TWI748799B - Metallic material and method for manufacturing the same - Google Patents

Abstract

The present invention relates to metallic material and a method for manufacturing the same. The method for manufacturing the metallic material electrodeposits metallic ions within nanopores of a porous template by using pusle current to enhance an electrochemical activity of the metallic material manufactured by the method, thereby increasing an applicability of the metallic material.

Description

Metal material and its manufacturing method

The present invention relates to a metal material and a manufacturing method thereof, and particularly relates to a metal material with high electrochemical activity and a manufacturing method thereof.

Metal-organic framework (MOF) and covalent-organic framework (COF) have high specific surface area, regular porosity and adjustable structure. Furthermore, after the MOF and COF films are formed on the surface of the conductive substrate, active sites can be constructed in them. Therefore, materials based on MOF and COF films have great potential for electrochemical applications (such as electrocatalysis and charge storage). Recently, the use of MOF and COF films to develop electrochemically active materials has gradually attracted attention, especially metal materials.

At present, spray coating (spray coating) a MOF film on the surface of a conductive substrate, and then electro-depositing cobalt oxide by a constant potential method. Although cobalt oxide can be electrically connected to the conductive substrate, it cannot enter the nanopores of the MOF film. It can only be electrodeposited on the surface of the MOF and its periphery, so it cannot effectively improve its specific surface area and electrochemical activity.

Another method of using MOF to electrodeposit metal is to deposit the metal on the MOF film in a potentiostatic or potentiodynamic method, and then repeatedly wash the electrodeposited with deionized water, hydrochloric acid and hydrogen peroxide solution. Metal to make powdered metal materials. When the powdered metal material is applied in the electrochemical field, it is necessary to coat the powdered metal material on the conductive substrate by spray coating or drop-casting. This will result in a larger gap between the powdered metal material and the conductive substrate, which will increase the electrical resistance. Furthermore, since the powdery metal material is connected to the conductive substrate, the specific surface area of the powdery metal material is reduced, and the activity of the powdery metal material is greatly reduced.

In view of this, it is urgent to develop a new manufacturing method of metal materials to improve the above-mentioned shortcomings of conventional metal materials and manufacturing methods.

In view of the above-mentioned problems, one aspect of the present invention is to provide a method for manufacturing a metal material. This manufacturing method uses pulsed current to electrodeposit metal ions in the nanopores of the hole template to enhance the electrochemical activity of the prepared metal material, thereby increasing the applicability of the metal material.

Another aspect of the present invention is to provide a metal material. This metal material is produced by the aforementioned manufacturing method of metal material.

According to one aspect of the present invention, a method for manufacturing a metal material is provided. The manufacturing method of this metal material includes providing a template substrate including a conductive substrate and a hole template, placing the template substrate in an electrolyte, and electrodepositing a metal precursor in the plurality of nano-holes and conductive substrates of the hole template. On the surface of the material to obtain the metal material, the electrodeposition is carried out by applying a pulse current to the template substrate. The hole template is arranged on the conductive substrate, and the electrolyte contains a metal precursor, and the metal precursor corresponds to the metal material.

According to an embodiment of the present invention, the pore diameter of these nano-holes is 1 nm to 5 nm.

According to another embodiment of the present invention, the hole template includes an electrically insulating organic framework.

According to another embodiment of the present invention, the pause time of the pulse current is 0.1 to 10 seconds.

According to another embodiment of the present invention, the pulse current application time is 0.1 to 10 seconds.

According to another embodiment of the present invention, the concentration of the metal precursor in the electrolyte is not less than 0.01M.

According to another embodiment of the present invention, the hydration size of the metal precursor is not greater than 0.5 nm.

According to another embodiment of the present invention, before providing the template substrate, the manufacturing method of the metal material optionally includes forming a hole template on the conductive substrate by a solvothermal method.

Another aspect of the present invention is to provide a metal material. This metal material is produced by the aforementioned metal material manufacturing method.

According to an embodiment of the present invention, the active metal ratio of the metal material is not less than 15%.

The method for manufacturing the metal material of the present invention uses pulsed current to electrodeposit metal ions in the nanopores in the hole template to enhance the electrochemical activity of the metal material, thereby increasing the applicability of the metal material.

The manufacture and use of the embodiments of the present invention are discussed in detail below. However, it can be understood that the embodiments provide many applicable inventive concepts, which can be implemented in various specific contents. The specific embodiments discussed are for illustration only, and are not intended to limit the scope of the present invention.

The "metallic material" referred to herein in the present invention refers to the metallic material confined to the nanopores to increase the activity of the metallic material. Secondly, the manufacturing method of the metal material of the present invention uses the hole template formed on the conductive substrate as the template substrate to start electrodeposition from the bottom of the hole template (that is, the interface between the template and the conductive substrate), and Electrodeposition is not started from the surface of the hole template, where the template substrate contains an electrically insulating organic framework.

Furthermore, this manufacturing method uses pulse electrodeposition to avoid insufficient or excessively high concentrations of metal precursors in the nanopores. Therefore, the manufacturing method of the present invention can prepare the metal material confined in the nanopore to enhance its electrochemical activity, thereby increasing its applicability.

Please refer to FIG. 1, the method 100 for manufacturing a metal material first provides a template substrate, as shown in operation 110. The template substrate includes a conductive substrate and a hole template, and the hole template is disposed on the conductive substrate. The conductive substrate is not particularly limited, and may be a conductive material known to those with ordinary knowledge in the technical field of the present invention, such as an FTO substrate or a metal substrate.

In some embodiments, the hole template may include an electrically insulating organic framework. In some specific examples, the electrically insulating organic framework may include a metal organic framework or a covalent organic framework. For example, the metal organic framework may include, but is not limited to, MOF-808, MOF-802, MOF-841, MOF-804, MOF-805, MOF-806, MOF-177, HKUST-1, UiO-66, UiO- 67, PCN-222, MIL-101 and MOF-525. In addition, the covalent organic framework may include, but is not limited to, COF-1, COF-5, COF-6, COF-102, COF-105, COF-108, and MF-8.

In some embodiments, the hole template has a plurality of nano-holes, and the pore diameter of these nano-holes is 1 nm to 5 nm. When the pore diameter of the nanopore is within the aforementioned range, the electrochemical activity of the metal material produced can be improved. Preferably, the pore diameter of the nano-holes is 1 nm to 3 nm.

In some embodiments, before providing the template substrate, the manufacturing method 100 of the metal material may optionally include a forming step. This forming step is to form a hole template on the conductive substrate. In some specific examples, the forming step can be accomplished using a solvothermal method.

It is said that the conventional technology uses electrospraying or coating to form a template on the conductive substrate, which is easy to cause a gap between the conductive substrate and the template. Therefore, the metal material is directly deposited on the conductive substrate and this gap. The probability that it cannot be deposited in the nano-holes in the hole template. Therefore, compared with the conventional technology, the metal material manufacturing method 100 uses the solvothermal method to directly grow the hole template from the surface of the conductive substrate. Therefore, there is no gap between the hole template and the conductive substrate of the present invention, so the metal material can be electrically charged. Deposited in the nanoholes of the hole template.

Please refer to FIG. 1 again. After the aforementioned operation 110, the template substrate is placed in the electrolyte, as shown in operation 120. The electrolyte contains a metal precursor, and the metal precursor is a metal ion corresponding to the metal material. When the metal precursor is not a metal ion corresponding to the metal material, the metal produced by electrodeposition will be different from the metal material, and the expected metal material cannot be obtained.

In some embodiments, the electrolyte may include inorganic acid ions, metal precursors, and other ions that can form complexes with the metal precursors. For example, the inorganic acid ion may include, but is not limited to, sulfate ion, sulfite ion, nitrate ion, carbonate ion, and phosphate ion. Other ions may include, but are not limited to, halogen ions, tetrafluoroboric acid, hexafluorophosphoric acid, bis(trifluoromethanesulfonyl)imide, and tris. The aforementioned inorganic acid ions and other ions are not specifically limited, but the main purpose is not to affect the stability of the template substrate.

In addition, the metal precursor contains metal ions that can be reduced to metal materials. In some embodiments, the metal precursor may include transition metal ions, preferably transition metal ions in the first column of the periodic table, and more preferably cobalt (II and III) ions and nickel (II and III) ions.

In some specific examples, the concentration of the metal precursor is not less than 0.01M. When the concentration of the metal precursor is in the aforementioned range, during the electrodeposition process, the metal precursor can diffuse into the nanopores of the hole template through the concentration difference to supplement the metal precursor consumed by the previous electrodeposition. It can maintain the progress of electrodeposition in nanopores. Preferably, the concentration of the metal precursor can be 0.01M to 0.05M.

The hydration size of the metal precursor referred to in the present invention refers to the size of the hydrate formed when the metal precursor is dissolved in water and surrounded by water molecules. In some specific examples, the hydration size of the metal precursor is not greater than 0.5 nm. When the hydration size of the metal precursor is within the aforementioned range, the metal precursor can enter the nanoholes in the hole template to be reduced to metal atoms and be electrodeposited in the nanoholes. Preferably, the hydration size of the metal precursor can be 0.2 nm to 1.0 nm.

After the aforementioned operation 120, metal ions are electrodeposited in the plurality of nano-holes in the hole template and on the surface of the conductive substrate to obtain a metal material, as shown in operation 130. The aforementioned electrodeposition is accomplished by applying pulsed current to the template substrate. When the template substrate includes a hole template, the metal material is electrodeposited from the bottom of the hole template from bottom to top to confine the deposition in the nano-holes of the hole template, and the non-electrodeposited metal material is deposited on the outer surface of the hole template. In addition, when the electrodeposition is not completed using pulsed current, the metal material is easy to be electrodeposited on the surface of the hole template instead of in the nano-hole, thus reducing the electrochemical activity of the metal material.

The pulse current system applies current for a period of time (called the application time), then stops applying the current, and then continues for another time (called the pause time). During the application time, the metal precursor in the nano-hole is electrodeposited, and during the pause time, the metal precursor outside the nano-hole diffuses into the nano-hole by the concentration difference to supplement the metal consumed by the electrodeposition. The precursor is prepared for the next electrodeposition.

In some embodiments, the pause time of the pulse current is 0.1 to 10 seconds. When the pause time of the pulse current is in the aforementioned range, the metal precursor can diffuse into the nanopores through the concentration difference when the current is temporarily applied to supplement the metal precursor consumed by the previous electrodeposition, so it can be maintained Electrodeposition in nanopores. Preferably, the pause time of the pulse current can be 5 seconds to 10 seconds.

In some specific examples, when the pore size of the nano-hole of the hole template is 1 nm to 5 nm, the pause time of the pulse current is 0.1 second to 10 seconds. Preferably, the larger the diameter of the nanohole, the shorter the pause time, and the smaller the diameter of the nanohole, the longer the pause time. Since the larger the diameter of the nanopore, the faster the diffusion rate of the metal precursor, so the pause time can be shorter.

In some embodiments, the pulse current application time is 0.1 to 10 seconds. When the application time of the pulse current is in the aforementioned range, an appropriate amount of electricity is provided so that the metal precursor in the electrolyte is electrodeposited into a metal material, and the concentration of the metal precursor in the nanopore is reduced, so when the pulse current is temporarily applied At the time, the metal precursor can be filled into the nano-hole. Preferably, the pulse current application time is 5 seconds to 10 seconds.

In some embodiments, the number of cycles of the pulse current is 100 to 400 times, preferably 200 times. The sum of the pause time of the aforementioned pulse current and the adjacent application time is the time of one cycle, and the combination of the corresponding pause current operation and the current application operation is the current operation of one cycle. When the number of cycles is 100 to 400, the total amount of electricity provided is sufficient to form an appropriate amount of metal material (that is, an appropriate amount of load) by electrodeposition, thereby facilitating the electrodeposition of the metal material in the nanopore.

Another object of the present invention is to provide a metal material. This metal material is produced by the aforementioned metal material manufacturing method. The metal material is deposited on the surface of the conductive substrate and in the nanoholes in the hole template, and has good electrochemical activity. Therefore, the metal material does not need to be removed from the hole template, but can be directly applied to the field of electrochemical detection and catalysis.

However, traditionally, the metal material electrodeposited on the MOF film (as a template) needs to be removed from the MOF film due to insufficient electrochemical activity and cannot be used directly, and the metal material after the removal is in powder form. Therefore, the powdered metal material needs to be coated on the conductive substrate before it can be used as an electrode. Therefore, during the coating process, adhesion problems between the powdered metal material and the conductive substrate may occur, or the powdered metal material will decrease its specific surface area and reduce its electrochemical activity after being spread on the conductive substrate. Therefore, compared with the traditional powdered metal material and its manufacturing method, the manufacturing method of the metal material of the present invention is simpler (reduction steps are reduced), and the prepared metal material can be used directly, so the metal material can be improved The applicability.

It is said that metal materials can be used in fields related to electrochemical activity. In some embodiments, metal materials can be applied to electrochemical detection elements, such as electrodes or probes. In other embodiments, metal materials can be applied to electrochemical catalytic reactions, such as catalysts. In some specific examples, metal materials can be used as electrodes to detect oxides in water.

As mentioned above, the hole template may include an electrically insulating organic framework. When the hole template uses an electrically insulating organic framework, the organic framework is quite stable in acidic and neutral environments, and can maintain structural integrity during the electrochemical reaction process, and can prevent the electrochemical induction of metal materials in the process Aggregate, thereby enhancing the direct applicability of metal materials.

In some embodiments, the loading amount of the metal material per unit area in the hole template is not less than 5×10 ^-9 mol/cm ² . When the loading amount per unit area of the metal material in the hole template is in the aforementioned range, the metal material is electrodeposited in the nano-holes in the hole template, and has a larger specific surface area than the metal film deposited on the plane. Has better electrochemical activity. Preferably, the aforementioned loading amount is not less than 1×10 ^-8 mol/cm ² .

In some embodiments, the active metal fraction of the metal material is not less than 15%. When the active metal ratio of the metal material is in the aforementioned range, the electrochemical activity of the prepared electrode can be improved. Preferably, the aforementioned active metal ratio is not less than 20%.

The following examples are used to illustrate the application of the present invention, but they are not intended to limit the present invention. Anyone who is familiar with the art can make various changes and modifications without departing from the spirit and scope of the present invention.

Preparation of metal organic framework

The metal-organic framework is a metal-organic framework of MOF-808 structure and is prepared by solvothermal method. Wash the FTO substrate (fluorine-doped tin oxide, resistance value 7Ω/sq, and area 3cm×1.25cm) with ultrasonic waves in soapy water and acetone for 10 minutes. After drying the FTO substrate with nitrogen, the FTO substrate was soaked in 10 mL of 0.5 mM trimesic acid (H ₃ BTC) in dimethylformamide (DMF) solution overnight at room temperature. Then, the aforementioned FTO substrate was dried in an oven at 80° C. to obtain the treated FTO substrate.

In addition, add 27.5mg H ₃ BTC, 40mg zirconyl chloride octahydrate, 5mL DMF and 5mL formic acid to a 20mL scintillation vial equipped with a urea cap and Teflon lining , And mixed with ultrasound for 5 minutes to obtain a mixed solution. Then, with the conductive side facing down, immerse the treated FTO substrate in the aforementioned mixed solution. Next, seal the aforementioned screw scintillation counter bottle and place it at the bottom of a gravity convection oven, set the temperature at 80°C, and go through 48 hours. After the metal organic framework (represented by MOF-808 below) is formed on the treated FTO substrate, the metal organic framework film is rinsed three times with DMF to ensure complete solvent exchange. After drying at 80° C. under vacuum, a template substrate (represented by MOF-808/FTO hereinafter) was prepared, and the pore diameter of the metal-organic framework of the nano-pores was 1.8 nm.

Preparation of metal materials and electrodes containing them

Example

The preparation of the metal material in the embodiment uses a three-pole electrochemical system for electrodeposition, with platinum wires as the counter electrode, and Ag/AgCl/NaCl (3M) electrode (brand name: BASi) as the reference electrode. Use polyimide electrical insulating tape to adjust the exposed area of MOF-808/FTO to 1cm ² , and use it as the working electrode. In addition, the cobalt ion (II) of cobalt sulfate is used as the metal precursor (with a hydration size of 0.21 nm), and the electrolyte is 20 mL of a methanol solution of 0.05 M cobalt(II) sulfate heptahydrate.

At room temperature, pulse chronopotential electrodeposition was performed. Pass the working electrode with a cathode current of 0.1 mA/cm ² for 10 seconds, and then pause for 10 seconds. The aforementioned passing and suspending process is regarded as one cycle, and it has gone through 200 cycles in total. The total amount of electricity per unit area passing through the working electrode is 0.2C/cm ² , and the cobalt metal material is electrodeposited in the nano-holes of MOF-808. After the electrodeposition is completed, the working electrode is rinsed with methanol several times, and the working electrode is dried to obtain the cobalt metal material of the embodiment and the electrode containing it (hereinafter referred to as Co@MOF-808/FTO).

Comparative example 1

In Comparative Example 1, the cobalt metal was deposited by the same method as in Example 1, except that the MOF-808 was not grown in Comparative Example 1, and the cobalt metal film was directly electrodeposited on the blank FTO substrate to prepare The FTO substrate (expressed as Co/FTO) with a cobalt metal film is obtained.

Evaluation method

1. Cobalt metal loading per unit area

The cobalt metal loading amount per unit area is the Co@MOF-808/FTO of the example and the Co/FTO of the comparative example 1 whose area has been measured, respectively, and immersed in 2mL of 2M hydrochloric acid aqueous solution overnight to completely dissolve the cobalt in both metallic material. Then respectively add 5 mL of 3wt% nitric acid aqueous solution to the aforementioned solution for dissolving the cobalt metal material to prepare both sample solutions. The inductively coupled plasma atomic emission spectrometer (manufactured by Horiba Scientific, model JY 2000-2) was used to measure the inductively coupled plasma atomic emission spectra of the sample solution to obtain the concentration of cobalt metal in the sample solution. The dilution ratio is converted to the aforementioned area to obtain the amount of cobalt metal electrodeposited in the MOF-808 per unit area, and the result is described in detail later.

2. Measurement of active metal ratio

The measurement of the active metal ratio is based on the Co@MOF-808/FTO of the example. In the 0.05M MOPS buffer (pH=7.3), the potential is switched from +0.8V to 0.0V (relative to Ag/AgCl/NaCl (3M)), measure the current-type Jt curve (current density-time curve), and obtain the integrated power from the current-type Jt curve, and calculate the Co@MOF-808 of the embodiment based on the aforementioned cobalt metal load per unit area /FTO ratio of active metal, the results are detailed later.

3. Measurement of X-ray diffraction spectrum

The X-ray diffraction spectrum is measured by using an X-ray diffractometer (manufactured by Bruker, model D8 Discover) to collect the diffraction spectrum of the MOF-808/FTO and the Co@MOF-808/FTO of the embodiment, and use X-ray powder diffraction spectra (manufactured by Rigaku, model ultima IV) collect the diffraction patterns of powdered MOF-808, and these diffraction patterns are shown in FIG. 2.

4. Scanning electron microscope image and energy dispersive X-ray spectrum analysis

Scanning electron microscope (SEM) images and energy dispersive X-ray spectroscopy (EDS) analysis were performed using a scanning electron microscope (manufactured by Hitachi, model SU-8010) for MOF-808/FTO and Co@ MOF-808/FTO took pictures and collected data, and the results are shown in Figures 3A to 3B and 4A to 4B.

5. Test of electrochemical activity

The electrochemical activity test is carried out using an electrochemical workstation (manufactured by CH Instruments, model CHI6273E), which uses the same three-pole electrochemical system as the electrodeposition, but with FTO, MOF-808/FTO, and comparison The Co/FTO of Example 1 and the Co@MOF-808/FTO of Example were used as working electrodes. The electrolyte is a buffer solution prepared by dissolving 0.1M 3-(N-morpholino) propanesulfonic acid (MOPS) solution and 0.1M sodium hydroxide solution in deionized water (pH=7.3), and add 0mM, 0.2mM or 0.4mMH ₂ O ₂ solution to the electrolyte respectively, and measure the current density of the oxidation and reduction peaks of the aforementioned four electrodes by cyclic voltammetry (CV) , To evaluate its electrochemical activity, the results are shown in Figure 5 and Figures 6A to 6C.

6. Test of current type detection of H ₂ O ₂

The test of amperometric detection of H ₂ O ₂ is to apply +0.8V potential (relative to Ag/AgCl/NaCl(3M)) in 0.05M MOPS buffer (pH=7.3) to detect H ₂ O ₂ concentration. _{Add H 2} O ₂ aqueous solutions of different concentrations from low concentration to high concentration every 100 seconds, and record the response current value to obtain _{the calibration curve of H 2} O ₂ concentration versus current density. The results are detailed in Rear.

First, in terms of the manufacturing method, according to the results of the cobalt metal loading per unit area, the data of Co@MOF-808/FTO in the example is 3.5×10 ^-8 mol/cm ² , which is higher than the Co/ in Comparative Example 1. The FTO data (4.2×10 ^-9 mol/cm ² ) is one level, so MOF-808 as a hole template can increase the loading of cobalt metal materials.

Furthermore, according to the result of the active metal ratio, the active metal ratio of Co@MOF-808/FTO in the embodiment is 21%, so the metal material produced by the pulse current manufacturing method of the embodiment has a high active metal ratio.

In addition, please refer to FIG. 2, which shows the X-ray diffraction spectra of MOF-808/FTO, Co@MOF-808/FTO of the examples, and powdered MOF-808. The diffraction peaks of MOF-808/FTO and Co@MOF-808/FTO of the examples are at 4.4, 8.4, 8.8, 10.0 and 11.0 degrees, and these diffraction peaks are the same as those of powdered MOF-808. It can be seen that MOF-808 was successfully formed on the FTO substrate, and the crystallinity of MOF-808 was still retained after the cobalt metal material was electrodeposited.

Secondly, please refer to FIGS. 3A and 3B, which are respectively the SEM images of MOF-808/FTO and Co@MOF-808/FTO of the embodiment. The Co@MOF-808/FTO of the embodiment still has a morphology similar to the surface of the MOF-808/FTO without electrodeposition, and the outer surface of the MOF-808 is covered by no significant electrodeposited cobalt particles.

Furthermore, please refer to Figures 4A and 4B. These two figures are respectively the cross-section of a MOF-808 crystal in Co@MOF-808/FTO of the embodiment for the EDS line scan position and its mapping image for elemental analysis of zirconium and cobalt. . The distribution of zirconium and cobalt overlap each other at the cross-section of the MOF-808 crystal. Therefore, from the aforementioned X-ray diffraction spectrum, SEM images, and the analysis results of zirconium and cobalt elements, it can be known that the manufacturing method of the embodiment can electrodeposit cobalt metal material in the nano-holes of MOF-808, but not on its outer surface.

Please refer to Figure 5, which shows the measurement of FTO substrate, MOF-808/FTO, Co/FTO of Comparative Example 1 and Co@MOF-808/FTO of Examples in a MOPS buffer solution (pH=7.3) Voltammetry graph. The cyclic voltammetry curves of FTO substrate and MOF-808/FTO show negligible current. The cyclic voltammetry curve of Co/FTO of Comparative Example 1 shows a weak reduction and oxidation peak (which also appears in Figure 6B described later) at about 0.9V. Compared with the Co/FTO of Comparative Example 1, the current density of Co@MOF-808/FTO of the Example is one level higher. Therefore, compared with the flat cobalt metal coating prepared in Comparative Example 1, the cobalt metal material prepared by the porous template (ie, MOF-808) has higher electrochemical activity.

Please refer to Figures 6A to 6C, which respectively show the cyclic voltammetry curves of MOF-808/FTO, Co/FTO of Comparative Example 1, and Co@MOF-808/FTO of Examples for H ₂ O _{2 detection.} In the three figures, the increasing trend of _{H 2} O ₂ concentration is indicated by the direction of the arrow. The cyclic voltammetry curve of MOF-808/FTO shows negligible current. Compared with the Co/FTO of Comparative Example 1, the catalytic current density of Co@MOF-808/FTO of the examples is higher, so the Co@MOF-808/FTO produced by the manufacturing method of the examples is more effective than H ₂ O ₂ It has higher sensitivity and better detection applicability.

In addition, according to the results of the amperometric detection H ₂ O ₂ test, the detection limit (LOD) (based on the signal to noise ratio of 3) of the cobalt metal material prepared by the manufacturing method of the embodiment is 1.3 μM, and the linear range is It is 10 μM to 450 μM, and the sensitivity is 382.27 μA/mMcm ² . Please refer to Table 1. Compared with the materials of the cobalt metal oxide substrate reported in the literature, the Co@MOF-808/FTO of the embodiment has better sensitivity.

Table 1 Material Sensitivity (μA/mMcm ² ) Detection limit (μM) Co@MOF-808/FTO 382.27 1.3 Co ₃ O ₄ nanowire 230.00 1.4 Cobalt oxide with spinel structure 90.54 0.7

In summary, the manufacturing method of the metal material of the present invention is to start the electrodeposition of the metal material from the bottom of the hole template from bottom to top, and the pulse electrodeposition method is used to avoid insufficient or excessive concentration of the metal precursors in the nano-holes. The preparation of metal materials confined to the nanopores, thereby enhancing the electrochemical activity of the prepared metal materials, and increasing the applicability of the metal materials.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention. Anyone with ordinary knowledge in the technical field of the present invention can make various changes and modifications without departing from the spirit and scope of the present invention. Retouching, therefore, the scope of protection of the present invention shall be subject to the scope of the attached patent application.

100: method 110, 120, 130: Operation

In order to have a more complete understanding of the embodiments of the present invention and their advantages, please refer to the following description and the corresponding drawings. It must be emphasized that the various features are not drawn to scale and are for illustration purposes only. The contents of the related drawings are described as follows: FIG. 1 is a flowchart of a method for manufacturing a metal material according to an embodiment of the present invention. Figure 2 shows the X-ray diffraction spectra of MOF-808/FTO, Co@MOF-808/FTO and powdered MOF-808. Figure 3A is an SEM image of MOF-808/FTO. Figure 3B is an SEM image of Co@MOF-808/FTO of the embodiment. 4A is a schematic diagram of the EDS line scan position of a cross section of a MOF-808 crystal of Co@MOF-808/FTO of the embodiment. Fig. 4B is an EDS line scan mapping image of the elemental analysis of zirconium and cobalt shown in Fig. 4A. Figure 5 shows the cyclic voltammetry curves of FTO substrate, MOF-808/FTO, Co/FTO of Comparative Example 1 and Co@MOF-808/FTO of Examples measured in MOPS buffer solution (pH=7.3) picture. Fig. 6A shows the cyclic voltammetry curve of _{H 2} O ₂ detected by MOF-808/FTO. FIG. 6B is a graph showing the cyclic voltammetry curve of _{H 2} O ₂ detected by Co/FTO of Comparative Example 1. FIG. FIG. 6C shows the cyclic voltammetry curve of Co@MOF-808/FTO for detecting H ₂ O _{2 of the embodiment.}

100: method

110, 120, 130: Operation

Claims (8)

A method for manufacturing a metal material includes: providing a template substrate, wherein the template substrate includes a conductive substrate and a hole template, the hole template is disposed on the conductive substrate, and the hole template has a plurality of nanometers Holes; placing the template substrate in an electrolyte, wherein the electrolyte contains a metal precursor, and the metal precursor corresponds to the metal material; electrodepositing the metal precursor in the nanoholes and the On a surface of a conductive substrate to obtain the metal material, wherein the electrodeposition is performed by applying a pulse current to the template substrate. A pause time of the pulse current is 0.1 to 10 seconds, and the pulse current One application time is 0.1 seconds to 10 seconds, and after the metal precursor is electrodeposited, the manufacturing method of the metal material does not remove the hole template. The method for manufacturing a metal material according to claim 1, wherein one of the nano-holes has a diameter of 1 nm to 5 nm. The method for manufacturing a metal material according to claim 1, wherein the hole template includes an electrically insulating organic framework. The method for manufacturing a metal material according to claim 1, wherein a concentration of the metal precursor in the electrolyte is not less than 0.01M. The method for manufacturing a metal material according to claim 1, wherein a hydration size of the metal precursor is not greater than 0.5 nm. The method for manufacturing a metal material according to claim 1, wherein before providing the template substrate, the method for manufacturing the metal material further comprises forming the hole template on the conductive substrate by a solvothermal method. A metal material produced by the method of manufacturing a metal material according to any one of claims 1 to 6. The metal material according to claim 7, wherein the proportion of one active metal of the metal material is not less than 15%.

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