CN113437314A - Nitrogen-doped carbon-supported low-content ruthenium and Co2Three-function electrocatalyst of P nano particle and preparation method and application thereof - Google Patents

Nitrogen-doped carbon-supported low-content ruthenium and Co2Three-function electrocatalyst of P nano particle and preparation method and application thereof Download PDF

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CN113437314A
CN113437314A CN202110731615.1A CN202110731615A CN113437314A CN 113437314 A CN113437314 A CN 113437314A CN 202110731615 A CN202110731615 A CN 202110731615A CN 113437314 A CN113437314 A CN 113437314A
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catalyst
zif
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CN113437314B (en
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詹天荣
丁瑶
祁洪运
王磊
林健健
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Baoshilai New Materials Technology Suzhou Co ltd
Suzhou 30 Billion Technology Co ltd
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Qingdao University of Science and Technology
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Abstract

Nitrogen-doped carbon-loaded low-content ruthenium and Co2P nano-particle three-function electrocatalyst, 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 atmosphere2The 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, which is mainly caused byModification of Co for the introduction of low levels of noble metals2The 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

Nitrogen-doped carbon-supported low-content ruthenium and Co2Three-function electrocatalyst of P nano particle and its preparing methodAnd applications
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 Co2A 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.
Background art:
energy technologies such as fuel cells and metal-air batteries attract people's 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. At present, the catalyst used for ORR and HER reactions is mainly Pt and alloy thereof, and the catalyst used for OER reactions is mainly IrO2And RuO2However, these precious metals are rare in nature, and it is important to develop a novel, efficient and inexpensive electrocatalyst, in which a carbon-based non-precious metal catalyst has attracted a great deal of attention as a catalyst that is 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. ZIF-8 or ZIF-67 is formed by reacting zinc nitrate hexahydrate or cobalt nitrate hexahydrate with 2-methylimidazole, and considering the low boiling point of Zn, the zinc oxide can be used as a sacrificial template to remove metal Zn by a high-temperature calcination method to prepare a single-metal porous carbon material, realize heteroatom doping to further adjust the electronic property and the surface polarity, and improve the electrochemical catalytic activity of the composite material. It is now common to dope N, S, B, P or the like with heteroatoms that can be substituted for certain sp in the graphite lattice2The 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 amount of carbon nano-material is prepared by using ZIF as a precursor at presentThe method has the advantages of good performance, but the method for preparing 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 Ru2P 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 Co2The 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-Co2P/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 more ideal ORR reaction process, and has good long-term stability and excellent methanol tolerance. When the hydrogen is catalytically evolved, the concentration reaches 10mA/cm2The overpotential generated was only 43 mV. 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 content2A 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 Co2The 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-Co2A P/NC electrocatalyst;
the other purpose of the invention is to provide a nitrogen-doped carbon-loaded low-content ruthenium and Co2The 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 and transparent solution, weighing 508mg of cobalt acetate tetrahydrate, and 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 30 min; weighing 3.28g of 2-methylimidazole, dissolving in 40mL of deionized water, adding the solution into the solution, stirring for 24 hours, centrifuging, 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)Co2preparation of P/NC
Taking a proper amount of Zn-Co-ZIF @ PA-Co, putting the Zn-Co-ZIF @ PA-Co into a magnetic boat, placing the magnetic boat in the center of a tube furnace, and placing N2Heating to 700-1000 ℃ at a heating rate of 2-10 ℃/min as protective gas, and keeping the temperature for two hours to obtain a product Co2P/NC；
(d)Ru-Co2Preparation of P/NC
Weighing 50mg of Co obtained in step (c)2Dispersing the P/NC catalyst in 20mL deionized water, and violently stirring for 30min to obtain Co2P/NC dispersion; 0.5mL of RuCl3·xH2O aqueous solution was dropwise added to the above Co2P/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-Co2P/NC；
Wherein RuCl3·xH2The concentration of the O aqueous solution is 10 mg/mL; the content of Ru in the catalyst is lower than 2.6 at%, the elements Ru, Co and P are uniformly distributed, the average particle size of the catalyst is 400-450nm, and the Co in the catalyst is2The average particle diameter of P is 5-30 nm.
The invention also aims to provide nitrogen-doped carbon loaded low-content ruthenium and Co2The three-function electrocatalyst of the P nano-particle is applied to the catalysis of a cathode ORR, an anode OER of electrolyzed water 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 which is calcined at high temperatureLoaded with Co2The 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-Co2P/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 more ideal ORR reaction process, and has good long-term stability and excellent methanol tolerance. When the hydrogen is catalytically evolved, the concentration reaches 10mA/cm2The overpotential generated was only 43 mV.
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 noble metal Ru is lower than 2.6 at%, other raw materials are easy to purchase and prepare, the resources are rich, the price is lower, the operation is easy, and the large-scale production is facilitated;
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 supported low-content noble metal Ru and Co2The 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 20 wt% Pt/C and RuO2Compared 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 12Scanning Electron micrograph (B) of P/NC and Ru-Co obtained in example 12P/NC transmission electron micrograph (C).
FIG. 2 shows Ru-Co obtained in example 12P/NC, comparisonNPC obtained in example 1 and Co obtained in comparative example 22P/NC modifies ORR linear sweep voltammograms of RDEs, respectively.
FIG. 3 shows Ru-Co obtained in example 12ORR kinetic profiles of P/NC modified RDEs and corresponding K-L profiles.
FIG. 4 shows Ru-Co obtained in example 12P/NC and Pt/C catalyst modification of RDE for methanol tolerance map.
FIG. 5 shows Ru-Co obtained in example 12P/NC modifies the I-t plot of RDE at a constant voltage of 0.2V.
FIG. 6 shows Ru-Co obtained in example 12P/NC, NPC from comparative example 1 and Co from comparative example 22P/NC modifies the HER linear sweep voltammogram of the RDE, respectively.
FIG. 7 shows Ru-Co obtained in example 12P/NC, NPC from comparative example 1 and Co from comparative example 22P/NC modifies the OER linear sweep voltammogram of the RDE, respectively.
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 and transparent solution, weighing 508mg of cobalt acetate tetrahydrate, and 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 30 min; weighing 3.28g of 2-methylimidazole, dissolving in 40mL of deionized water, adding the solution into the solution, stirring for 24 hours, centrifuging, 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)Co2preparation of P/NC
Taking a proper amount of Zn-Co-ZIF @ PA-Co, putting the Zn-Co-ZIF @ PA-Co into a magnetic boat, placing the magnetic boat in the center of a tube furnace, and placing N2AsThe temperature of the protective gas is raised to 800 ℃ at the heating rate of 2 ℃/min, and the temperature is kept for two hours to obtain the product Co2P/NC。
(d)Ru-Co2Preparation of P/NC
Weighing 50mg of Co obtained in step (c)2Dispersing the P/NC catalyst in 20mL deionized water, and violently stirring for 30min to obtain Co2A dispersion of P/NC; 0.5mL of RuCl3·xH2Dropwise adding the above Co into O aqueous solution2P/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-Co2P/NC; obtaining Ru-Co2The content of Ru in the P/NC catalyst is 2.54 at%;
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)Co2preparation 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 placing the magnetic boat in the center of a tube furnace. N is a radical of2As protective gas, heating to 900 ℃ at the heating rate of 2 ℃/min, and keeping the temperature for two hours to obtain the product Co2P/NC。
(d)Ru-Co2Preparation of P/NC
Prepared according to the method and conditions of step (d) in example 1; obtaining Ru-Co2The content of Ru in the P/NC catalyst was 2.42 at%;
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)Co2preparation of P/NC
Taking a proper amount of Zn-Co-ZIF@ PA-Co is put in a magnetic boat which is placed in the center of a tube furnace, N2As protective gas, heating to 1000 ℃ at the heating rate of 2 ℃/min, and keeping the temperature for two hours to obtain the product Co2P/NC。
(d)Ru-Co2Preparation of P/NC
Prepared according to the method and conditions of step (d) in example 1; obtaining Ru-Co2The content of Ru in the P/NC catalyst was 2.36 at%;
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)Co2preparation 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 placing the magnetic boat in the center of a tube furnace. N is a radical of2As protective gas, heating to 900 ℃ at the heating rate of 4 ℃/min, and keeping the temperature for two hours to obtain the product Co2P/NC。
(d)Ru-Co2Preparation of P/NC
Prepared according to the method and conditions of step (d) in example 1; obtaining Ru-Co2The content of Ru in the P/NC catalyst was 2.42 at%;
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)Co2preparation 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 placing the magnetic boat in the center of a tube furnace. N is a radical of2As protective gas, heating to 900 ℃ at the heating rate of 10 ℃/min, and keeping the temperature for two hours to obtain the product Co2P/NC。
(d)Ru-Co2Preparation of P/NC
Prepared according to the method and conditions of step (d) in example 1; obtaining Ru-Co2The content of Ru in the P/NC catalyst is 2.31 at%;
comparative example 1:
(a) preparation of cobalt phytate (PA-Zn)
Weighing 158mg and 0.17mmol of sodium phytate at room temperature, dissolving the sodium phytate in 50mL of deionized water, magnetically stirring the solution to form a uniform and transparent solution, weighing 303.44mg and 1.02mmol of zinc nitrate hexahydrate, and adding the solution to form a white solution;
(b) preparation of Zn-ZIF @ PA-Zn
Weighing 1.34g of zinc nitrate hexahydrate and 3mmol of zinc nitrate hexahydrate, adding the zinc nitrate hexahydrate into the zinc phytate solution in the step (a), and performing ultrasonic dispersion for 30 min; weighing 3.28g of 2-methylimidazole, dissolving in 40mL of deionized water, adding the solution into the solution, stirring for 24 hours, centrifuging, 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 a proper amount of Zn-ZIF @ PA-Zn, placing the magnetic boat in the center of a tube furnace, and placing N2As protective gas, the temperature is raised to 900 ℃ at the heating rate of 2 ℃/min, and the temperature is kept for two hours to obtain the product NPC.
Comparative example 2:
(a) preparation of cobalt phytate (PA-Co)
Weighing 158mg of sodium phytate and 0.17mmol of sodium phytate at room temperature, dissolving the sodium phytate and 0.17mmol of sodium phytate in 50mL of deionized water, magnetically stirring the solution to form a uniform and transparent solution, weighing 508mg of cobalt acetate tetrahydrate and 1.02mmol of cobalt acetate, and adding the solution to form a purple solution;
(b) preparation of Zn-Co-ZIF @ PA-Co
Weighing 373.62mg, 1.5mmol cobalt acetate tetrahydrate and 446.2mg, 1.5mmol zinc nitrate hexahydrate, adding into the cobalt phytate solution in the step (a), and performing ultrasonic dispersion for 30 min; weighing 3.28g of 2-methylimidazole, dissolving in 40mL of deionized water, adding the solution into the solution, stirring for 24 hours, centrifuging, collecting precipitate, washing with deionized water and ethanol for three times respectively, and drying to obtain a catalyst precursor Co-ZIF @ PA-Co;
(c)Co2preparation of P/NC
Taking a proper amount of Zn-Co-ZIF @ PA-Co, putting the Zn-Co-ZIF @ PA-Co into a magnetic boat, placing the magnetic boat in the center of a tube furnace, and placing N2As protective gas, heating to 800 ℃ at the heating rate of 2 ℃/min, and keeping the temperature for two hours to obtain the product Co2P/NC。
FIG. 1 shows Zn-Co-ZIF @ PA-Co and Co obtained in example 1(A) and example 1(B)2Scanning Electron microscopy of P/NC and Ru-Co obtained in example 12P/NC (C) transmission electron microscope picture. 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＝Jk -1+(Bω1/2)-1
B＝0.62n F C0 D0 2/3v1/6
Wherein F is 96485C/mol, C0＝1.2×10-3mol/L，D0＝1.9×10-5cm2/s，v＝0.01cm2/s。
FIG. 2 shows Ru-Co obtained in example 12P/NC, NPC from comparative example 1 and Co from comparative example 22P/NC modifies ORR linear sweep voltammograms of RDEs, respectively. As can be seen from FIG. 2, the low content of noble metal-doped Ru-Co2P/NC has the highest initial potential and current density, which indicates that the noble metal Ru is doped with Co2The 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 reaction2Electrochemical activity ratio of P/NC Co2P/NC and metal-free NPC are preferred.
FIG. 3 shows Ru-Co obtained in example 12Kinetic 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, and nearly no HO is generated2 -4 electron transfer process of the product, thereby illustrating Ru-Co2The ORR process catalyzed by the P/NC modified electrode is an ideal 4-electron reaction mechanism.
FIG. 4 shows Ru-Co obtained in example 12A methanol tolerance graph of P/NC catalyst modified RDE is shown, and an I-t curve in the graph shows that after 3mL of methanol is added into KOH electrolyte, the current retention rate is recovered to 91.5%, while the precious metal Pt/C catalyst is only recovered to 78.8%, which shows that the Ru-Co catalyst has high catalytic activity and high catalytic activity, and the like2P/NC has superior methanol interference resistance over Pt/C catalysts, which may be due to the ZIF-derived carbon matrix playing a key role in supporting the metal species active sites, enhancing the structural stability and catalytic stability of the catalyst.
FIG. 5 shows Ru-Co obtained in example 12P/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-Co2The 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 12P/NC, NPC from comparative example 1 and Co from comparative example 22P/NC modifies the HER linear sweep voltammogram of the RDE, respectively. Ru-Co as shown2The P/NC has the minimum initial potential and the maximum current density in the range of 0-0.6V. Meanwhile, when the current density is-10 mA/cm2In the presence of Ru-Co2P/NC has the lowest overpotential, which is obviously superior to Co2P/NC and NPC. The results show that the introduction of low content of noble metal ruthenium effectively reduces the overpotential thereof. The main reason is 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 ruthenium and Co2The P nano particles increase electrochemical active sites, are more favorable for electron conduction, and greatly improve the electrocatalytic performance of the material, soThe lowest overpotential is exhibited.
FIG. 7 shows Ru-Co obtained in example 12P/NC, NPC from comparative example 1 and Co from comparative example 22P/NC modifies the OER linear sweep voltammogram of the RDE, respectively. Ru-Co as shown2The P/NC has the minimum initial potential and the maximum current density in the measured potential interval. Meanwhile, when the current density is 10mA/cm2In the presence of Ru-Co2P/NC has the lowest overpotential, which is obviously superior to Co2P/NC and NPC. The results show that the introduction of low content of noble metal ruthenium effectively reduces the overpotential thereof. The main reason is that the carbonized material inherits the Zn-Co-ZIF porous structure, and the introduction of the low-content noble metal Ru changes Co2The 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 Co2The 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 reacts with a cobalt phytate solution, purple solid is collected and calcined at high temperature to obtain nitrogen-doped carbon-supported Co2Nanocomposite of P nanoparticles by adsorption of RuCl3·xH2O introducing a small amount of noble metal ruthenium into the composite catalyst to obtain the three-function electrocatalyst marked as Ru-Co2P/NC；
The nitrogen-doped carbon supports low content of ruthenium and Co2The 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 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 30 min; weighing 3.28g of 2-methylimidazole, dissolving in 40mL of deionized water, adding the solution into the solution, stirring for 24 hours, centrifuging, 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)Co2preparation of P/NC
Taking a proper amount of Zn-Co-ZIF @ PA-Co, putting the magnetic boat in the center of a tube furnace, and placing N2Heating to 700-1000 ℃ at a heating rate of 2-10 ℃/min as protective gas, and keeping the temperature for two hours to obtain a product Co2P/NC；
(d)Ru-Co2Preparation of P/NC
Weighing 50mg of Co obtained in step (c)2Dispersing the P/NC catalyst in 20mL deionized water, and violently stirring for 30min to obtain Co2P/NC dispersion; 0.5mL of RuCl3·xH2O aqueous solution was dropwise added to the above Co2P/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-Co2P/NC；
Wherein RuCl3·xH2The concentration of the O aqueous solution is 10 mg/mL; the content of Ru in the catalyst is lower than 2.6 at%, the elements Ru, Co and P are uniformly distributed, the average particle size of the catalyst is 400-450nm, and the Co in the catalyst is2The average particle diameter of P is 5-30 nm.
2. The nitrogen-doped carbon supported low-content ruthenium and Co according to claim 12The 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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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113862693A (en) * 2021-10-13 2021-12-31 中国海洋大学 Preparation method and application of nitrogen-doped mesoporous carbon-loaded high-dispersion Ru nanoparticle catalyst
CN114318362A (en) * 2021-12-24 2022-04-12 复旦大学 Ruthenium nanocluster hydrogen evolution electrocatalyst and super-assembly method thereof
CN114481204A (en) * 2022-01-26 2022-05-13 青岛科技大学 Preparation of cobalt phosphide-supported noble metal nano material
CN116078413A (en) * 2022-12-13 2023-05-09 青岛科技大学 Low-noble metal phosphide electrocatalyst based on microbial template derivatization and preparation method and application thereof
CN116581307A (en) * 2023-06-19 2023-08-11 广东格林赛福能源科技有限公司 S-doped NC/Co/Cs 2 Se/CoSe catalyst, preparation method and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109012749A (en) * 2018-08-14 2018-12-18 青岛科技大学 Nonmetallic difunctional VPO catalysts and its preparation method and application based on ZIF-8 phosphorus sulphur codope
CN109065897A (en) * 2018-08-14 2018-12-21 青岛科技大学 Phosphorus-doped porous carbon-coated cobaltosic oxide oxygen reduction catalyst and preparation method and application thereof
US20190067706A1 (en) * 2017-08-29 2019-02-28 Uchicago Argonne, Llc Carbon dioxide reduction electro catalysts prepared for metal organic frameworks
CN109841854A (en) * 2017-11-29 2019-06-04 中国科学院大连化学物理研究所 A kind of nitrogen-doped carbon-supported antozone reducing catalyst and preparation method thereof
CN110523424A (en) * 2019-08-15 2019-12-03 广西师范大学 One kind being based on Ru/NPC-CoxO catalyst for preparing hydrogen and preparation method
CN111001427A (en) * 2019-12-24 2020-04-14 山西大学 Cobalt-nitrogen co-doped carbon-based electrocatalyst material and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20190067706A1 (en) * 2017-08-29 2019-02-28 Uchicago Argonne, Llc Carbon dioxide reduction electro catalysts prepared for metal organic frameworks
CN109841854A (en) * 2017-11-29 2019-06-04 中国科学院大连化学物理研究所 A kind of nitrogen-doped carbon-supported antozone reducing catalyst and preparation method thereof
CN109012749A (en) * 2018-08-14 2018-12-18 青岛科技大学 Nonmetallic difunctional VPO catalysts and its preparation method and application based on ZIF-8 phosphorus sulphur codope
CN109065897A (en) * 2018-08-14 2018-12-21 青岛科技大学 Phosphorus-doped porous carbon-coated cobaltosic oxide oxygen reduction catalyst and preparation method and application thereof
CN110523424A (en) * 2019-08-15 2019-12-03 广西师范大学 One kind being based on Ru/NPC-CoxO catalyst for preparing hydrogen and preparation method
CN111001427A (en) * 2019-12-24 2020-04-14 山西大学 Cobalt-nitrogen co-doped carbon-based electrocatalyst material and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HUI QI 等: "Bimetallic ZIF-Derived Co/N-Codoped Porous Carbon Supported Ruthenium Catalysts for Highly Efficient Hydrogen Evolution Reaction", 《NANOMATERIALS》 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113862693A (en) * 2021-10-13 2021-12-31 中国海洋大学 Preparation method and application of nitrogen-doped mesoporous carbon-loaded high-dispersion Ru nanoparticle catalyst
CN113862693B (en) * 2021-10-13 2023-08-08 中国海洋大学 Preparation method and application of nitrogen-doped mesoporous carbon-loaded high-dispersion Ru nanoparticle catalyst
CN114318362A (en) * 2021-12-24 2022-04-12 复旦大学 Ruthenium nanocluster hydrogen evolution electrocatalyst and super-assembly method thereof
CN114318362B (en) * 2021-12-24 2023-08-29 复旦大学 Ruthenium nanocluster hydrogen evolution electrocatalyst and super-assembly method thereof
CN114481204A (en) * 2022-01-26 2022-05-13 青岛科技大学 Preparation of cobalt phosphide-supported noble metal nano material
CN114481204B (en) * 2022-01-26 2023-11-03 青岛科技大学 Preparation of cobalt phosphide loaded noble metal nano material
CN116078413A (en) * 2022-12-13 2023-05-09 青岛科技大学 Low-noble metal phosphide electrocatalyst based on microbial template derivatization and preparation method and application thereof
CN116581307A (en) * 2023-06-19 2023-08-11 广东格林赛福能源科技有限公司 S-doped NC/Co/Cs 2 Se/CoSe catalyst, preparation method and application thereof
CN116581307B (en) * 2023-06-19 2024-01-30 广东格林赛福能源科技有限公司 S-doped NC/Co/Cs 2 Se/CoSe catalyst, preparation method and application thereof

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