CN113437314B - Nitrogen-doped carbon-supported low-content ruthenium and Co 2 Three-function electrocatalyst of P nano particle and preparation method and application thereof - Google Patents
Nitrogen-doped carbon-supported low-content ruthenium and Co 2 Three-function electrocatalyst of P nano particle and preparation method and application thereof Download PDFInfo
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Abstract
Nitrogen-doped carbon loaded low-content ruthenium and Co 2 P nano-particle three-function electrocatalyst and preparation method and application thereof. The method prepares the Co-loaded catalyst by calcining Zn-Co-ZIF serving as a template and sodium phytate serving as a phosphorus source in an inert atmosphere 2 The P nano particle nitrogen-doped carbon nano composite introduces low-content noble metal ruthenium into the composite through adsorption, and the composite inherits the porous structure of ZIF. The obtained catalyst has good catalytic performance of hydrogen evolution, oxygen evolution and oxygen reduction reaction in an alkaline medium, mainly because the introduction of low-content noble metal changes Co 2 The electronic structure of P is added with active sites, the nitrogen-doped carbon substrate derived from Zn-Co-ZIF is used as the active sites to play a key supporting role, the conduction of electrons and the desorption of reaction intermediates are facilitated, and the catalyst has potential application value in the fields of new energy conversion and storage.
Description
The technical field is as follows:
the invention belongs to the field of new energy material technology and electrochemical catalysis, and particularly relates to nitrogen-doped carbon loaded low-content ruthenium and Co 2 A trifunctional electrocatalyst for P nanoparticles; also relates to a preparation method of the catalyst and an electro-catalysis application of the catalyst in a cathode oxygen reduction reaction, an anode oxygen evolution reaction of electrolyzed water and a cathode hydrogen evolution reaction of an alkaline fuel cell.
The background art comprises the following steps:
energy technologies such as fuel cells and metal air batteries have attracted much attention due to their advantages of efficient energy conversion, environmental friendliness, and the like. Oxygen Reduction Reaction (ORR), oxygen Evolution Reaction (OER) and Hydrogen Evolution Reaction (HER) are key electrode processes for a variety of sustainable energy technologies, but all three have the problem of slow kinetics. The catalysts currently used for ORR and HER reactions are mainly Pt and its alloy, and the catalyst for OER reaction is mainly IrO 2 And RuO 2 However, these precious metals are rare in nature, and it is important to develop a novel, efficient and inexpensive electrocatalyst, and among these, a carbon-based non-precious metal catalyst has attracted much attention as a catalyst most likely to replace the above precious metals.
ZIF, namely a zeolite imidazolate framework material, is a porous crystal material and has the characteristics of high stability and high porosity. ZIF is mainly used for high efficiency catalysis and separation processes. The ZIF-8 or ZIF-67 is prepared by reacting zinc nitrate hexahydrate or cobalt nitrate hexahydrate with 2-methylimidazole, can be used as a sacrificial template to remove metal Zn by a high-temperature calcination method to prepare a monometallic porous carbon material in consideration of the low boiling point of Zn, realizes heteroatom doping to further adjust the electronic property and the surface polarity, and improves the electrochemical catalytic activity of the composite material. It is now common to dope heteroatoms such as N, S, B, P, etc. which can be substituted for some sp in the graphite lattice 2 The hybridized carbon atoms change the electronic characteristics of the carbon material, and further improve the catalytic activity and stability of the carbon material. The introduction of low levels of noble metals generally greatly alters catalyst performance. Although certain performance is achieved in the preparation of carbon nano-materials by taking ZIF as a precursor at present, the preparation of nitrogen-doped carbon-loaded low-content ruthenium and Co by taking Zn-Co-ZIF as a template and a precursor, taking sodium phytate as a P source and introducing a low-content noble metal Ru is not seen yet 2 P nano-particle nano-composite and reports on research of three-functional electro-catalytic performances of ORR, OER and HER.
The method takes Zn-Co-ZIF as a template, and the Zn-Co-ZIF reacts with a cobalt phytate solution to obtain purple solid, and the purple solid is calcined at high temperature to obtain the loaded Co 2 The P nano particle nitrogen is doped with the carbon nano compound, and then the low content of noble metal ruthenium is introduced into the compound through the adsorption effect to obtain the Ru-Co 2 P/NC electrocatalyst. The obtained three-functional catalyst has high conductivity and catalytic performance, effectively reduces overpotential of ORR, OER and HER, shows that the ORR process is a 4 electron catalytic mechanism through a Rotating Disk Electrode (RDE) and a rotating disk electrode (RRDE), and is a more ideal ORR reaction process, and the catalystHas good long-term stability and excellent methanol tolerance. When the hydrogen is catalytically evolved, the concentration reaches 10mA/cm 2 The overpotential generated was only 43mV. The method has important theoretical and practical significance for developing low-content noble metal doped carbon-based electrochemical catalysts and energy conversion and storage devices.
The invention content is as follows:
in view of the deficiencies of the prior art and the need for research and application in the art, it is an object of the present invention to provide a nitrogen-doped carbon loaded low ruthenium and Co content 2 A trifunctional electrocatalyst for P nanoparticles; taking Zn-Co-ZIF as a template, reacting the Zn-Co-ZIF with a cobalt phytate solution, collecting the obtained purple solid, and calcining at high temperature to obtain the Co-loaded Co 2 The P nano particle nitrogen-doped carbon nano composite is introduced into the composite through adsorption to obtain the Ru-Co 2 A P/NC electrocatalyst;
the other purpose of the invention is to provide a nitrogen-doped carbon-loaded low-content ruthenium and Co 2 The preparation method of the P nano particle three-function electrocatalyst specifically comprises the following steps:
(a) Preparation of cobalt phytate (PA-Co)
Weighing 158mg of sodium phytate, dissolving the sodium phytate in 50mL of deionized water, magnetically stirring the sodium phytate at room temperature to form a uniform transparent solution, and then weighing 508mg of cobalt acetate tetrahydrate, adding the cobalt acetate tetrahydrate into the solution to form a purple solution;
(b) Preparation of Zn-Co-ZIF @ PA-Co
Weighing 373.62mg of cobalt acetate tetrahydrate and 446.2mg of zinc nitrate hexahydrate, adding into the cobalt phytate solution in the step (a), and performing ultrasonic dispersion for 30min; weighing 3.28g of 2-methylimidazole, dissolving in 40mL of deionized water, adding the solution into the solution, stirring for 24 hours, centrifugally collecting precipitate, washing with deionized water and ethanol for three times respectively, and drying to obtain a catalyst precursor Zn-Co-ZIF @ PA-Co;
(c)Co 2 preparation of P/NC
Taking appropriate amount of Zn-Co-ZIF @ PA-Co, placing in a magnetic boat, placing the magnetic boat in the center of a tube furnace, N 2 As protective gas, heating to 700-1000 ℃ at the heating rate of 2-10 ℃/min, and keeping the temperature for two hours to obtain the productCo 2 P/NC；
(d)Ru-Co 2 Preparation of P/NC
Weighing 50mg of Co obtained in step (c) 2 Dispersing the P/NC catalyst in 20mL deionized water, and violently stirring for 30min to obtain Co 2 P/NC dispersion; 0.5mL of RuCl 3 ·xH 2 O aqueous solution was dropwise added to the above Co 2 P/NC dispersion liquid; stirring the mixed solution at 1000rpm for 24h, centrifuging, collecting precipitate, washing with deionized water and anhydrous ethanol for three times respectively, and drying to obtain the electrocatalyst Ru-Co 2 P/NC；
Wherein RuCl 3 ·xH 2 The concentration of the O water solution is 10mg/mL; the catalyst has Ru content lower than 2.6at%, ru, co and P elements distributed homogeneously, average grain size of 400-450nm and Co content 2 The average particle diameter of P is 5-30nm.
The invention also aims to provide a nitrogen-doped carbon supported low-content ruthenium and Co 2 The P nano-particle three-function electrocatalyst is applied to catalysis of a cathode ORR, an anode OER and a cathode HER of an alkaline fuel cell.
The method takes Zn-Co-ZIF as a template, and the Zn-Co-ZIF reacts with a cobalt phytate solution to obtain purple solid, and the purple solid is calcined at high temperature to obtain the loaded Co 2 The P nano particle nitrogen-doped carbon nano composite is introduced into the composite through adsorption to obtain the Ru-Co 2 P/NC electrocatalyst. The obtained three-functional catalyst has high conductivity and catalytic performance, effectively reduces overpotentials of ORR, OER and HER, shows that the ORR process is a 4-electron catalytic mechanism through a Rotating Disk Electrode (RDE) and a rotating disk electrode (RRDE), is a relatively ideal ORR reaction process, and has good long-term stability and excellent methanol tolerance. When the hydrogen evolution reaction is catalyzed, the concentration reaches 10mA/cm 2 The overpotential generated was only 43mV.
Compared with the prior art, the invention has the following main advantages and beneficial effects:
1) The three-function electrocatalyst has the advantages that the content of the precious metal Ru is lower than 2.6at%, other raw materials are easy to purchase and prepare, the resources are rich, the price is low, the operation is easy, and the large-scale production is convenient;
2) The tri-functional oxygen catalyst has good methanol tolerance, methanol is added into 0.1mol/L KOH electrolyte, and the catalyst has no obvious attenuation compared with commercial Pt/C;
3) The three-function electrocatalyst of the invention is a loaded low-content precious metal Ru and Co 2 The nitrogen-doped carbon material of the P nano particles has better ORR, OER and HER catalytic activities, and has obvious advantages compared with the unilateral ORR activity of a non-noble metal/nonmetal catalyst reported in the current research;
4) The three-function electrocatalyst of the invention is mixed with commercial 20wt% Pt/C and RuO 2 Compared with the catalyst, the stability of the catalyst is obviously improved, and the catalyst can keep good catalytic activity in a fuel cell and an electrolytic water device for a long time.
Description of the drawings:
FIG. 1 is a scanning electron micrograph (A) of Zn-Co-ZIF @ PA-Co obtained in example 1 and Co obtained in example 1 2 Scanning Electron micrograph (B) of P/NC and Ru-Co obtained in example 1 2 P/NC transmission electron micrograph (C).
FIG. 2 shows Ru-Co obtained in example 1 2 P/NC, NPC obtained in comparative example 1 and Co obtained in comparative example 2 2 P/NC modifies ORR linear sweep voltammograms of RDEs, respectively.
FIG. 3 shows Ru-Co obtained in example 1 2 ORR kinetic profiles of P/NC modified RDE and corresponding K-L profiles.
FIG. 4 shows Ru-Co obtained in example 1 2 P/NC and Pt/C catalyst modification of RDE for methanol tolerance map.
FIG. 5 shows Ru-Co obtained in example 1 2 P/NC modified RDE I-t plot at constant voltage of 0.2V.
FIG. 6 shows Ru-Co obtained in example 1 2 P/NC, NPC obtained in comparative example 1 and Co obtained in comparative example 2 2 The HER linear sweep voltammogram of the RDE was modified by P/NC respectively.
FIG. 7 shows Ru-Co obtained in example 1 2 P/NC, NPC obtained in comparative example 1 and Co obtained in comparative example 2 2 P/NC modifies O of RDE respectivelyER linear sweep voltammogram.
The specific implementation mode is as follows:
for a further understanding of the invention, reference will now be made to the following examples and drawings, which are not intended to limit the invention in any way.
Example 1:
(a) Preparation of cobalt phytate (PA-Co)
Weighing 158mg of sodium phytate, dissolving the sodium phytate in 50mL of deionized water, magnetically stirring the sodium phytate at room temperature to form a uniform transparent solution, and then weighing 508mg of cobalt acetate tetrahydrate, adding the cobalt acetate tetrahydrate into the solution to form a purple solution;
(b) Preparation of Zn-Co-ZIF @ PA-Co
Weighing 373.62mg of cobalt acetate tetrahydrate and 446.2mg of zinc nitrate hexahydrate, adding into the cobalt phytate solution in the step (a), and performing ultrasonic dispersion for 30min; weighing 3.28g of 2-methylimidazole, dissolving in 40mL of deionized water, adding the solution into the solution, stirring for 24 hours, centrifugally collecting precipitate, washing with deionized water and ethanol for three times respectively, and drying to obtain a catalyst precursor Zn-Co-ZIF @ PA-Co;
(c)Co 2 preparation of P/NC
Taking appropriate amount of Zn-Co-ZIF @ PA-Co, placing in a magnetic boat, placing the magnetic boat in the center of a tube furnace, N 2 As protective gas, heating to 800 ℃ at the heating rate of 2 ℃/min, and keeping the temperature for two hours to obtain the product Co 2 P/NC。
(d)Ru-Co 2 Preparation of P/NC
Weighing 50mg of Co obtained in step (c) 2 Dispersing the P/NC catalyst in 20mL deionized water, and violently stirring for 30min to obtain Co 2 A dispersion of P/NC; 0.5mL of RuCl 3 ·xH 2 Dropwise adding the above Co into O aqueous solution 2 P/NC dispersion liquid; stirring the mixed solution at 1000rpm for 24h, centrifuging, collecting precipitate, washing with deionized water and anhydrous ethanol for three times, and drying to obtain the electrocatalyst Ru-Co 2 P/NC; the obtained Ru-Co 2 The content of Ru in the P/NC catalyst is 2.54at%;
example 2:
(a) Preparation of cobalt phytate (PA-Co)
Prepared according to the method and conditions of step (a) in example 1;
(b) Preparation of Zn-Co-ZIF @ PA-Co
Prepared according to the method and conditions of step (b) in example 1;
(c)Co 2 preparation of P/NC
Taking a proper amount of Zn-Co-ZIF @ PA-Co to be put into a magnetic boat, and putting the magnetic boat in the center of the tube furnace. N is a radical of 2 As protective gas, heating to 900 ℃ at the heating rate of 2 ℃/min, and keeping the temperature for two hours to obtain the product Co 2 P/NC。
(d)Ru-Co 2 Preparation of P/NC
Prepared according to the method and conditions of step (d) in example 1; the obtained Ru-Co 2 The content of Ru in the P/NC catalyst is 2.42at%;
example 3:
(a) Preparation of cobalt phytate (PA-Co)
Prepared according to the method and conditions of step (a) in example 1;
(b) Preparation of Zn-Co-ZIF @ PA-Co
Prepared according to the method and conditions of step (b) in example 1;
(c)Co 2 preparation of P/NC
Taking appropriate amount of Zn-Co-ZIF @ PA-Co, placing in a magnetic boat, placing the magnetic boat in the center of a tube furnace, N 2 As protective gas, heating to 1000 ℃ at the heating rate of 2 ℃/min, and keeping the temperature for two hours to obtain the product Co 2 P/NC。
(d)Ru-Co 2 Preparation of P/NC
Prepared according to the method and conditions of step (d) in example 1; obtaining Ru-Co 2 The content of Ru in the P/NC catalyst was 2.36at%;
example 4:
(a) Preparation of cobalt phytate (PA-Co)
Prepared according to the method and conditions of step (a) in example 1;
(b) Preparation of Zn-Co-ZIF @ PA-Co
Prepared according to the method and conditions of step (b) in example 1;
(c)Co 2 preparation of P/NC
Taking a proper amount of Zn-Co-ZIF @ PA-Co, putting the Zn-Co-ZIF @ PA-Co into a magnetic boat, and putting the magnetic boat in the center of a tube furnace. N is a radical of hydrogen 2 As protective gas, heating to 900 ℃ at the heating rate of 4 ℃/min, and keeping the temperature for two hours to obtain the product Co 2 P/NC。
(d)Ru-Co 2 Preparation of P/NC
Prepared according to the method and conditions of step (d) in example 1; obtaining Ru-Co 2 The content of Ru in the P/NC catalyst is 2.42at%;
example 5:
(a) Preparation of cobalt phytate (PA-Co)
Prepared according to the method and conditions of step (a) in example 1;
(b) Preparation of Zn-Co-ZIF @ PA-Co
Prepared according to the method and conditions of step (b) in example 1;
(c)Co 2 preparation of P/NC
Taking a proper amount of Zn-Co-ZIF @ PA-Co, putting the Zn-Co-ZIF @ PA-Co into a magnetic boat, and putting the magnetic boat in the center of a tube furnace. N is a radical of 2 As protective gas, heating to 900 ℃ at the heating rate of 10 ℃/min, and keeping the temperature for two hours to obtain the product Co 2 P/NC。
(d)Ru-Co 2 Preparation of P/NC
Prepared according to the method and conditions of step (d) in example 1; the obtained Ru-Co 2 The content of Ru in the P/NC catalyst is 2.31at%;
comparative example 1:
(a) Preparation of cobalt phytate (PA-Zn)
Weighing 158mg of sodium phytate and 0.17mmol of sodium phytate at room temperature, dissolving the sodium phytate in 50mL of deionized water, magnetically stirring the sodium phytate and the deionized water to form a uniform and transparent solution, weighing 303.44mg of zinc nitrate hexahydrate and 1.02mmol of zinc nitrate, and adding the zinc nitrate hexahydrate into the solution to form a white solution;
(b) Preparation of Zn-ZIF @ PA-Zn
Weighing 1.34g of zinc nitrate hexahydrate and adding the zinc nitrate hexahydrate into the zinc phytate solution in the step (a), and performing ultrasonic dispersion for 30min; weighing 3.28g of 2-methylimidazole, dissolving in 40mL of deionized water, adding the solution into the solution, stirring for 24 hours, centrifugally collecting precipitate, washing with deionized water and ethanol for three times respectively, and drying to obtain a catalyst precursor Zn-ZIF @ PA-Zn;
(c) Preparation of NPC
Taking appropriate amount of Zn-ZIF @ PA-Zn, placing in magnetic boat, placing the magnetic boat in the center of tube furnace, and placing N 2 Heating to 900 ℃ at the heating rate of 2 ℃/min as protective gas, and keeping the temperature for two hours to obtain the product NPC.
Comparative example 2:
(a) Preparation of cobalt phytate (PA-Co)
Weighing 158mg of sodium phytate at room temperature, dissolving 0.17mmol of the sodium phytate in 50mL of deionized water, magnetically stirring to form a uniform transparent solution, weighing 508mg of cobalt acetate tetrahydrate and adding 1.02mmol of the cobalt acetate tetrahydrate into the solution to form a purple solution;
(b) Preparation of Zn-Co-ZIF @ PA-Co
Weighing 373.62mg,1.5mmol of cobalt acetate tetrahydrate and 446.2mg,1.5mmol of zinc nitrate hexahydrate, adding into the cobalt phytate solution in the step (a), and performing ultrasonic dispersion for 30min; weighing 3.28g of 2-methylimidazole, dissolving in 40mL of deionized water, adding the solution into the solution, stirring for 24 hours, centrifugally collecting precipitate, washing with deionized water and ethanol for three times respectively, and drying to obtain a catalyst precursor Co-ZIF @ PA-Co;
(c)Co 2 preparation of P/NC
Taking appropriate amount of Zn-Co-ZIF @ PA-Co, placing in magnetic boat, placing the magnetic boat in the center of tube furnace, N 2 As protective gas, heating to 800 ℃ at the heating rate of 2 ℃/min, and keeping the temperature for two hours to obtain the product Co 2 P/NC。
FIG. 1 shows Zn-Co-ZIF @ PA-Co and Co obtained in example 1 (A) and example 1 (B) 2 Scanning Electron microscopy of P/NC and Ru-Co obtained in example 1 2 P/NC (C) transmission electron micrograph. As can be seen from FIG. A, the precursor is hexagonal and has a rough surface. After calcination, the hexagonal sheet-like structure inherited by the precursor is clearly visible in panel B. And the graph C shows that the morphology of the material is not influenced after low-content noble metal ruthenium is introduced, and the nano particles are distributed on the nitrogen-doped carbon matrix.
Electrocatalysis performance test is carried out in a three-electrode system, a saturated Ag/AgCl electrode is used as a reference electrode, OER and HER performance tests select a carbon rod to be used as a counter electrode, and a 1M KOH solution is used as electrolyte; the ORR performance test selects a platinum wire as a counter electrode and 0.1M KOH solution as electrolyte. The RDE test result is processed by a Koutecky-Levich formula, and the electron transfer number (n) can be calculated from the slope (B) of a K-L curve.
J -1 ＝J k -1 +(Bω 1/2 ) -1
B＝0.62n F C 0 D 0 2/3 v 1/6
Wherein F =96485C/mol, C 0 ＝1.2×10 -3 mol/L，D 0 ＝1.9×10 -5 cm 2 /s，v＝0.01cm 2 /s。
FIG. 2 shows Ru-Co obtained in example 1 2 P/NC, NPC from comparative example 1 and Co from comparative example 2 2 P/NC modifies ORR linear sweep voltammograms of RDEs, respectively. As can be seen from FIG. 2, the low content of noble metal-doped Ru-Co 2 P/NC has the highest initial potential and current density, which indicates that the noble metal Ru is doped with Co 2 The P has synergistic effect, so that the performance of the catalyst is improved, the active sites are increased, the surface property of the catalyst is improved, and the Ru-Co is subjected to reaction 2 Electrochemical activity ratio of P/NC Co 2 P/NC and metal-free NPC are preferred.
FIG. 3 shows Ru-Co obtained in example 1 2 Kinetic parameters from ORR studies performed with P/NC modified RDE. The results show that the number of electron transfers in the ORR catalytic process is about 3.98, close to no HO 2 - 4 electron transfer process of the product, thereby illustrating Ru-Co 2 The ORR process catalyzed by the P/NC modified electrode is an ideal 4-electron reaction mechanism.
FIG. 4 shows Ru-Co obtained in example 1 2 A methanol tolerance graph of the P/NC catalyst modified RDE shows that the current retention rate is recovered to 91.5% and the precious metal Pt/C catalyst is only recovered to 78.8% after 3mL of methanol is added into KOH electrolyte, which indicates that Ru-Co catalyst is adopted 2 P/NC has superior methanol interference resistance over Pt/C catalysts, probably because the ZIF-derived carbon matrix plays a key role in supporting the active sites of the metal species, enhancing the catalystStructural stability and catalytic stability.
FIG. 5 shows Ru-Co obtained in example 1 2 P/NC modifies the I-t plot of RDE at a constant voltage of 0.2V. As can be seen from the figure, in the 40000s test, ru-Co 2 The performance of P/NC is only attenuated by 11%, good long-term stability is shown, the P/NC has important significance in the application of new energy in the future, and has potential application value in the field of modification materials of various fuel cell cathodes.
FIG. 6 shows Ru-Co obtained in example 1 2 P/NC, NPC from comparative example 1 and Co from comparative example 2 2 P/NC modifies the HER linear sweep voltammogram of the RDE, respectively. Ru-Co as shown 2 The P/NC has the minimum initial potential and the maximum current density in the interval of 0-0.6V. Meanwhile, when the current density is-10 mA/cm 2 In the presence of Ru-Co 2 P/NC has the lowest overpotential, which is obviously superior to Co 2 P/NC and NPC. The results show that the introduction of low content of noble metal ruthenium effectively reduces the overpotential thereof. The method is mainly characterized in that the carbonized carbon material inherits the Zn-Co-ZIF porous structure, and the nitrogen-doped carbon matrix derived from the carbonized carbon material carries low content of ruthenium and Co 2 The P nano particles increase electrochemical active sites, are more beneficial to electron conduction, and greatly improve the electrocatalytic performance of the material, so that the lowest overpotential is shown.
FIG. 7 shows Ru-Co obtained in example 1 2 P/NC, NPC obtained in comparative example 1 and Co obtained in comparative example 2 2 P/NC modifies the OER linear sweep voltammogram of the RDE, respectively. Ru-Co as shown 2 The P/NC has the minimum initial potential and the maximum current density in the measured potential interval. Meanwhile, when the current density is 10mA/cm 2 In the presence of Ru-Co 2 P/NC has the lowest overpotential, which is obviously superior to Co 2 P/NC and NPC. The results show that the introduction of low content of noble metal ruthenium effectively reduces the overpotential thereof. The method is mainly characterized in that the carbonized material inherits the Zn-Co-ZIF porous structure, and the introduction of the low-content noble metal Ru changes Co 2 The electronic structure of P is more conductive to electrons, and shows the lowest overpotential.
Claims (2)
1.Nitrogen-doped carbon-loaded low-content ruthenium and Co 2 The P nano particle three-function electrocatalyst is characterized in that the catalyst takes Zn-Co-ZIF as a template, and after the Zn-Co-ZIF is reacted with cobalt phytate dispersion liquid, purple solid is collected and calcined at high temperature to obtain nitrogen-doped carbon-supported Co 2 Nanocomposite of P nanoparticles by adsorption of RuCl 3 ‧xH 2 O introducing a small amount of noble metal ruthenium into the composite catalyst to obtain the three-function electrocatalyst, which is marked as Ru-Co 2 P/NC；
The nitrogen-doped carbon supports low content of ruthenium and Co 2 The preparation method of the P nano-particle three-function electrocatalyst is characterized by comprising the following specific steps of:
(a) Preparation of cobalt phytate (PA-Co)
Weighing 158mg of sodium phytate, dissolving the sodium phytate in 50mL of deionized water, magnetically stirring the sodium phytate at room temperature to form a uniform and transparent solution, weighing 508mg of cobalt acetate tetrahydrate, and adding the cobalt acetate tetrahydrate into the solution to form a purple dispersion liquid;
(b) Preparation of Zn-Co-ZIF @ PA-Co
Weighing 373.62mg of cobalt acetate tetrahydrate and 446.2mg of zinc nitrate hexahydrate, adding into the cobalt phytate dispersion liquid in the step (a), and performing ultrasonic dispersion for 30min; weighing 3.28g of 2-methylimidazole, dissolving in 40mL of deionized water, adding the dispersion into the deionized water, stirring for 24 hours, centrifugally collecting precipitate, washing with deionized water and ethanol for three times respectively, and drying to obtain a catalyst precursor Zn-Co-ZIF @ PA-Co;
(c) Co 2 preparation of P/NC
Taking appropriate amount of Zn-Co-ZIF @ PA-Co, placing in a magnetic boat, placing the magnetic boat in the center of a tube furnace, and placing N 2 Heating to 700 to 1000 ℃ at the heating rate of 2 to 10 ℃/min as protective gas, and keeping the temperature for two hours to obtain a product Co 2 P/NC；
(d) Ru-Co 2 Preparation of P/NC
Weighing 50mg of Co obtained in step (c) 2 Dispersing the P/NC catalyst in 20mL deionized water, and violently stirring for 30min to obtain Co 2 P/NC dispersion; 0.5mL of RuCl 3 ‧xH 2 O aqueous solution was added dropwise to the above Co 2 P/NC dispersion liquid; mixing and dispersingStirring the solution at 1000rpm for 24h, centrifuging, collecting the precipitate, washing with deionized water and absolute ethyl alcohol respectively for three times, and drying to obtain the electrocatalyst Ru-Co 2 P/NC；
Wherein RuCl 3 ‧xH 2 The concentration of the O aqueous solution is 10mg/mL; the catalyst has Ru content lower than 2.6at%, ru, co and P elements distributed homogeneously, average grain size of 400-450nm and Co content 2 The average particle size of P is 5-30nm.
2. The nitrogen-doped carbon supported low-content ruthenium and Co according to claim 1 2 The P nanoparticle three-function electrocatalyst is characterized in that the catalyst is used for hydrogen evolution, oxygen evolution and oxygen reduction reactions in alkaline electrolyte.
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