CN115425240A - Preparation method and application of flower-shaped ferroelectric phosphide catalyst - Google Patents
Preparation method and application of flower-shaped ferroelectric phosphide catalyst Download PDFInfo
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- 238000006722 reduction reaction Methods 0.000 claims description 9
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention relates to a preparation method and application of a flower-shaped ferroelectric phosphide catalyst. The preparation method is simple, the cost is low, the efficiency is high, and the prepared flower-shaped iron phosphide catalyst has large specific surface area, so that the contact area between the electrolyte and the material is larger, more active sites participating in catalysis are provided, and the excellent oxygen reduction electrocatalysis characteristic is shown. ORR reaction in 0.1M KOH, initial potential (0.922V vs. RHE), half-wave potential (0.822V vs. RHE), and diffusion limiting current (5.480 mA cm) of commercial Pt/C better than 20% were obtained ‑2 ) And perform inExcellent methanol tolerance and stability.
Description
Technical Field
The invention belongs to the technical field of new energy materials, and particularly relates to a preparation method and application of a flower-shaped ferroelectric phosphide catalyst.
Background
With the rapid development of global economy, traditional fossil fuels such as coal, oil and natural gas are being largely consumed, and the energy crisis is increasingly prominent. Meanwhile, the human life health is seriously threatened by the environmental pollution problem caused by carbon oxides, sulfides, nitrogen oxides and the like generated during the combustion of fossil fuels. Therefore, in order to solve the energy crisis and alleviate the pressure of environmental pollution, it is necessary to develop clean, efficient, and sustainable novel energy. Fuel Cells (Fuel Cells) are a type of power generation device that directly converts chemical energy stored in a Fuel and an oxidant into electrical energy. The fuel cell is suitable for various fuels, is not limited by Carnot cycle, has the advantages of high energy conversion efficiency, less environmental pollution and the like, is considered as a preferred novel high-efficiency environment-friendly power generation technology in the 21 st century, and is widely concerned by the scientific and engineering fields. Currently, although research and development of fuel cells are being pursued and great progress has been made in various countries of the world, large-scale commercial applications are still limited by high manufacturing costs. It is known that both cathode and anode reactions of a fuel cell need to be performed under the action of a catalyst, especially the Oxygen Reduction Reaction (ORR) kinetics of the cathode is slower, and the use of a large amount of noble metal platinum catalyst makes the cell cost prohibitive. At the same time, poor stability also affects the operating performance and service life of the fuel cell. Therefore, the development of cheap, easily available and high-stability oxygen reduction catalysts is a fundamental solution for reducing the cost of fuel cells and improving the performance and service life of the fuel cells.
Among various earth-rich compounds, transition Metal Phosphide (TMPs) -based electrocatalysts have recently been widely used. The phosphorus atom in TMP plays a key role in HER. Due to its high electronegativity, the P atom can trap electrons from the metal atom. In addition, negatively charged P can act as a base, trapping positively charged protons during ORR. Generally, there are three main routes for the synthesis of TMP, depending on the different phosphorus sources. One is by using hypophosphite (NaH) 2 PO 2 And NH 4 H 2 PO 2 ) In situ generation of Phosphine (PH) as a phosphorus source 3 ) The gas-solid reaction scheme of (1). However, such a synthetic process would beToxic and pyrophoric PH3 products are released. Another route is solution phase synthesis using an organic phosphine (e.g. tri-n-octylphosphine or triphenylphosphine as the phosphorus source). However, this process is subject to pyrolysis due to the corrosive and flammable nature of the organic agents. Direct reduction of metal phosphate at elevated temperatures (. Alpha. -800 ℃ C.) is another method for producing TMP. Unfortunately, this strategy requires not only hazardous gas (H) 2 ) And the product always has a macroscopic size with irregular morphology. In order to solve the problems in the prior art, the invention provides a preparation method and application of a flower-shaped ferroelectric phosphide catalyst, the method is simple, the cost is low, the efficiency is high, the prepared ferroelectric phosphide catalyst is flower-shaped, the appearance improves the specific surface area of the material, the contact area between an electrolyte and the material is larger, more active sites participate in catalysis, and excellent oxygen reduction electrocatalysis characteristics and stability are shown.
Disclosure of Invention
Aiming at the defects of the prior art, the flower-shaped iron phosphide catalyst provided by the invention is simple in preparation method, low in cost and high in efficiency, and the specific surface of the material is improved, so that the contact area between an electrolyte and the material is larger, more active sites participate in catalysis, and excellent oxygen reduction electrocatalysis characteristics are shown.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a flower-shaped phosphide ferroelectric catalyst comprises the following steps:
the method comprises the following steps: dissolving melamine in deionized water at a certain temperature until a transparent solution is formed;
step two: adding a certain amount of ATMP into the solution and stirring for a certain time, and forming a supramolecular gel precursor when the mixture is naturally cooled to room temperature;
step three: adding ferric salt into the supermolecule gel precursor solution obtained in the step two, continuously stirring for a certain time, centrifuging, and drying to obtain a light yellow product;
step four: and (4) placing the light yellow product formed in the step three into a tubular furnace, and calcining at high temperature in a protective gas atmosphere to obtain the flower-shaped ferroelectric phosphide catalyst.
Further, in the first step, the molar volume range of the melamine is 0.2 to 0.5mol/L, and the temperature is 85 to 100 DEG o And C.
Further, in the second step, the mass concentration of the ATMP aqueous solution is 50 wt% -75 wt%, and the volume range of the added ATMP is 0.6-1.0 mL.
Further, in the second step, the stirring time is 3-10 min;
further, in step three, the iron salt may be Fe (NO) 3 ) 2 . 9H 2 O、FeCl 3 And FeSO 4 . 7H 2 And O, wherein the molar weight of the added iron salt is 1 to 2mmol.
Further, in the third step, the stirring time is 2-10min.
Further, in the fourth step, the protective atmosphere may be one of nitrogen, argon or argon/hydrogen gas.
Further, in the fourth step, the calcination temperature is between 900 to 1000 o C, the heating rate is 2 to 6 o C/min, and the heat preservation time is 2 to 4 hours.
A method for preparing a flower-shaped phosphorized ferroelectric catalyst, which introduces ATMP organic phosphonic acid ligand to achieve the purpose of in-situ phosphorization, and the greatest advantage of the in-situ phosphorization is to prepare a catalyst material with a regular morphology. Meanwhile, the introduced melamine is used as a carbon source, has reducibility and promotes the generation of iron phosphide.
The application of the flower-shaped iron phosphide catalyst is characterized in that the flower-shaped iron phosphide catalyst prepared by the preparation method is uniform and regular in surface appearance.
The application of flower-shaped phosphide ferroelectric catalyst as ORR reaction in alkaline electrolyte. ORR reaction in 0.1M KOH gives an onset potential (0.858V vs. RHE) comparable to commercial 20% Pt/C, and a diffusion limiting current (4.850 mA cm) -2 ) And exhibits excellent methanol tolerance and stability.
Compared with the prior art, the technical scheme provided by the invention has the following remarkable effects:
the flower-shaped ferroelectric phosphide catalyst disclosed by the invention is easy to purchase, cheap and easy to obtain as well as convenient for large-scale production.
In the preparation process of the flower-shaped ferroelectric phosphide catalyst, the ATMP organic phosphonic acid ligand is introduced to achieve the purpose of in-situ phosphorization, and the most advantage of the in-situ phosphorization is that the catalyst material with a regular shape is prepared. Meanwhile, the introduced melamine is used as a carbon source, has reducibility and promotes the generation of iron phosphide.
The flower-shaped phosphorized ferroelectric catalyst provided by the invention shows excellent oxygen reduction electrocatalytic characteristics, and can obtain an initial potential (0.858V vs. RHE) and a diffusion limiting current (4.850 mA cm) which are equivalent to the commercial 20% Pt/C through an ORR reaction in 0.1M KOH -2 ) And exhibits excellent methanol tolerance and stability.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
FIG. 1 is an X-ray diffraction pattern of a FeP/NPC catalyst obtained in example 1 according to the present invention;
FIG. 2 is a SEM photograph of the FeP/NPC catalyst obtained in example 1 of the present invention;
FIG. 3 is a plot of (A) Linear sweep voltammogram of the FeP/NPC catalyst obtained in example 1 of the present invention, (B) Linear sweep voltammogram of the FeP/NPC catalyst and a 20% commercial Pt/C modified rotating disk electrode (RRDE) in 0.1M KOH solution, (C) stability, and (D) methanol tolerance.
Detailed Description
For a further understanding of the present invention, reference will now be made to the following detailed description taken in conjunction with the accompanying drawings and examples.
Example 1:
the method comprises the following steps: 0.2 mol/L melamine is added at 85 o C until a clear solution is formed, denoted as solution A；
Step two: adding 0.6 mL of ATMP with the mass concentration of 50wt.% into the solution A, stirring for 2 min, and forming a supramolecular gel precursor when the mixture is naturally cooled to room temperature, wherein the supramolecular gel precursor is marked as solution B;
step three: mixing Fe (NO) 3 ) 2 . 9H 2 Adding O into the solution B, continuously stirring for 5 min, centrifuging, and drying to obtain a light yellow product which is marked as C;
step four: placing the C in a tube furnace, and performing nitrogen protection atmosphere at room temperature by 2 o The temperature rises to 900 ℃ at the temperature rising rate of C/min oC Calcining at high temperature for 2 h to obtain the flower-shaped ferroelectric phosphide catalyst.
Example 2:
the method comprises the following steps: 0.3 mol/L melamine is added at 90 o C, dissolving in deionized water until a transparent solution is formed, and marking as a solution A;
step two: adding 0.8 mL of ATMP with the mass concentration of 60 wt.% into the solution A, stirring for 3 min, and forming a supramolecular gel precursor which is marked as a solution B when the mixture is naturally cooled to room temperature;
step three: 1 mmol of Fe (NO) 3 ) 2 . 9H 2 Adding O into the solution B, continuously stirring for 3 min, centrifuging, and drying to obtain a light yellow product, which is marked as C;
step four: placing the C into a tube furnace, and performing temperature control at room temperature and 4 ℃ in a nitrogen protective gas atmosphere o The temperature rises to 900 ℃ at the temperature rising rate of C/min oC Calcining at high temperature for 2 h to obtain the flower-shaped ferroelectric phosphide catalyst.
Example 3:
the method comprises the following steps: 0.3 mol/L melamine is added at 95 o C, dissolving in deionized water until a transparent solution is formed, and marking as a solution A;
step two: adding 0.8 mL of ATMP with the mass concentration of 60 wt.% into the solution A, stirring for 5 min, and forming a supramolecular gel precursor which is marked as a solution B when the mixture is naturally cooled to room temperature;
step three: 2mmol of FeCl 3 Adding into the solution B, stirring for 8 min, centrifuging, and drying to obtain a light yellow product C;
step four: placing the C into a tube furnace, and performing temperature control at room temperature and 4 ℃ in a nitrogen protective gas atmosphere o The temperature rises to 925 ℃ at the temperature rising rate of C/min oC Calcining at high temperature for 2 h to obtain the flower-shaped ferroelectric phosphide catalyst.
Example 4:
the method comprises the following steps: 0.4 mol/L melamine is added at 95 o C, dissolving in deionized water until a transparent solution is formed, and marking as a solution A;
step two: adding 1.0mL of ATMP with the mass concentration of 75wt.% into the solution A, stirring for 6 min, and forming a supramolecular gel precursor which is marked as a solution B when the mixture is naturally cooled to room temperature;
step three: 2mmo of FeSO 4 . 7H 2 Adding O into the solution B, continuously stirring for 10min, centrifuging, and drying to obtain a light yellow product which is marked as C;
step four: placing the C into a tube furnace, and performing nitrogen protection atmosphere at room temperature and 5 degrees centigrade o The temperature rises to 950 ℃ at the temperature rise rate of C/min oC Calcining at high temperature for 4h to obtain the flower-shaped ferroelectric phosphide catalyst.
Example 5:
the method comprises the following steps: 0.5mol/L melamine is added at 100 o C, dissolving the mixture in deionized water until a transparent solution is formed, and marking as a solution A;
step two: adding 1.0mL of ATMP with the mass concentration of 75wt.% into the solution A, stirring for 10min, and forming a supramolecular gel precursor which is marked as a solution B when the mixture is naturally cooled to room temperature;
step three: 2mmo FeSO 4 . 7H 2 Adding O into the solution B, continuously stirring for 10min, centrifuging, and drying to obtain a light yellow product which is marked as C;
step four: placing the C into a tube furnace, and performing reaction at room temperature and 6 ℃ under a nitrogen protective gas atmosphere o The temperature rises to 1000 at a temperature rise rate of C/min oC Calcining at high temperature for 4h to obtain the flower-shaped ferroelectric phosphide catalyst.
FIG. 1 is an X-ray diffraction pattern of a FeP/NPC catalyst obtained in example 1 according to the present invention, and it can be seen from FIG. 1 that a series of diffraction peaks for FeP/NPC can be indexed as FeP phase (JCPDS No. 39-0809).
FIG. 2 is a SEM photograph of the FeP/NPC catalyst obtained in example 1 according to the present invention. FIG. 2 shows that FeP/NPC has flower-like shape and relatively uniform size, and the size is between 500 nm-1 um. The appearance is relatively complete.
FIG. 3 is a graph of (A) linear sweep voltammogram of a FeP/NPC catalyst obtained in example 1 according to the present invention; linear sweep voltammograms of FeP/NPC catalyst and 20% commercial Pt-modified rotating disk electrode (RRDE) in 0.1M KOH solution, (C) stability and (D) methanol tolerance plots. As shown in fig. 3A, at N 2 (dotted line) and O 2 (solid line) saturated electrolyte at 10mV s -1 The scanning rate of (c) performs CVs. Compared with the initial potential, the initial potential of the FeP/NPC catalyst (Eonset = 0.922V) is better than that of the commercial Pt/C catalyst (0.911V) of 20%. LSV testing was performed on all catalysts at 1600rpm and the results are shown in FIG. 3B. Half-wave potential (0.822V) and diffusion limiting Current Density (5.480 mA cm) of FeP/NPC -2 ) And also superior to 20% of commercial Pt/C (0.816V, 5.380mA cm) -2 ). Direct Methanol Fuel Cells (DMFCs) are clean energy conversion devices, but the problem of methanol crossover from the anode to the cathode can severely reduce the activity of the catalyst to catalyze the cathode oxygen reduction reaction and the efficiency of the fuel cell. Therefore, it remains a challenge to develop a highly efficient stable catalyst having both excellent ORR catalytic activity and methanol poisoning resistance. Methanol resistance of FeP/NPC and Pt/C was measured by chronoamperometry (i-t). As shown in FIG. 3C, the flower-like FeP/NPC material is in O 2 The solution is reacted in a saturated 0.1M KOH electrolyte for 500 minutes, the current density is only lost by about 5 percent, and the Pt/C loss is about 16 percent, which shows that the flower-shaped FeP/NPC material has good stability in an alkaline medium. As shown in fig. 3D, the effect of 3.0M methanol on the flower-like FeP/NPC material was insignificant and the current density decreased by about 5% after 600 seconds of addition of 3.0M methanol to 10.0ml of 0.1M KOH electrolyte. The results show that the flower-shaped FeP/NPC material has excellent methanol permeation resistance.
Those of ordinary skill in the art will understand that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (11)
1. A preparation method of a flower-shaped phosphide ferroelectric catalyst is characterized by comprising the following steps:
the method comprises the following steps: dissolving melamine in deionized water at a certain temperature until a transparent solution is formed;
step two: adding a certain amount of aminotrimethylene phosphonic Acid (ATMP) into the solution, stirring for a certain time, and forming a supramolecular gel precursor when the mixture is naturally cooled to room temperature;
step three: adding ferric salt into the supermolecule gel precursor solution obtained in the step two, continuously stirring for a certain time, centrifuging, and drying to obtain a light yellow product;
step four: and (4) placing the light yellow product formed in the third step into a tubular furnace for high-temperature calcination, and obtaining the flower-shaped ferroelectric phosphide catalyst in a protective gas atmosphere.
2. The method for preparing a flower-like phosphide ferroelectric catalyst as claimed in claim 1, wherein: in the first step, the molar volume range of the melamine is 0.2-0.5 mol/L, and the temperature is between 85-100 ℃.
3. The method for preparing a flower-like phosphide ferroelectric catalyst as claimed in claim 1, wherein: in the second step, the mass concentration of the ATMP aqueous solution is 50wt.% to 75wt.%, and the volume range of the added ATMP is 0.6 mL to 1.0mL.
4. The method for preparing a flower-like phosphide ferroelectric catalyst as claimed in claim 1, wherein: in the second step, the stirring time is 3-10min.
5. The method for preparing a flower-like phosphide ferroelectric catalyst as claimed in claim 1, wherein: in step three, the iron salt may be Fe (NO) 3 ) 2 .9H 2 O、FeCl 3 And FeSO 4 .7H 2 O, the molar weight of the added ferric salt is 1-2 mmol.
6. The method for preparing a flower-like phosphide ferroelectric catalyst according to claim 1, wherein: in the third step, the stirring time is 2-10min.
7. The method for preparing a flower-like phosphide ferroelectric catalyst as claimed in claim 1, wherein: in step four, the protective atmosphere may be one of nitrogen, argon, or argon/hydrogen gas.
8. The method for preparing a flower-like phosphide ferroelectric catalyst as claimed in claim 1, wherein: in the fourth step, the calcining temperature is 900-1000 ℃, the heating rate is 2-6 ℃/min, and the heat preservation time is 2-4 h.
9. The method for preparing a flower-shaped ferroelectric catalyst for phosphorization according to claim 1, wherein ATMP organophosphonic acid ligand is introduced to achieve the purpose of in-situ phosphorization, and the most advantage of in-situ phosphorization is to prepare a catalyst material with regular morphology. Meanwhile, the introduced melamine is used as a carbon source, has reducibility and promotes the generation of iron phosphide.
10. A flower-shaped phosphide ferroelectric catalyst, characterized in that the flower-shaped phosphide ferrite reduction electrocatalyst is prepared by the preparation method as claimed in any one of claims 1 to 8.
11. Use of a flower-shaped phosphide ferroelectric catalyst prepared by the preparation method as described in any one of claims 1 to 8, wherein said flower-shaped phosphide ferroelectric catalyst is used for oxygen reduction reaction in an alkaline electrolyte.
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