CN112376070B - Multi-principal-element alloy nano catalyst capable of efficiently separating out oxygen, and preparation method and application thereof - Google Patents
Multi-principal-element alloy nano catalyst capable of efficiently separating out oxygen, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a multi-principal-element alloy nano catalyst with high-efficiency oxygen precipitation, a preparation method and application thereof, belonging to the technical field of catalysts, wherein the catalyst consists of FeCoNiCu multi-principal-element alloy nano particles, is a cubic crystal system with a FeNi alloy structure, and has a space group Fm3 m; the molar ratio of Fe, Co, Ni and Cu is 1:1:1: 1. The method of the invention firstly utilizes a microwave-assisted polyol method to prepare FeCoNiCu nano multi-principal element alloy, provides a new preparation process for the field of nano multi-principal element alloy synthesis, and the prepared nano structure of the multi-principal element alloy electrocatalyst has excellent conductivity, and the rough surface is beneficial to exposing more active sites, thereby improving the catalytic activity.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a high-efficiency oxygen precipitation multi-principal-element alloy nano catalyst, and a preparation method and application thereof.
Background
In the water decomposition reaction, the reaction kinetics of anodic oxygen evolution involving four-electron reaction is rather slow, which is the step with the highest energy consumption in the water decomposition reaction, and is a great obstacle to the development of energy storage and conversion fields such as water electrolysis, fuel cells and the like. At present, noble metals used for catalyzing oxygen precipitation reaction have high cost and are easy to corrode, non-noble metals also have the problems of poor stability and poor activity, and how to enable the oxygen precipitation reaction catalyst to reach acceptable catalytic activity and service life under the condition of low content of noble metals even without noble metals becomes a difficult problem which is urgently needed to be overcome at present, and is also a problem generally concerned by scientific researchers. The alloy catalyst containing a plurality of metal principal elements has excellent catalytic activity due to coordination, geometric effects, and the like. The nano-sized multi-principal-element alloy powder is widely applied to the field of catalysis, and is paid much attention to because of having better performance than single metal nano-particles.
The methods for preparing the multi-principal element alloy nanoparticles reported at present comprise the following steps: chemical reduction method, carbothermic oscillation method, plasma arc method, scanning probe photoetching technology and the like, although the methods are many, the conditions of simple process, low cost and batch preparation can be achieved, so that the development of a new process for synthesizing the multi-principal-element alloy nano particles is particularly important.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides the high-efficiency oxygen precipitation multi-principal-element alloy nano-catalyst, the preparation method and the application thereof, the FeCoNiCu nano multi-principal-element alloy is prepared by using the microwave-assisted polyol method for the first time, a new preparation process is provided for the field of nano multi-principal-element alloy synthesis, the nano structure of the prepared multi-principal-element alloy electrocatalyst has excellent conductivity, and the rough surface is favorable for exposing more active sites, so that the catalytic activity is improved. The specific technical scheme is as follows:
a multi-principal-element alloy nano catalyst for efficient oxygen precipitation is composed of FeCoNiCu multi-principal-element alloy nano particles, and is a cubic crystal system with a FeNi alloy structure, and a space group Fm3 m; the molar ratio of Fe, Co, Ni and Cu is 1:1:1: 1;
the particle size of the catalyst is 100-200 nm;
the preparation method of the high-efficiency oxygen precipitation multi-principal-element alloy nano catalyst comprises the following steps:
step 1, preparing precursor metal salt solution:
(1) weighing metal salts corresponding to four elements according to the molar ratio of iron to cobalt to nickel to copper of 1:1:1:1, completely dissolving the metal salts in polyhydric alcohol, sealing, and stirring for 3-12 h until the solution is completely clarified and uniform to prepare a metal salt polyhydric alcohol clarified solution A;
(2) dropwise adding NaOH polyol solution into the metal salt polyol clarified solution A, and adjusting the pH of the solution to 9-12 to obtain precursor metal salt solution B;
pouring the precursor metal salt solution B into a container, carrying out microwave heating under the air condition, and then naturally cooling to room temperature to prepare a solution C;
step 3, centrifugal washing:
centrifuging the solution C, washing the precipitate obtained by centrifuging, and thoroughly washing away residual organic solvent and impurities to obtain a solid D;
and 4, drying:
and drying the solid D in an oven at the temperature of 60-80 ℃ to obtain the high-efficiency oxygen precipitation multi-principal-element alloy nano catalyst, wherein the molar ratio of Fe, Co, Ni and Cu atoms in the high-efficiency oxygen precipitation multi-principal-element alloy nano catalyst is 1:1:1: 1.
In the step 1(1), the metal salt is one or a mixture of nitrate, chloride and acetate; the polyalcohol is one or a mixed solution of two of ethylene glycol and pentaerythritol;
in the step 1(1), the using amount of the polyhydric alcohol is not less than the solubility of the metal salt, so that the metal salt is completely dissolved;
in the step 1(1), the sealing is realized by adopting a preservative film, and the stirring is magnetic stirring;
in the step 1(2), the concentration of NaOH polyalcohol solution is 0.1-1 mol L-1；
In the step 2, the container is a single-mouth flask; the microwave heating adopts a microwave oven with a reflux device, the heating power is 800w, the heating time is 5-9 min, and the microwave heating mode is continuous heating without intermittence;
in the step 3, absolute ethyl alcohol is adopted for washing;
in the step 4, an oven is adopted for drying, the drying temperature is 60-80 ℃, and the drying time is more than or equal to 12 hours;
the high-efficiency oxygen precipitation multi-principal-element alloy nano catalyst is used as a working electrode in catalyzing oxygen precipitation reaction under alkaline conditions, and the specific method comprises the following steps:
(1) mixing 3-5 mg of efficient oxygen precipitation multi-principal-element alloy nano catalyst, 0.25-0.5 mL of dispersing agent and 10-50 mu L of ethanol solution of perfluorosulfonic acid-polytetrafluoroethylene copolymer to form a solution;
(2) ultrasonically treating the solution for 30-120 min to prepare a suspension, dripping the suspension on a carbon paper electrode, wherein the loading amount of a catalyst is 0.2-1 mg/cm-2And the electrode is used as a working electrode after being naturally dried.
In the step (1), the mass fraction of the ethanol solution of the perfluorosulfonic acid-polytetrafluoroethylene copolymer is 5-20%; the dispersing agent is one or a mixture of N, N-Dimethylformamide (DMF), isopropanol and deionized water;
in the step (2), the area of the carbon paper electrode is 0.18cm2。
Compared with the prior art, the high-efficiency oxygen precipitation multi-principal-element alloy nano catalyst and the preparation method and the application thereof have the beneficial effects that:
firstly, the multi-principal element alloy nanoparticles contained in the nano multi-principal element alloy catalyst consist of four low-cost elements of Fe, Co, Ni and Cu, and have cost advantages compared with the existing noble metal oxidation catalyst substances such as ruthenium oxide, iridium oxide and the like with better performance in the field of catalytic oxygen precipitation reaction.
Secondly, the multi-principal element alloy nanoparticles contained in the nano multi-principal element alloy electrocatalyst are of a typical FeNi alloy structure cubic crystal system, and have Fm3m space group, and the multi-principal element characteristics enable the phase structure to be relatively stable. The particle diameter is 100-200 nm, and the particle has a rough surface, so that abundant active sites can be provided for an electrocatalysis process.
The nano multi-principal-element alloy electrocatalyst alloy disclosed by the invention has excellent conductivity, is rough in surface, can expose a large number of active sites, and shows excellent catalytic activity. Under the alkaline condition, the multi-principal-element alloy electrocatalyst is measured to catalyze the oxygen to be separated outThe overpotential of the reaction is 250-270 mV at a current density of 10mA cm-2, the Tafel slope is 40-60 mV dec-1, and the overpotential is 10mA cm-2-2And 50mA cm-2At a current density of 10h, the current hardly decayed in the i-t stability test, and at 10mA cm-2The corresponding voltage is almost unchanged within 10 hours of continuous voltage, and the catalyst has good catalytic activity and stability.
The polyol is mainly used as a reducing agent and has the function of reducing metal ions to form multi-principal-element alloy nanoparticles. The purpose of the NaOH polyalcohol solution is to adjust the pH value of the solution, so that the reduction capability of the polyalcohol solution reaches the optimal level, and the formation of multi-principal element alloy nano particles is facilitated. When the pH value is too low, the reduction capability of the solution is weak, all metal ions cannot be completely reduced to form multi-principal-element nano alloy particles, and when the pH value is too high, the solution can form precipitates to influence the formation of the multi-principal-element alloy nano particles.
Fifthly, the invention adopts a simple microwave-assisted polyol method to prepare the electrocatalyst containing FeCoNiCu nano multi-principal element alloy for the first time, the method is easy to implement and has low cost; provides a new idea for the low-cost batch preparation of FeCoNiCu multi-principal-element alloy.
In conclusion, the invention starts with the development of a new process of the FeCoNiCu multi-principal-element alloy nano electro-catalyst, and the microwave-assisted polyol method has low cost, simple process and short time consumption, so that the cost is reduced, the process is simplified, and the mass production can be realized.
Drawings
FIG. 1 is an SEM topography of a high efficiency oxygen precipitation multi-principal element alloy nano-catalyst of example 1;
FIG. 2 is an XRD pattern of a high efficiency oxygen precipitating multi-host alloy nanocatalyst of examples 1-5: wherein, (a) is an XRD picture of the high-efficiency oxygen precipitation multi-principal-element alloy nano catalyst in the embodiment 1; (b) an XRD picture of the high-efficiency oxygen precipitation multi-principal-element alloy nano catalyst in example 2 is shown; (c) an XRD picture of the high-efficiency oxygen precipitation multi-principal-element alloy nano-catalyst in example 3 is shown; (d) an XRD picture of the high-efficiency oxygen precipitation multi-principal-element alloy nano-catalyst in example 4 is shown; (e) an XRD picture of the high-efficiency oxygen precipitation multi-principal-element alloy nano-catalyst in example 5 is shown;
FIG. 3 is a LSV diagram of a FeCoNiCu multi-principal element alloy electrocatalyst in example 1(FeCoNiCu-5min) of the present invention;
FIG. 4 is Tafel diagram of a high efficiency oxygen precipitation multi-principal element alloy nanocatalyst of example 1;
FIG. 5 is EIS diagram of the high efficiency oxygen precipitation multi-principal element alloy nano-catalyst of example 1;
FIG. 6 is a graph of the chronoamperometric (. eta.10) of the high efficiency oxygen evolution multi-principal-element alloy nanocatalyst of example 1;
FIG. 7 is a graph of the chronoamperometric (. eta.50) of the high efficiency oxygen evolution multi-principal-element alloy nanocatalyst of example 1;
FIG. 8 is a graph of the chronoamperometric (. eta.10) of the high efficiency oxygen evolution multi-principal-element alloy nanocatalyst of example 1.
Detailed Description
The invention will be further described with reference to specific embodiments and figures 1 to 8, but the invention is not limited to these embodiments.
Example 1
A multi-principal-element alloy nano catalyst for efficient oxygen precipitation is composed of FeCoNiCu multi-principal-element alloy nano particles, and is a cubic crystal system with a FeNi alloy structure, and a space group Fm3 m; the molar ratio of Fe, Co, Ni and Cu is 1:1:1: 1; the particle diameter of the high-efficiency oxygen precipitation multi-principal-element alloy nano catalyst is 100 nm.
A preparation method of a multi-principal-element alloy nano catalyst with high-efficiency oxygen precipitation comprises the following steps:
step 1, preparing precursor metal salt solution:
weighing ferric nitrate nonahydrate (0.1641g), cobalt nitrate hexahydrate (0.1176g), nickel nitrate hexahydrate (0.1187g) and copper nitrate trihydrate (0.0976g) by using a balance, completely dissolving the weighed metal salts into 100ml of ethylene glycol, sealing the ethylene glycol by using a preservative film, and stirring the ethylene glycol on a magnetic stirrer for 3 hours until the solution is completely clarified and uniform to prepare a metal salt polyol clarified solution A; dropwise adding NaOH polyalcohol solution with the concentration of 1M into the metal salt polyalcohol clarified solution A, and adjusting the pH of the solution to 11 to obtain precursor metal salt solution B;
pouring the precursor metal salt solution B into a single-mouth flask, and continuously heating in a microwave oven with a reflux device under the air; under the power of 800w, the heating time is 5min, and after the heating is finished, the solution is naturally cooled to the room temperature to obtain a solution C;
step 3, centrifugal washing:
centrifuging the solution C, washing the precipitate obtained by centrifuging with absolute ethyl alcohol, and thoroughly washing off residual organic solvent and impurities in the precipitate to obtain a solid D;
and 4, drying:
and drying the solid D in a 60 ℃ oven for 12h to obtain the multi-principal-element alloy nano catalyst separated by high-efficiency oxygen.
The high-efficiency oxygen precipitation multi-principal-element alloy nano catalyst is used as a working electrode in catalyzing oxygen precipitation reaction under alkaline conditions, and the specific method comprises the following steps:
(1) weighing 5mg of high-efficiency oxygen precipitation multi-principal-element alloy nano catalyst, adding 0.5mL of N, N-Dimethylformamide (DMF) and 30 mu L of ethanol solution of perfluorosulfonic acid-polytetrafluoroethylene copolymer with the mass fraction of 5%, and carrying out ultrasonic treatment for 30min to prepare suspension; dropping 20 μ L of the suspension into a 0.18cm area2The electrode is used as a working electrode after being naturally dried on the carbon paper, and the loading capacity of the catalyst is 1mg/cm-2Establishing a three-electrode system by using an Hg/HgO electrode as a reference electrode and a platinum wire as a counter electrode, wherein the electrolyte is 1M KOH; and (3) carrying out electrochemical performance test on the Shanghai Chenghua electrochemical workstation: the scan rate of LSV is 1mV s-1Ohmic compensation is 90%; voltage versus reversible hydrogen electrode, LSV (Linear potential Scan) curve, scan rate 1mV s-1。
From the SEM result of fig. 1, the multi-principal element alloy electrocatalyst nanoparticle is uniformly dispersed and has a uniform particle size, the particle diameter is about 50nm, and it can be seen that the particle surface is rough, such a morphology is favorable for exposing more active sites, and improving the catalytic activity of the material. The XRD result of FIG. 2(a) shows that the alloy in the catalyst has a FeNi alloy structureThe existence of Fm3m space group indicates that the alloy component contained in the catalyst is a multi-principal-element alloy. The multi-principal element makes the phase structure more stable, which is beneficial to improving the stability of the catalyst. The nano-sized multi-principal-element alloy particles increase the contact area with the electrolyte, and can provide rich active sites for the electrocatalysis process. 3-8 show that the multi-principal element alloy electrocatalyst catalyzes the oxygen evolution reaction to obtain the current density of 10mA cm through electrochemical performance test-2The overpotential is 256mV, the Tafel slope is 47mV dec-1Electrochemical impedance significantly lower than 11 Ω at 10mA cm-2And 50mA cm-2At a current density of 10h, the current hardly decayed in the i-t stability test, and at 10mA cm-2The corresponding voltage is almost unchanged within 10 hours of continuous voltage, and the catalyst has good catalytic activity and stability.
Example 2
A multi-principal-element alloy nano catalyst for efficient oxygen precipitation is composed of FeCoNiCu multi-principal-element alloy nano particles, and is a cubic crystal system with a FeNi alloy structure, and a space group Fm3 m; the molar ratio of Fe, Co, Ni and Cu is 1:1:1: 1; the particle diameter of the high-efficiency oxygen precipitation multi-principal-element alloy nano catalyst is 100 nm.
A preparation method of a multi-principal-element alloy nano catalyst with high-efficiency oxygen precipitation comprises the following steps:
step 1, preparing precursor metal salt solution:
weighing ferric nitrate nonahydrate (0.1641g), cobalt nitrate hexahydrate (0.1176g), nickel nitrate hexahydrate (0.1187g) and copper nitrate trihydrate (0.0976g) by using a balance, completely dissolving the weighed metal salts into 100ml of ethylene glycol, sealing the ethylene glycol by using a preservative film, and stirring the ethylene glycol on a magnetic stirrer for 3 hours until the solution is completely clarified and uniform to prepare a metal salt polyol clarified solution A; dropwise adding NaOH polyalcohol solution with the concentration of 1M into the metal salt polyalcohol clarified solution A, and adjusting the pH of the solution to 11 to obtain precursor metal salt solution B;
pouring the precursor metal salt solution B into a single-mouth flask, and continuously heating in a microwave oven with a reflux device under the air; under the power of 800w, the heating time is 6min, and after the heating is finished, the solution is naturally cooled to the room temperature to obtain a solution C;
step 3, centrifugal washing:
centrifuging the solution C, washing the precipitate obtained by centrifuging with absolute ethyl alcohol, and thoroughly washing off residual organic solvent and impurities in the precipitate to obtain a solid D;
and 4, drying:
and drying the solid D in a 60 ℃ oven for 12h to obtain the multi-principal-element alloy nano catalyst separated by high-efficiency oxygen.
The high-efficiency oxygen precipitation multi-principal-element alloy nano catalyst is used as a working electrode in catalyzing oxygen precipitation reaction under alkaline conditions, and the specific method comprises the following steps:
weighing 5mg of high-efficiency oxygen precipitation multi-principal-element alloy nano catalyst, adding 0.5mL of N, N-Dimethylformamide (DMF) and 30 mu L of ethanol solution of perfluorosulfonic acid-polytetrafluoroethylene copolymer with the mass fraction of 5%, and carrying out ultrasonic treatment for 30min to prepare suspension. And (3) dripping 20 mu L of the suspension on carbon paper with the area of 0.18cm2, naturally airing, and then using the electrode as a working electrode, a catalyst load of 1mg/cm & lt-2 & gt, an Hg/HgO electrode as a reference electrode, a platinum wire as a counter electrode, establishing a three-electrode system, wherein the electrolyte is 1M KOH. And (3) carrying out electrochemical performance test on the Shanghai Chenghua electrochemical workstation. The scan rate of LSV is 1mV s-1, and the ohmic compensation is 90%; voltage versus reversible hydrogen electrode, LSV (Linear potential Scan) curve, scan rate 1mV s-1。
From the XRD result of fig. 2(b), it was revealed that the alloy in the catalyst existed in the FeNi alloy structure cubic system, Fm3m space group, indicating that the alloy component contained in the catalyst was definitely a multi-principal-element alloy. The multi-principal element makes the phase structure more stable, which is beneficial to improving the stability of the catalyst. The nano-sized multi-principal-element alloy particles increase the contact area with the electrolyte, and can provide rich active sites for the electrocatalysis process.
Example 3
A multi-principal-element alloy nano catalyst for efficient oxygen precipitation is composed of FeCoNiCu multi-principal-element alloy nano particles, and is a cubic crystal system with a FeNi alloy structure, and a space group Fm3 m; the molar ratio of Fe, Co, Ni and Cu is 1:1:1: 1; the particle diameter of the high-efficiency oxygen precipitation multi-principal-element alloy nano catalyst is 100 nm.
A preparation method of a multi-principal-element alloy nano catalyst with high-efficiency oxygen precipitation comprises the following steps:
step 1, preparing precursor metal salt solution:
weighing ferric nitrate nonahydrate (0.1641g), cobalt nitrate hexahydrate (0.1176g), nickel nitrate hexahydrate (0.1187g) and copper nitrate trihydrate (0.0976g) by using a balance, completely dissolving the weighed metal salts into 100ml of ethylene glycol, sealing the ethylene glycol by using a preservative film, and stirring the ethylene glycol on a magnetic stirrer for 3 hours until the solution is completely clarified and uniform to prepare a metal salt polyol clarified solution A; dropwise adding NaOH polyalcohol solution with the concentration of 1M into the metal salt polyalcohol clarified solution A, and adjusting the pH of the solution to 11 to obtain precursor metal salt solution B;
pouring the precursor metal salt solution B into a single-mouth flask, and continuously heating in a microwave oven with a reflux device under the air; under the power of 800w, the heating time is 7min, and after the heating is finished, the solution is naturally cooled to the room temperature to obtain a solution C;
step 3, centrifugal washing:
centrifuging the solution C, washing the precipitate obtained by centrifuging with absolute ethyl alcohol, and thoroughly washing off residual organic solvent and impurities in the precipitate to obtain a solid D;
and 4, drying:
and drying the solid D in a 60 ℃ oven for 12h to obtain the multi-principal-element alloy nano catalyst separated by high-efficiency oxygen.
The high-efficiency oxygen precipitation multi-principal-element alloy nano catalyst is used as a working electrode in catalyzing oxygen precipitation reaction under alkaline conditions, and the specific method comprises the following steps:
weighing high-efficiency oxygen precipitation multi-principal-element alloy nano catalyst 5mg, adding 0.5mL of N, N-Dimethylformamide (DMF) and 30 mu L of ethanol solution of perfluorosulfonic acid-polytetrafluoroethylene copolymer with mass fraction of 5%, and performing ultrasonic treatment for 30min to prepare suspension. And (3) dripping 20 mu L of the suspension on carbon paper with the area of 0.18cm2, naturally airing, and then using the electrode as a working electrode, a catalyst load of 1mg/cm & lt-2 & gt, an Hg/HgO electrode as a reference electrode, a platinum wire as a counter electrode, establishing a three-electrode system, wherein the electrolyte is 1M KOH. And (3) carrying out electrochemical performance test on the Shanghai Chenghua electrochemical workstation. The scan rate of LSV is 1mV s-1, and the ohmic compensation is 90%; voltage versus reversible hydrogen electrode, LSV (Linear potential Scan) curve, scan rate 1mV s-1。
From the XRD result of fig. 2(c), it was revealed that the alloy in the catalyst existed in the FeNi alloy structure cubic system, Fm3m space group, indicating that the alloy component contained in the catalyst was definitely a multi-principal-element alloy. The multi-principal element makes the phase structure more stable, which is beneficial to improving the stability of the catalyst. The nano-sized multi-principal-element alloy particles increase the contact area with the electrolyte, and can provide rich active sites for the electrocatalysis process.
Example 4
A multi-principal-element alloy nano catalyst for efficient oxygen precipitation is composed of FeCoNiCu multi-principal-element alloy nano particles, and is a cubic crystal system with a FeNi alloy structure, and a space group Fm3 m; the molar ratio of Fe, Co, Ni and Cu is 1:1:1: 1; the particle diameter of the high-efficiency oxygen precipitation multi-principal-element alloy nano catalyst is 100 nm.
A preparation method of a multi-principal-element alloy nano catalyst with high-efficiency oxygen precipitation comprises the following steps:
step 1, preparing precursor metal salt solution:
weighing ferric nitrate nonahydrate (0.1641g), cobalt nitrate hexahydrate (0.1176g), nickel nitrate hexahydrate (0.1187g) and copper nitrate trihydrate (0.0976g) by using a balance, completely dissolving the weighed metal salts into 100ml of ethylene glycol, sealing the ethylene glycol by using a preservative film, and stirring the ethylene glycol on a magnetic stirrer for 3 hours until the solution is completely clarified and uniform to prepare a metal salt polyol clarified solution A; dropwise adding NaOH polyhydric alcohol solution with the concentration of 1M into the metal salt polyhydric alcohol clarified solution A, and adjusting the pH of the solution to 11 to obtain precursor metal salt solution B;
pouring the precursor metal salt solution B into a single-mouth flask, and continuously heating in a microwave oven with a reflux device under the air; under the power of 800w, the heating time is 8min, and after the heating is finished, the solution is naturally cooled to the room temperature to obtain a solution C;
step 3, centrifugal washing:
centrifuging the solution C, washing the precipitate obtained by centrifuging with absolute ethyl alcohol, and thoroughly washing off residual organic solvent and impurities in the precipitate to obtain a solid D;
and 4, drying:
and drying the solid D in a 60 ℃ oven for 12h to obtain the multi-principal-element alloy nano catalyst separated by high-efficiency oxygen.
The high-efficiency oxygen precipitation multi-principal-element alloy nano catalyst is used as a working electrode in catalyzing oxygen precipitation reaction under alkaline conditions, and the specific method comprises the following steps:
weighing 5mg of the multi-principal element alloy catalyst, adding 0.5mL of N, N-Dimethylformamide (DMF) and 30 mu L of ethanol solution of 5% of perfluorosulfonic acid-polytetrafluoroethylene copolymer by mass fraction, and carrying out ultrasonic treatment for 30min to prepare suspension. And (3) dripping 20 mu L of the suspension on carbon paper with the area of 0.18cm2, naturally airing, and then using the electrode as a working electrode, a catalyst load of 1mg/cm & lt-2 & gt, an Hg/HgO electrode as a reference electrode, a platinum wire as a counter electrode, establishing a three-electrode system, wherein the electrolyte is 1M KOH. And (3) carrying out electrochemical performance test on the Shanghai Chenghua electrochemical workstation. The scan rate of LSV is 1mV s-1, and the ohmic compensation is 90%; voltage versus reversible hydrogen electrode, LSV (Linear potential Scan) curve, scan rate 1mV s-1。
From the XRD result of fig. 2(d), it was revealed that the alloy in the catalyst existed in the FeNi alloy structure cubic system, Fm3m space group, indicating that the alloy component contained in the catalyst was definitely a multi-principal alloy. The multi-principal element makes the phase structure more stable, which is beneficial to improving the stability of the catalyst. The nano-sized multi-principal-element alloy particles increase the contact area with the electrolyte, and can provide rich active sites for the electrocatalysis process.
Example 5
A multi-principal-element alloy nano catalyst for efficient oxygen precipitation is composed of FeCoNiCu multi-principal-element alloy nano particles, and is a cubic crystal system with a FeNi alloy structure, and a space group Fm3 m; the molar ratio of Fe, Co, Ni and Cu is 1:1:1: 1; the particle diameter of the high-efficiency oxygen precipitation multi-principal-element alloy nano catalyst is 100 nm.
A preparation method of a multi-principal-element alloy nano catalyst with high-efficiency oxygen precipitation comprises the following steps:
step 1, preparing precursor metal salt solution:
weighing ferric nitrate nonahydrate (0.1641g), cobalt nitrate hexahydrate (0.1176g), nickel nitrate hexahydrate (0.1187g) and copper nitrate trihydrate (0.0976g) by using a balance, completely dissolving the weighed metal salts into 100ml of ethylene glycol, sealing the ethylene glycol by using a preservative film, and stirring the ethylene glycol on a magnetic stirrer for 3 hours until the solution is completely clarified and uniform to prepare a metal salt polyol clarified solution A; dropwise adding NaOH polyhydric alcohol solution with the concentration of 1M into the metal salt polyhydric alcohol clarified solution A, and adjusting the pH of the solution to 11 to obtain precursor metal salt solution B;
pouring the precursor metal salt solution B into a single-mouth flask, and continuously heating in a microwave oven with a reflux device under the air; under the power of 800w, the heating time is 9min, and after the heating is finished, the solution is naturally cooled to the room temperature to obtain a solution C;
step 3, centrifugal washing:
centrifuging the solution C, washing the precipitate obtained by centrifuging with absolute ethyl alcohol, and thoroughly washing off residual organic solvent and impurities in the precipitate to obtain a solid D;
and 4, drying:
and drying the solid D in a 60 ℃ oven for 12h to obtain the multi-principal-element alloy nano catalyst separated by high-efficiency oxygen.
The high-efficiency oxygen precipitation multi-principal-element alloy nano catalyst is used as a working electrode in catalyzing oxygen precipitation reaction under alkaline conditions, and the specific method comprises the following steps:
weighing 5mg of the multi-principal element alloy catalyst, adding 0.5mL of N, N-Dimethylformamide (DMF) and 30 mu L of perfluorosulfonic acid-polytetrafluoroethylene with the mass fraction of 5%And (3) carrying out ultrasonic treatment on an ethanol solution of the ethylene copolymer for 30min to prepare a suspension. Dropping 20 μ L of the suspension into a 0.18cm area2After the carbon paper is naturally dried, the electrode is used as a working electrode, the loading capacity of a catalyst is 1mg/cm & lt-2 & gt, the Hg/HgO electrode is used as a reference electrode, a platinum wire is used as a counter electrode, a three-electrode system is established, and the electrolyte is 1M KOH. And (3) carrying out electrochemical performance test on the Shanghai Chenghua electrochemical workstation. The scan rate of LSV was 1mV s-1 with an ohmic compensation of 90%.
From the XRD result of fig. 2(e), it was revealed that the alloy in the catalyst existed in the FeNi alloy structure cubic system, Fm3m space group, indicating that the alloy component contained in the catalyst was definitely a multi-principal-element alloy. The multi-principal element makes the phase structure more stable, which is beneficial to improving the stability of the catalyst. The nano-sized multi-principal-element alloy particles increase the contact area with the electrolyte, and can provide rich active sites for the electrocatalysis process.
Claims (10)
1. A multi-principal-element alloy nano catalyst for efficient oxygen precipitation is characterized in that the catalyst consists of FeCoNiCu multi-principal-element alloy nano particles, is a cubic crystal system with a FeNi alloy structure, and is a space group Fm3 m; the molar ratio of Fe, Co, Ni and Cu is 1:1:1: 1.
2. The high-efficiency oxygen precipitation multi-principal-element alloy nano catalyst as claimed in claim 1, wherein the particle size of the catalyst is 100-200 nm.
3. The preparation method of the high-efficiency oxygen precipitation multi-principal-element alloy nano catalyst as claimed in claim 1, characterized by comprising the following steps:
step 1, preparing precursor metal salt solution:
(1) weighing metal salts corresponding to four elements according to the molar ratio of iron to cobalt to nickel to copper of 1:1:1:1, completely dissolving the metal salts in polyhydric alcohol, sealing, and stirring for 3-12 h until the solution is completely clarified and uniform to prepare a metal salt polyhydric alcohol clarified solution A;
(2) dropwise adding NaOH polyol solution into the metal salt polyol clarified solution A, and adjusting the pH of the solution to 9-12 to obtain precursor metal salt solution B;
step 2, microwave treatment:
pouring the precursor metal salt solution B into a container, carrying out microwave heating under the air condition, and then naturally cooling to room temperature to prepare a solution C;
step 3, centrifugal washing:
centrifuging the solution C, washing the precipitate obtained by centrifuging, and thoroughly washing away residual organic solvent and impurities to obtain a solid D;
and 4, drying:
and drying the solid D in an oven at the temperature of 60-80 ℃ to obtain the high-efficiency oxygen precipitation multi-principal-element alloy nano catalyst, wherein the molar ratio of Fe, Co, Ni and Cu atoms in the high-efficiency oxygen precipitation multi-principal-element alloy nano catalyst is 1:1:1: 1.
4. The method for preparing the high efficiency oxygen evolution multi-principal element alloy nano catalyst according to claim 3, wherein in the step 1(1), the metal salt is one or a mixture of nitrate, chloride and acetate; the polyalcohol is one or a mixed solution of two of ethylene glycol and pentaerythritol; the using amount of the polyhydric alcohol is more than or equal to the solubility of the metal salt, so that the metal salt is completely dissolved; the sealing is realized by adopting a preservative film, and the stirring is magnetic stirring.
5. The method for preparing the high efficiency oxygen evolution multi-principal element alloy nano catalyst according to claim 3, wherein in the step 1(2), the concentration of NaOH polyalcohol solution is 0.1-1 mol L-1。
6. The method for preparing the high efficiency oxygen evolution multi-principal element alloy nano catalyst according to the claim 3, characterized in that in the step 2, the container is a single-neck flask; the microwave heating adopts a microwave oven with a reflux device, the heating power is 800w, the heating time is 5-9 min, and the microwave heating mode is continuous heating without intermittence.
7. The method for preparing the high efficiency oxygen evolution multi-principal element alloy nano catalyst according to claim 3, wherein in the step 3, the washing is carried out by absolute ethyl alcohol.
8. The preparation method of the high-efficiency oxygen precipitation multi-principal-element alloy nano catalyst according to claim 3, characterized in that in the step 4, an oven is adopted for drying, the drying temperature is 60-80 ℃, and the drying time is more than or equal to 12 h.
9. The application of the high-efficiency oxygen precipitation multi-principal-element alloy nano-catalyst as claimed in claim 1, which is used as a working electrode in a catalytic oxygen precipitation reaction under an alkaline condition, and is characterized in that the specific method comprises the following steps:
(1) mixing 3-5 mg of efficient oxygen precipitation multi-principal-element alloy nano catalyst, 0.25-0.5 mL of dispersing agent and 10-50 mu L of ethanol solution of perfluorosulfonic acid-polytetrafluoroethylene copolymer to form a solution;
(2) ultrasonically treating the solution for 30-120 min to prepare a suspension, dripping the suspension on a carbon paper electrode, wherein the loading amount of a catalyst is 0.2-1 mg/cm-2And the electrode is used as a working electrode after being naturally dried.
10. The application of the high-efficiency oxygen precipitation multi-principal-element alloy nano catalyst is characterized in that in the step (1), the mass fraction of an ethanol solution of the perfluorosulfonic acid-polytetrafluoroethylene copolymer is 5-20%; the dispersing agent is one or a mixture of N, N-Dimethylformamide (DMF), isopropanol and deionized water; in the step (2), the area of the carbon paper electrode is 0.18cm2。
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