CN111701607A - MnCo2O4@Ni2P/NF difunctional full-hydrolysis catalyst and preparation method and application thereof - Google Patents

MnCo2O4@Ni2P/NF difunctional full-hydrolysis catalyst and preparation method and application thereof Download PDF

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CN111701607A
CN111701607A CN202010545042.9A CN202010545042A CN111701607A CN 111701607 A CN111701607 A CN 111701607A CN 202010545042 A CN202010545042 A CN 202010545042A CN 111701607 A CN111701607 A CN 111701607A
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葛婧
张纹
夏涛
涂君
陈三平
谢钢
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Northwestern University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/187—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/28—Phosphorising
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The invention discloses MnCo with a heterogeneous interface2O4@Ni2P/NF difunctional catalyst for full hydrolysis. Firstly, preparing the MnCo loaded with the foamed nickel by a solvothermal method and high-temperature calcination2O4the/NF nanowire array precursor is further coated with Ni on the precursor serving as a template under the hydrothermal condition2(OH)2Nanosheet to form MnCo2O4@Ni2(OH)2a/NF composite structure precursor. Finally, the high-temperature in-situ phosphorization is carried out to prepare the catalystMnCo of heterointerface2O4@Ni2P/NF catalyst for full hydrolysis. Wherein, the catalyst grown on the foam nickel carrier in situ has more catalytic active sites and better stability, and simultaneously Ni2P-oriented MnCo2O4The charge transfer of (2) can effectively inhibit the Mn in the structure3+The induced ginger-Taylor distortion can improve the conductivity of the material, thereby synergistically improving the OER and HER performances of the material. The catalyst prepared by the invention has excellent difunctional full-hydrolytic performance and can be applied to water electrolysis.

Description

MnCo2O4@Ni2P/NF difunctional full-hydrolysis catalyst and preparation method and application thereof
Technical Field
The invention relates to MnCo with a heterogeneous interface2O4@Ni2P/NF difunctional full-hydrolytic catalyst and a preparation method and application thereof, belonging to the technical field of hydrolytic catalysts.
Background
With the energy crisis caused by the consumption of fossil fuels in the world and the increasing problem of environmental pollution, the search for efficient, clean and sustainable energy is becoming an important issue. Hydrogen has been developed as a renewable, economical and effective clean energy source. The electrolysis of water has gained wide attention as an efficient and sustainable method in the hydrogen production method. However, hydrogen production from water electrolysis requires a large overpotential drive due to the slow kinetics of the Oxygen Evolution Reaction (OER). At present, the noble metal catalyst IrO2，RuO2And Pt is considered to be a highly efficient catalyst for oxygen evolution reaction in alkaline environment. However, the scarcity of these precious metal elements on earth and the high development cost seriously hinder their application in actual production and life. Therefore, the development of the high-efficiency non-noble metal water electrolysis catalyst is significant. The first row transition elements of the periodic table of elements are of great interest because of the synergy between internal multiple states, abundant electrochemical redox reactions, and excellent cycling performance in alkaline solutions at high anodic potentials.
Among these, the cobalt-based spinel structure-based catalyst MCo2O4(M = Ni, Zn, Mn or Cu) shows excellent OER catalytic performance and can be used as potential non-noble metal OER catalystAnd (3) preparing. However, it was found that only Mn was measured3+Has been shown to be the active site of OER, but at the same time Mn3+Occupy octahedral centers of crystal lattices in spinel structure and produce ginger-taylor distortion, resulting in MnCo2O4Shows a decrease in OER catalytic performance for the purpose of improving MnCo2O4The inhibition of ginger-taylor distortion is an effective solution.
Disclosure of Invention
The invention aims to provide MnCo with a heterogeneous interface2O4@Ni2The P/NF difunctional full-hydrolytic catalyst, the preparation method and the application thereof are used for improving the applicability of the non-noble metal catalyst in the technical field of water electrolysis.
The realization process of the invention is as follows:
MnCo2O4@Ni2the P/NF difunctional full-hydrolysis catalyst is characterized in that: MnCo2O4@Ni2MnCo in P/NF component2O4And Ni2P forms a hetero-interface whose interface composition is MnCo2O4(311) And Ni2P（111），MnCo2O4JCPDS card number 23-1237 corresponding to the powder diffraction pattern of (1), Ni2JCPDS card No. 03-0953 corresponding to powder diffraction pattern of P, MnCo2O4@Ni2P is loaded on NF, and the NF is foamed nickel.
The above MnCo2O4@Ni2The morphology of P is Ni2The P nanosheet coated MnCo film with the diameter of 100-130 nanometers2O4The one-dimensional nanowire array structure is 15-30 microns in length, and the diameter of the nanowire composite nanosheet is 150-200 nanometers.
The above MnCo2O4@Ni2The preparation method of the P/NF difunctional full-hydrolysis catalyst comprises the following steps:
(1) dissolving soluble manganese salt (II), soluble cobalt salt (II), urea and ammonium fluoride in a mixed solvent of ethanol and water, adding foamed nickel NF, placing in a reaction kettle for reaction at 110-150 ℃, washing, drying and calcining the product to obtain the foamed nickel negativeLoaded MnCo2O4A nanowire array precursor;
(2) dissolving soluble nickel salt (II) and urea in water, and adding the MnCo obtained in the step (1)2O4/NF precursor, placing the precursor into a reaction kettle, and carrying out hydrothermal reaction at 90-120 ℃ to obtain MnCo2O4@Ni2(OH)2a/NF composite structure precursor;
(3) mixing MnCo2O4@Ni2(OH)2Performing high-temperature phosphating treatment on the precursor with the/NF composite structure and sodium hypophosphite by adopting a chemical vapor deposition method at the temperature of 300-400 ℃ in an argon atmosphere to obtain MnCo2O4@Ni2P/NF difunctional catalyst for full hydrolysis.
In the step (1), the following cleaning treatment is carried out before the foam nickel is used: firstly putting the foamed nickel into 3 mol/L hydrochloric acid for ultrasonic treatment for 15 min, washing the foamed nickel with ultrapure water, then respectively carrying out ultrasonic treatment on the foamed nickel in acetone, absolute ethyl alcohol and the ultrapure water for 15 min, and finally taking out the foamed nickel for natural drying.
In the steps (1) and (2), the soluble manganese salt (II), the soluble cobalt salt (II) and the soluble nickel salt (II) are selected from corresponding metal chloride, nitrate, acetate, formate and sulfate.
In the step (1), the volume ratio of the ethanol to the water is 1 (3-7), preferably 1: 5.
In the step (1), the molar ratio of the soluble manganese salt (II) to the soluble cobalt salt (II) is 1 (1-5). The inventors have found that more preferably, when the molar ratio of the soluble manganese salt (II) to the soluble cobalt salt (II) is 1:2, MnCo is obtained2O4The nanowire array is most uniform in size, and when the molar concentration range of the soluble cobalt salt (II) is 0.017-0.083M, the electrochemical performance is best.
In the step (1), the mol ratio of the soluble cobalt salt (II), the urea and the ammonium fluoride is (1-5): 1: 2.
in the step (1), the loading capacity of the single-sheet foamed nickel carrier is 0.32-0.46 mg/cm2。
In the step (2), the molar ratio of the soluble nickel salt (II) to the urea is (1-3): 3, the molar concentration of the soluble nickel salt (II) is 0.03-0.1M.
In the step (3), the MnCo2O4@Ni2(OH)2The precursor with the/NF composite structure is washed by ultrapure water and absolute ethyl alcohol respectively for three times before high-temperature phosphating treatment, and then dried in an oven at 60 ℃ for 8 hours.
In the step (3), the temperature rise rate of the high-temperature phosphating is 1-5 ℃/min, and the heat preservation time is 1-3 h. During phosphating, insufficient phosphating temperature and too short phosphating time can cause insufficient phosphating degree of the material; too high a phosphating temperature and too fast a temperature rise rate can lead to loss of the phosphorus source and structural collapse of the material. More preferably, the temperature of the high-temperature phosphating treatment is 350 ℃, the heating rate is 2 ℃/min, and the heat preservation time is 2 h.
The invention prepares MnCo through solvothermal method and calcination treatment2O4A precursor coated with Ni (OH)2The obtained MnCo2O4@Ni2(OH)2the/NF composite structure is subjected to in-situ high-temperature phosphating treatment to prepare MnCo with a heterogeneous interface2O4@Ni2P/NF difunctional catalyst for full hydrolysis.
The invention also provides the MnCo with the heterogeneous interface2O4@Ni2The water electrolysis application of the P/NF difunctional full-hydrolysis catalyst shows better electrocatalytic Oxygen Evolution Reaction (OER), electrocatalytic Hydrogen Evolution Reaction (HER) and full-hydrolysis reaction performances and reaches the level of commercial noble metals.
Ni2P is a bifunctional electrocatalyst with excellent performance, which has abundant active sites and metallic properties, which makes it highly conductive and fast electron transfer capability. Thus precursor MnCo2O4Nanowire as skeleton, Ni2P nanosheet introduced in-situ growth to form MnCo2O4@Ni2A P-hetero interface. The catalyst with the heterogeneous interface of the invention is MnCo2O4@Ni2The P/NF component contains MnCo2O4And Ni2P, whose interfacial composition is MnCo2O4(311) And Ni2P (111), the formation of a heterogeneous interface can effectively improve the charge transfer rate and the conductivity of the material, and effectively adjusts MnCo2O4The electron structure of (2) changes the density of the electron cloud of the active center, thereby inhibiting the distortion of ginger-Taylor and further enhancing the OER catalytic performance of the material. Under the synergistic effect of the two, the catalyst MnCo2O4@Ni2The OER catalytic performance of P/NF is obviously improved, Ni2P is a bifunctional electrocatalyst with excellent performance, and the catalyst shows excellent Hydrogen Evolution Reaction (HER) performance and can be used as a bifunctional water electrolysis catalyst. The invention effectively inhibits the OER performance attenuation caused by ginger-Taylor distortion by introducing a heterogeneous interface, so that the catalyst MnCo2O4@Ni2The OER, HER and total water splitting performance of the P/NF reach the commercial precious metal level.
Therefore, compared with the prior art, the invention has the beneficial effects that:
1. the catalyst has excellent Oxygen Evolution Reaction (OER) and Hydrogen Evolution Reaction (HER) performances under the condition of alkaline electrolyte, simultaneously shows better full-hydrolysis performance, and can be used as an efficient bifunctional full-hydrolysis catalyst;
2. the catalyst of the invention utilizes MnCo2O4And Ni2The mutual combination of P generates a heterojunction interface, and the heterojunction interface has high-efficiency electron transfer efficiency, a large surface active area and long-term catalytic stability;
3. ni in catalyst2The introduction of P regulates and controls MnCo2O4The surface electronic structure of (1) effectively inhibits Mn in octahedral crystal lattices3+The resulting ginger-taylor distortion and the resulting improvement in electrical conductivity and abundance of active catalytic sites;
4. the metal used by the catalyst is non-noble metal, and the high-efficiency and stable bifunctional full-hydrolysis catalyst is prepared under the condition of low cost;
5. the catalyst of the invention is prepared on a foamed nickel substrate. The catalyst is very convenient to use and can be directly used without being coated on the surface of an electrode or other conductive substrates.
Drawings
FIG. 1 shows MnCo of example 12O4@Ni2XRD pattern of P/NF heterojunction catalyst;
FIG. 2 shows MnCo of example 12O4@Ni2SEM image of P/NF heterojunction catalyst;
FIG. 3 shows MnCo of example 12O4@Ni2TEM image of P/NF heterojunction catalyst;
FIG. 4 shows MnCo of comparative example 12O4XRD pattern of/NF;
FIG. 5 is MnCo of comparative example 12O4SEM picture of/NF;
FIG. 6 is MnCo of comparative example 22O4@Ni(OH)2XRD pattern of/NF;
FIG. 7 shows MnCo of comparative example 22O4@Ni(OH)2SEM picture of/NF;
FIG. 8 shows MnCo of example 12O4@Ni2P/NF heterojunction catalyst, foam nickel NF, commercial noble metal Pt/C/NF and MnCo2O4/NF and MnCo2O4@Ni(OH)2A plot of hydrogen evolution reaction performance versus NF;
FIG. 9 shows MnCo of example 12O4@Ni2A hydrogen evolution reaction stability diagram of the P/NF heterojunction catalyst;
FIG. 10 shows MnCo of example 12O4@Ni2P/NF heterojunction catalyst, foam nickel NF and commercial noble metal RuO2/NF、MnCo2O4/NF and MnCo2O4@Ni(OH)2Comparative graph of oxygen evolution reaction performance of/NF;
FIG. 11 shows MnCo of example 12O4@Ni2An oxygen evolution reaction stability diagram of the P/NF heterojunction catalyst;
FIG. 12 shows MnCo of example 12O4@Ni2P/NF heterojunction catalyst and commercial noble metal RuO2The electrolytic water performance of/NF-Pt/C is compared with that of the original electrolytic water;
FIG. 13 shows MnCo of example 12O4@Ni2P/NF heterojunction catalyst and commercial noble metal RuO2Comparative plot of electrolyzed water stability of/NF-Pt/C.
Detailed description of the invention
In order to better illustrate the implementation and advantageous effects of the present invention, the present invention is further illustrated by the following examples, comparative examples and experimental examples, but not by way of limitation of the scope of the implementation of the present invention.
Example 1
This example provides a MnCo with a hetero-interface2O4@Ni2The preparation method of the P/NF difunctional full-hydrolysis catalyst comprises the following specific steps:
(1) firstly putting foam Nickel (NF) into 3 mol/L hydrochloric acid for ultrasonic treatment for 15 min, taking out the foam nickel, respectively putting the foam nickel into acetone, absolute ethyl alcohol and ultrapure water for ultrasonic treatment for 15 min, and finally taking out the foam nickel for natural drying;
(2) dissolving 0.099g of manganese chloride, 0.29 g of cobalt nitrate, 0.061 g of urea and 0.074 g of ammonium fluoride in a mixed solution of 25 mL of ultrapure water and 5 mL of absolute ethyl alcohol, putting a piece of cleaned and dried 1 cm × 2.5.5 cm NF into a reaction kettle for sealing, carrying out thermal reaction at 120 ℃ for 12 h, then taking out a sample, washing the sample with the ultrapure water and the absolute ethyl alcohol for three times respectively, drying, and calcining in the air at 400 ℃ for 2 h to obtain MnCo2O4a/NF nanowire array precursor;
(3) MnCo prepared in the step (2)2O4the/NF nanowire array precursor is put into 15 mL of aqueous solution containing 0.145 g of nickel nitrate and 0.090g of urea, transferred into a reaction kettle, sealed and reacted for 6 h at 100 ℃. Taking out the obtained sample, washing the sample with ultrapure water and absolute ethyl alcohol for three times respectively, and drying to obtain MnCo2O4@Ni2(OH)2a/NF composite structure precursor;
(4) mixing MnCo2O4@Ni2(OH)2before/NF composite structureAnd putting the precursor and sodium hypophosphite into a tubular furnace, heating to 350 ℃ at the heating rate of 2 ℃/min, pyrolyzing for 2 h, and introducing flowing Ar gas into the tubular furnace in the phosphating process. Cooling to room temperature to obtain MnCo with a heterogeneous interface2O4@Ni2P/NF difunctional catalyst for full hydrolysis.
The catalyst obtained in example 1 was examined, and fig. 1, 2 and 3 respectively show MnCo prepared in this example2O4@Ni2XRD, SEM and TEM images of P/NF heterojunction catalysts.
Comparative example 1
Comparative example 1 provided an electrocatalyst, MnCo2O4/NF was MnCo treated by the same treatment method as used in example 12O4/NF nanowire array precursor.
The catalyst obtained in comparative example 1 was examined, and fig. 4 and 5 are XRD and SEM images, respectively, of the catalyst prepared in this comparative example.
Comparative example 2
Comparative example 2 provides an electrocatalyst, MnCo2O4@Ni(OH)2/NF was MnCo treated by the same treatment method as used in example 12O4@Ni2(OH)2a/NF composite structure precursor.
The catalyst obtained in comparative example 2 was examined, and fig. 6 and 7 are XRD and SEM images, respectively, of the catalyst prepared in this comparative example.
Comparative example 3
The catalyst provided by the comparative example is the existing Pt/C catalyst, the catalyst is coated on the foamed nickel after being subjected to ultrasonic dispersion in ethanol, and the loading capacity of a single foamed nickel carrier is 0.43-0.48 mg/cm2。
Comparative example 4
The catalyst provided by the comparative example is the existing RuO2The catalyst is coated on the foamed nickel after being subjected to ultrasonic dispersion in ethanol, and the loading capacity of the single-piece foamed nickel carrier is 0.42-0.46 mg/cm2。
Experimental example 1
Respectively with MnCo of example 12O4@Ni2P/NF heterojunction catalyst, MnCo of comparative example 12O4/NF, MnCo of comparative example 22O4@Ni2(OH)2The HER performance test was performed using Pt/C/NF as the test sample and Pt/C/NF as the commercial noble metal of comparative example 3. With MnCo of example 12O4@Ni2And (3) taking the P/NF heterojunction catalyst as a test sample to perform HER stability test. An electrolytic cell is selected as a container, a test sample is a working electrode, a platinum sheet is a counter electrode, a saturated calomel electrode is a reference electrode, and an electrolyte is a 1mol/L potassium hydroxide solution. All voltage ranges mentioned herein are with respect to the Reversible Hydrogen Electrode (RHE).
HER performance test conditions: temperature: room temperature; LSV scan rate: 1 mV/s; LSV test voltage range: -1.0-0V; current compensation: 90 percent.
HER stability test conditions: temperature: room temperature; current density: 10mA/cm2(ii) a And (3) testing time: for 20 hours.
The results of comparison after the above-mentioned test under the above-mentioned method and conditions are shown in FIGS. 8 and 9, from which MnCo can be seen2O4@Ni2The P/NF heterojunction catalyst has HER catalytic performance close to that of the commercial noble metal Pt/C/NF of the comparative example 3 and has the current density of 10mA/cm2The overpotential was 57 mV. The catalyst is used at the current density of 10mA/cm2The performance of the catalyst is not changed greatly after the hydrogen evolution reaction is carried out for 20 hours.
Experimental example 2
Respectively with MnCo of example 12O4@Ni2P/NF heterojunction catalyst, MnCo of comparative example 12O4/NF, MnCo of comparative example 22O4@Ni2(OH)2/NF and RuO, a commercial noble metal of comparative example 42the/NF was used as a test sample to conduct the OER performance test. With MnCo of example 12O4@Ni2And (3) taking the P/NF heterojunction catalyst as a test sample, and carrying out an OER stability test. An electrolytic cell is selected as a container, a test sample is a working electrode, a platinum sheet is a counter electrode, a saturated calomel electrode is a reference electrode, and an electrolyte is a 1mol/L potassium hydroxide solution.
OER test conditions: temperature: room temperature; LSV scan rate: 1 mV/s; LSV test voltage range: 1.0-2.0V; current compensation: 90 percent.
OER stability test conditions: temperature: room temperature; current density: 10mA/cm2(ii) a And (3) testing time: and (5) 20 h.
The results of comparison after the above-mentioned test under the above-mentioned method and conditions are shown in FIGS. 10 and 11, from which MnCo can be seen2O4@Ni2The P/NF heterojunction catalyst has excellent OER catalytic performance and stability. The catalyst is used at the current density of 10mA/cm2The overpotential was 240 mV and at a current density of 10mA/cm2The performance of the catalyst is not greatly changed after the oxygen evolution reaction is carried out for 20 hours.
Experimental example 3
Respectively with MnCo of example 12O4@Ni2P/NF heterojunction catalyst and commercial noble metal RuO assembled in comparative example 3 and comparative example 42the/NF-Pt/C electrode pair is used as a test sample to carry out the test of the full hydrolytic performance and the stability. An electrolytic bath is selected as a container, a test sample is a working electrode, and the electrolyte is 1mol/L potassium hydroxide solution.
Electrolytic water performance test conditions: temperature: room temperature; LSV scan rate: 1 mV/s; LSV test voltage range: -1.0-0V; current compensation: 90 percent.
Electrolytic water stability test conditions: temperature: room temperature; current density: 10mA/cm2(ii) a And (3) testing time: and (5) 30 h.
The results of comparison after the above-mentioned test under the above-mentioned method and conditions are shown in FIGS. 12 and 13, from which MnCo can be seen2O4@Ni2P/NF heterojunction catalysts with commercial noble metal RuO assembled similarly to comparative examples 3 and 42Excellent full-hydrolytic catalytic performance of a/NF-Pt/C electrode pair, with the current density of 10mA/cm2The electrolytic voltage is 1.63V, and the electrolyte has very good stability and the current density is 10mA/cm2The performance of the catalyst is not greatly changed after 30 hours of electrolysis.
In conclusion, the MnCo with the heterogeneous interface provided by the invention2O4@Ni2The P/NF difunctional full-hydrolysis catalyst has excellent catalytic performance and stability in the aspect of water electrolysis of alkaline electrolyte, is simple to prepare and has good application prospect.

Claims (10)

1.MnCo2O4@Ni2The P/NF difunctional full-hydrolysis catalyst is characterized in that: MnCo2O4@Ni2MnCo in P/NF component2O4And Ni2P forms a hetero-interface whose interface composition is MnCo2O4(311) And Ni2P（111），MnCo2O4JCPDS card number 23-1237 corresponding to the powder diffraction pattern of (1), Ni2JCPDS card No. 03-0953 corresponding to powder diffraction pattern of P, MnCo2O4@Ni2P is loaded on NF, and the NF is foamed nickel.
2. The MnCo of claim 12O4@Ni2The P/NF difunctional full-hydrolysis catalyst is characterized in that: MnCo2O4@Ni2The morphology of P is Ni2The P nanosheet coated MnCo film with the diameter of 100-130 nanometers2O4The one-dimensional nanowire array structure is 15-30 microns in length, and the diameter of the nanowire composite nanosheet is 150-200 nanometers.
3.MnCo2O4@Ni2The preparation method of the P/NF difunctional full-hydrolytic catalyst is characterized by comprising the following steps:
(1) dissolving soluble manganese salt (II), soluble cobalt salt (II), urea and ammonium fluoride in a mixed solvent of ethanol and water, adding foamed nickel NF, placing in a reaction kettle for reaction at 110-150 ℃, washing, drying and calcining the product to obtain the foamed nickel-loaded MnCo2O4A nanowire array precursor;
(2) dissolving soluble nickel salt (II) and urea in water, and adding the MnCo obtained in the step (1)2O4the/NF precursor is put into a reaction kettle to carry out hydrothermal reaction at 90-120 ℃ to prepare MnCo2O4@Ni2(OH)2a/NF composite structure precursor;
(3) mixing MnCo2O4@Ni2(OH)2Performing high-temperature phosphating treatment on the precursor with the/NF composite structure and sodium hypophosphite by adopting a chemical vapor deposition method at the temperature of 300-400 ℃ in an argon atmosphere to obtain MnCo2O4@Ni2P/NF difunctional catalyst for full hydrolysis.
4. The MnCo of claim 32O4@Ni2The preparation method of the P/NF difunctional full-hydrolytic catalyst is characterized by comprising the following steps: in the steps (1) and (2), the soluble manganese salt (II), the soluble cobalt salt (II) and the soluble nickel salt (II) are selected from corresponding metal chloride, nitrate, acetate, formate and sulfate.
5. The MnCo of claim 32O4@Ni2The preparation method of the P/NF difunctional full-hydrolytic catalyst is characterized by comprising the following steps: in the step (1), the molar ratio of the soluble manganese salt (II) to the soluble cobalt salt (II) is 1 (1-5).
6. The MnCo of claim 32O4@Ni2The preparation method of the P/NF difunctional full-hydrolytic catalyst is characterized by comprising the following steps: in the step (1), the volume ratio of the ethanol to the water is 1 (3-7).
7. The MnCo of claim 32O4@Ni2The preparation method of the P/NF difunctional full-hydrolytic catalyst is characterized by comprising the following steps: in the step (1), the mol ratio of the soluble cobalt salt (II), urea and ammonium fluoride is (1-5): 1:2, the loading capacity of the single-sheet foamed nickel carrier is 0.32-0.46 mg/cm2。
8. The MnCo of claim 32O4@Ni2The preparation method of the P/NF difunctional full-hydrolytic catalyst is characterized by comprising the following steps: in the step (2), soluble nickelThe molar ratio of the salt (II) to the urea is (1-3): 3, the molar concentration of the soluble nickel salt (II) is 0.03-0.1M.
9. The MnCo of claim 32O4@Ni2The preparation method of the P/NF difunctional full-hydrolytic catalyst is characterized by comprising the following steps: in the step (3), the temperature rise rate of the high-temperature phosphating is 1-5 ℃/min, and the heat preservation time is 1-3 h.
10. MnCo of claim 12O4@Ni2The application of P/NF as double-function full-hydrolytic catalyst.
CN202010545042.9A 2020-06-15 2020-06-15 MnCo2O4@Ni2P/NF difunctional full-hydrolysis catalyst and preparation method and application thereof Pending CN111701607A (en)

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CN112909271A (en) * 2021-01-25 2021-06-04 华南理工大学 Integral transition metal phosphide electrocatalyst with sea urchin-shaped morphology and preparation method and application thereof
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CN112909271A (en) * 2021-01-25 2021-06-04 华南理工大学 Integral transition metal phosphide electrocatalyst with sea urchin-shaped morphology and preparation method and application thereof
CN113201752A (en) * 2021-03-30 2021-08-03 北京化工大学 Preparation method and application of CoNiP-P nano catalyst with rich heterojunction
CN113684501A (en) * 2021-07-19 2021-11-23 中国海洋大学 Nickel-iron-based phosphide electrocatalytic material and preparation method and application thereof
CN115044933A (en) * 2022-05-09 2022-09-13 海南大学 Ni 12 P 5 Or Ni 2 Preparation method and application of P nano array
CN115044933B (en) * 2022-05-09 2023-09-29 海南大学 Ni (nickel) 12 P 5 Or Ni 2 Preparation method and application of P nano array
WO2024002126A1 (en) * 2022-07-01 2024-01-04 中国科学院大连化学物理研究所 Preparation method for one-dimensional ni12p5/ni2p polycrystalline heterostructure catalyst used for efficient water oxidation

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