic materials. The porous structure TiO 2 electrode can effectively reduce reflection and transmission of incident light, obviously improve light absorption efficiency, and meanwhile, the porous structure also obviously shortens the distance of charge phase transport, so that the porous structure TiO 2 electrode has wide application in electrode materials of photoelectrochemistry water decomposition hydrogen production, dye sensitized solar cells and sensors and has good commercial value. In the energy storage field, the mesoporous TiO 2 nano-sheet is a bracket, so that an open channel and more contact area can be provided for the transportation of lithium ions and electrons, and the lithium storage performance is more excellent. In the field of catalysis, the mesoporous structure has rich surface active sites, and can effectively improve the catalytic reaction activity of various metal oxides (MoO 3、WO3、TiO2、Co3O4 and the like).
However, the existing preparation process of the porous monocrystalline-like compound is complex, the yield is low, a simple and effective method for preparing the porous metal compound in batches is lacked, and meanwhile, the preparation of the prepared porous monocrystalline-like metal compound is mostly powder, so that the recycling of materials is not facilitated. The former greatly increases the preparation cost of the porous monocrystalline-like compound, including time cost, capital cost, etc., which is unfavorable for commercial application, while the latter causes secondary pollution to the environment and limits the application field of the porous monocrystalline-like compound. There are few researches and applications on porous monocrystalline-like films at present, and there is a lack of a low-cost and simple way to prepare porous monocrystalline-like metal compound array films.
Disclosure of Invention
The invention aims to provide a preparation method of a porous metal compound array film, which realizes simple preparation and effective regulation of microscopic morphology of the porous metal compound array film and provides a realistic material and a method foundation for developing a film electrode for photoelectric conversion and storage devices based on the porous metal compound array film.
The technical scheme of the invention is as follows:
A preparation method of a porous metal compound array film comprises the steps of taking a metal substrate or a substrate with a metal coating deposited on the surface as a precursor, suspending the substrate above a mixed solution of water containing ammonium bifluoride and ethylene glycol, sealing the substrate in a reaction kettle for hydrothermal treatment, taking out a sample after cooling to room temperature, cleaning with deionized water, and drying to obtain an ammonium-metal oxyfluoride single crystal array film supported by the substrate; further after heat treatment under different atmospheres, the ammonium-metal oxyfluoride single crystal array film topology is converted into a porous metal compound array film.
The precursor is a metal matrix with various forms and a matrix with various surface deposited metal coatings.
In the preparation method of the porous metal compound array film, the mass ratio of water to glycol in the mixed solution of water containing ammonium bifluoride and glycol is 0-0.5, and the molar concentration of ammonium bifluoride is 0.01-1M.
The preparation method of the porous metal compound array film comprises the steps of carrying out hydrothermal treatment at the temperature of 80-220 ℃ for 0.5-24 hours.
According to the preparation method of the porous metal compound array film, when heat treatment is carried out under different atmospheres, the heat treatment atmosphere comprises one or more than two mixed gases selected from air, oxygen, nitrogen, argon, ammonia, helium, hydrogen sulfide, borane, methane, acetylene, carbon monoxide, carbon dioxide and sulfur dioxide.
The preparation method of the porous metal compound array film has the heat treatment temperature of 150-1200 ℃ and the heat treatment time of 0.1-24 h.
The preparation method of the porous metal compound array film comprises the steps of preparing a porous metal compound array film, wherein the microcosmic appearance of the porous metal compound comprises a sheet shape, a cone shape, a strip shape, a column shape or a block shape.
The preparation method of the porous metal compound array film comprises the following technical parameters: the thickness is 0.2-40 mu m, the porosity is 5-65%, and the average pore diameter is 1 nm-200 nm.
The design idea of the invention is as follows:
The current mode for obtaining the porous metal compound is mainly a template method, the preparation process is complex, the application cost is greatly increased, and meanwhile, the problems of effective removal of the template, low yield and the like exist. The template-free method represented by in-situ topological phase transformation can effectively avoid the problems, and is an ideal mode for preparing the porous metal compound. The porous metal compound is directly constructed on a metal matrix (or a matrix with a metal coating deposited on the surface) in situ through a topological transformation process, and has great application value and significance in the field of (photo) electro-catalysis and storage. Meanwhile, the porous structure is beneficial to doping of heterogeneous elements, so that the electronic structure of the transition metal compound is modulated, and the change of the electronic structure has important significance in the fields of (photo) electro-catalysis and storage, and can optimize the overpotential of the electrode catalytic reaction and the selectivity of a catalytic product, improve the conductivity of the electrode, introduce pseudocapacitance and the like. The invention considers the preparation of the porous metal compound array film and the doping regulation and control of the hetero atoms together, and develops a preparation method of the porous metal compound array film by the cooperation of topology transformation and doping modification.
The gas-phase hydrothermal method is a novel method for preparing the corresponding metal compound film nanostructure on a metal matrix, but the traditional gas-phase hydrothermal method has the problems that the saturated vapor pressure is large, meanwhile, the ionization constant of water increases along with the rising of the hydrothermal reaction temperature, the reaction degree is increased, the reaction rate of gasified reactants and the metal matrix is too high, and meanwhile, the hydroxyl groups on the metal surface are mutually dehydrated to form bridging oxygen bonds due to the gas-phase hydrothermal method, so that an oxide film is easy to prepare, and the preparation of a multi-element metal oxide film substance is difficult to realize. The vapor phase solvothermal method is constructed by using high-boiling point organic solvents such as ethylene glycol, so that the saturated vapor pressure of the reaction can be effectively reduced, the etching rate of reactants to a substrate is effectively reduced, and a small amount of water is introduced in the invention to dissolve ammonium bifluoride and provide an oxygen source for ammonium-metal oxyfluoride. Therefore, compared with a gas-phase hydrothermal mode, the gas-phase solvent can weaken the mutual dehydration of hydroxyl groups on the surface of a product to form bridging oxygen bonds and reduce the reaction rate, so that the reaction of ammonium bifluoride, water and a metal substrate can be effectively realized. Thus, an ammonium-metal oxyfluoride single crystal array film can be obtained.
The invention has the advantages and beneficial effects that:
1. The invention realizes the simple and controllable preparation of the porous metal compound array film by a simple template-free method and simple heat treatment and by utilizing the topological transformation process, and provides a realistic material and a method foundation for developing the high-efficiency film electrode for the photoelectric conversion and storage device based on the porous metal compound array film;
2. The invention adopts an environment-friendly synthesis method with simple steps, which is beneficial to large-scale production;
3. The precursor adopted by the invention is a metal substrate or a substrate with a metal coating deposited on the surface, so that the method has rich resources and is easy to store, prepare and use;
4. The invention relates to a universal preparation method of a porous metal compound array film, which is not aimed at a certain substance;
5. the matrix supported porous metal compound array film prepared by the invention has high porosity and can be applied to the fields of batteries, capacitors, (photo) electro-catalysis and the like.
Drawings
FIG. 1 XRD pattern of bulk NH 4TiOF3 single crystal array film supported on metallic titanium substrate, with the abscissa being diffraction angle 2 theta (diffraction) and the ordinate being diffraction peak intensity (a.u.).
FIG. 2A Scanning Electron Microscope (SEM) photograph of the obtained bulk NH 4TiOF3 single crystal array supported by the metallic titanium substrate.
FIG. 3 XRD patterns of the resulting porous titanium dioxide (TiO 2) array films supported on a metallic titanium substrate, with the abscissa representing the diffraction angle 2 theta (depth) and the ordinate representing the diffraction peak intensity (a.u.).
FIG. 4 is a Scanning Electron Microscope (SEM) photograph of the obtained metallic titanium matrix supported massive porous titanium dioxide (TiO 2) array film.
FIG. 5 ultraviolet-visible absorption spectra of the resulting metallic titanium matrix supported bulk porous titanium dioxide (TiO 2) array film, with the abscissa representing wavelength (nm) and the ordinate representing absorbance (a.u.).
FIG. 6A Scanning Electron Microscope (SEM) photograph of a sheet-like porous titanium dioxide (TiO 2) array film supported by the resulting metallic titanium substrate.
FIG. 7 shows the XRD pattern of the resulting tantalum metal matrix supported cone (NH 4)2Ta2O3F6 single crystal array film) with the diffraction angle 2 theta (diffraction) on the abscissa and the diffraction peak intensity (a.u.).
Fig. 8. Cone (NH 4)2Ta2O3F6 single crystal array thin film Scanning Electron Microscope (SEM) photograph of the resulting tantalum metal matrix support.
FIG. 9. UV-visible absorption spectra of the resulting tantalum metal matrix supported cone (NH 4)2Ta2O3F6 array film), with the abscissa representing wavelength (nm) and the ordinate representing absorbance (a.u.).
FIG. 10 shows XRD patterns of a conical porous tantalum nitride (Ta 3N5) single crystal array film supported by a metal tantalum substrate, wherein the abscissa is diffraction angle 2 theta (depth) and the ordinate is diffraction peak intensity (a.u.).
FIG. 11 is a thin film Scanning Electron Microscope (SEM) photograph of a conical porous tantalum nitride (Ta 3N5) single crystal array supported by the resulting metal tantalum matrix.
FIG. 12 ultraviolet-visible absorption spectra of the resulting metallic tantalum matrix supported, tapered porous tantalum nitride (Ta 3N5) array films, with the abscissa representing wavelength (nm) and the ordinate representing absorbance (a.u.).
FIG. 13 shows XRD patterns of a flaky NH 4WOF3 single crystal array supported by a tungsten wire mesh substrate, wherein the abscissa is diffraction angle 2 theta (devire) and the ordinate is diffraction peak intensity (a.u.).
Fig. 14. A thin film Scanning Electron Microscope (SEM) photograph of a sheet NH 4WOF3 single crystal array supported by the resulting tungsten wire mesh substrate.
FIG. 15 XRD pattern of a single crystal array of bulk porous tungsten oxide (WO 3) supported on a tungsten wire mesh substrate, with the diffraction angle 2. Theta. (depth) on the abscissa and the diffraction peak intensity (a.u.) on the ordinate.
FIG. 16A Scanning Electron Microscope (SEM) photograph of a bulk porous tungsten oxide (WO 3) single crystal array supported by a tungsten wire mesh substrate.
Detailed Description
In the specific implementation process, the invention provides a preparation method of a porous metal compound array film, which takes a metal matrix (or a matrix with a metal coating deposited on the surface) as a precursor, and the precursor is suspended above a mixed solution of water containing ammonium bifluoride and ethylene glycol, sealed in a reaction kettle for hydrothermal treatment, after the hydrothermal treatment is carried out for a period of time, a sample is taken out after the sample is cooled to room temperature, a large amount of deionized water is used for cleaning and drying, thus obtaining the ammonium-metal oxyfluoride single crystal array film supported by the matrix, and after further heat treatment under air and other atmospheres (such as Ar, H 2,H2S,NH3 and the like), the ammonium-metal oxyfluoride single crystal array film is topologically converted into the porous metal compound array film. Wherein, the concrete characteristic lies in:
1. The precursor is a metal matrix with various forms and a matrix with various surface deposited metal coatings;
2. in the water and glycol mixed solution, the mass ratio of water to glycol is 0-0.5, and the preferred mass ratio is 0-0.15;
3. the molar concentration of the ammonium bifluoride is 0.01-1M, preferably 0.01-0.1M;
4. The temperature of the hydrothermal treatment is 80-220 ℃, preferably 120-160 ℃, and the time of the hydrothermal treatment is 0.5-24 h, preferably 3-12 h;
5. the heat treatment is heat treatment under different atmospheres, wherein the treatment atmosphere comprises one or more than two mixed gases selected from air, oxygen, nitrogen, argon, ammonia, helium, hydrogen sulfide, borane, methane, acetylene, carbon monoxide, carbon dioxide and sulfur dioxide gas, and preferably air, oxygen, nitrogen, argon, ammonia and hydrogen;
6. The heat treatment temperature is 150-1200 ℃, preferably 300-700 ℃, and the treatment time is 0.1-180 h, preferably 0.2-2 h;
7. The microcosmic appearance of the porous metal compound comprises a sheet shape, a rod shape, a strip shape, a column shape, a block shape and the like.
The present invention will be described in further detail with reference to examples and drawings.
Example 1
Using commercial metallic titanium as a substrate, firstly 10mL of Ethylene Glycol (EG) and 1mL of water were measured, then 25mg of ammonium bifluoride (chemical formula NH 4HF2) was weighed, stirred for a period of time, the solution was transferred to a 100mL stainless steel reaction vessel lined with polytetrafluoroethylene, a sample holder was placed, and the metallic titanium substrate was placed on the sample holder. After the reaction kettle is sealed, carrying out hydrothermal treatment for 7 hours at 150 ℃, taking out a reaction sample, cleaning with deionized water and drying with nitrogen to obtain a blocky NH 4TiOF3 single crystal array film supported by a metallic titanium substrate (as shown in figures 1 and 2). After 1h of treatment in an air atmosphere at 450 ℃, a porous metal compound array film supported on a metal titanium substrate is obtained (see fig. 3 and 4). As shown in fig. 5, the bulk NH 4TiOF3 single crystal array film and the bulk porous titania (TiO 2) array film supported by the metallic titanium substrate have uv-vis absorption spectra.
In this embodiment, the technical parameters of the porous metal compound array film are as follows: the thickness is 2-10 mu m, the porosity is 5-65%, and the average pore diameter is 1-100 nm.
Example 2
The commercial metallic titanium is used as a substrate, firstly 10mL EG and 1mL water are measured, then 25mg ammonium bifluoride (with a chemical formula of NH 4HF2) is weighed, after stirring for a period of time, the solution is transferred into a 100mL stainless steel reaction kettle with polytetrafluoroethylene as a lining, a sample holder is placed, and then the metallic titanium substrate is placed on the sample holder. And after the reaction kettle is sealed, carrying out hydrothermal treatment for 7 hours at 140 ℃, taking out a reaction sample, cleaning with deionized water, and drying with nitrogen to obtain the sheet-shaped NH 4TiOF3 single crystal array film supported by the metallic titanium substrate. After 1h of treatment in an air atmosphere at 450 ℃, a flaky porous titanium dioxide (TiO 2) array film supported on a metallic titanium substrate is obtained (as shown in figure 6).
In this embodiment, the technical parameters of the porous metal compound array film are as follows: the thickness is 10-40 μm, the porosity is 5-65%, and the average pore diameter is 1-50 nm.
Example 3
Using commercial tantalum metal as a substrate, firstly weighing 10mL EG and 1mL water, then weighing 50mg ammonium bifluoride (chemical formula is NH 4HF2), stirring for a period of time, transferring the solution into a 100mL stainless steel reaction kettle with polytetrafluoroethylene lining, placing a sample holder, and placing the tantalum metal substrate on the sample holder. After the reaction kettle is sealed, carrying out hydrothermal treatment for 7h at 140 ℃, taking out a reaction sample, cleaning with deionized water and drying with nitrogen to obtain a conical (NH 4)2Ta2O3F6 single crystal array film supported by a metal tantalum substrate (as shown in figures 7 and 8), and carrying out ammonia atmosphere treatment for 6h at 1050 ℃ to obtain a conical porous tantalum nitride (Ta 3N5) array film supported by the metal tantalum substrate (as shown in figures 10 and 11), wherein the conical (NH 4)2Ta2O3F6 single crystal array film supported by the metal tantalum substrate has an ultraviolet-visible absorption spectrum, and the conical porous tantalum nitride (Ta 3N5) single crystal array film supported by the metal titanium substrate has an ultraviolet-visible absorption spectrum, as shown in figure 9.
In this embodiment, the technical parameters of the porous metal compound array film are as follows: the thickness is 0.2-15 mu m, the porosity is 5-65%, and the average pore diameter is 1 nm-200 nm.
Example 4
Using commercial tungsten wire mesh as matrix, firstly weighing 10ml EG and 1ml water, then weighing 300mg ammonium bifluoride (chemical formula is NH 4HF2), stirring for a period of time, transferring the solution into a 100 mL stainless steel reaction kettle with polytetrafluoroethylene as lining, placing a sample holder, and placing the tungsten wire mesh matrix on the sample holder. After the reaction kettle is sealed, carrying out hydrothermal treatment for 7 hours at 140 ℃, taking out a reaction sample, cleaning with deionized water and drying with nitrogen to obtain a flaky NH 4WOF3 single crystal array film supported by a tungsten wire mesh substrate (as shown in figures 13 and 14). After 2 hours of treatment in an air atmosphere at 500 ℃, a bulk porous tungsten oxide (WO 3) array film supported on a tungsten wire mesh substrate was obtained (see fig. 15 and 16).
In this embodiment, the technical parameters of the porous metal compound array film are as follows: the thickness is 0.2-2 mu m, the porosity is 5-65%, and the average pore diameter is 1-100 nm.
The results of the examples show that the ammonium-metal oxyfluoride single crystal array film supported by the substrate can be obtained by taking a metal substrate (or a substrate with a metal coating deposited on the surface) as a precursor, suspending the precursor above a mixed solution of water containing ammonium bifluoride and ethylene glycol, sealing the mixed solution in a reaction kettle and performing hydrothermal treatment; further after heat treatment under different atmospheres, the ammonium-metal oxyfluoride single crystal array film topology is converted into a porous metal compound array film.
Claims (8)
1. A preparation method of a porous metal compound array film is characterized in that a metal matrix or a matrix with a metal coating deposited on the surface is taken as a precursor, the precursor is suspended above water containing ammonium bifluoride and glycol mixed solution, the solution is sealed in a reaction kettle for hydrothermal treatment, a sample is taken out after the solution is cooled to room temperature, deionized water is used for cleaning and drying, and the ammonium-metal oxyfluoride single crystal array film supported by the matrix is obtained; further performing heat treatment under different atmospheres, and topologically converting the ammonium-metal oxyfluoride single crystal array film into a porous metal compound array film; wherein the metal compound is TiO 2、WO3 or Ta 3N5.
2. The method for preparing a porous metal compound array film according to claim 1, wherein the precursor is a metal substrate of various forms and a substrate with various surface deposited metal coatings.
3. The method for producing a porous metal compound array film according to claim 1, wherein the mass ratio of water to ethylene glycol in the mixed solution of water containing ammonium bifluoride is 0 to 0.5 and the molar concentration of ammonium bifluoride is 0.01 to 1m.
4. The method for preparing a porous metal compound array film according to claim 1, wherein the hydrothermal treatment temperature is 80-220 ℃ and the hydrothermal treatment time is 0.5-24 hours.
5. The method for producing a porous metal compound array film according to claim 1, wherein the heat treatment atmosphere comprises one or a mixture of two or more gases selected from the group consisting of air, oxygen, nitrogen and argon when heat-treated in different atmospheres.
6. The method for producing a porous metal compound array film according to claim 1 or 5, wherein the heat treatment temperature is 150 to 1200 ℃ and the heat treatment time is 0.1 to 24 hours.
7. The method for preparing a porous metal compound array film according to claim 1, wherein the microscopic morphology of the porous metal compound comprises a plate shape, a cone shape, a ribbon shape, a column shape or a block shape.
8. The method for producing a porous metal compound array film according to claim 1, wherein the porous metal compound array film has the following technical parameters: the thickness is 0.2-40 μm, the porosity is 5-65%, and the average pore diameter is 1-200 nm.
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