CN110711597B - Co-Mo-P-O electrocatalyst and preparation method and application thereof - Google Patents
Co-Mo-P-O electrocatalyst and preparation method and application thereof Download PDFInfo
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- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 59
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 35
- 239000001257 hydrogen Substances 0.000 claims abstract description 35
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 17
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims abstract description 15
- 238000004070 electrodeposition Methods 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 8
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229940044175 cobalt sulfate Drugs 0.000 claims abstract description 6
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims abstract description 6
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000001509 sodium citrate Substances 0.000 claims abstract description 6
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 6
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 6
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 6
- 235000015393 sodium molybdate Nutrition 0.000 claims abstract description 6
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002105 nanoparticle Substances 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 71
- 229910052759 nickel Inorganic materials 0.000 claims description 35
- 238000005868 electrolysis reaction Methods 0.000 claims description 26
- 239000003792 electrolyte Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 3
- 239000008151 electrolyte solution Substances 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 44
- 229910052757 nitrogen Inorganic materials 0.000 description 22
- 238000012360 testing method Methods 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 238000000151 deposition Methods 0.000 description 7
- 230000008021 deposition Effects 0.000 description 7
- 238000004502 linear sweep voltammetry Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
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- 239000011734 sodium Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
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- 238000010586 diagram Methods 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 229910000474 mercury oxide Inorganic materials 0.000 description 4
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 4
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Images
Classifications
-
- 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
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- B01J35/33—
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
-
- 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
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a Co-Mo-P-O electrocatalyst and a preparation method and application thereof. The Co-Mo-P-O electrocatalyst is an amorphous nanoparticle film loaded on a conductive substrate and comprising four elements of Co, Mo, P and O. The preparation method comprises the steps of adopting a three-electrode electrochemical system, carrying out electrochemical deposition in an aqueous solution containing cobalt sulfate, sodium molybdate, sodium hypophosphite and sodium citrate, and respectively taking a conductive substrate, a platinum sheet and a saturated calomel electrode as a working electrode, a counter electrode and a reference electrode. The Co-Mo-P-O electrocatalyst is simple and easy to prepare, has excellent performances in the aspects of electrolytic water hydrogen evolution reaction, electrolytic water oxygen evolution reaction and complete electrolytic water application, and is expected to be industrially applied in large scale.
Description
Technical Field
The invention belongs to the field of electrocatalyst nano materials, and particularly relates to a Co-Mo-P-O electrocatalyst, and a preparation method and application thereof.
Background
With the increasing and developing demands of the global population, fossil energy sources such as coal, petroleum and the like are used in large quantities. The limited storage of these fossil energies and the environmental pollution caused by their use have forced the search for new clean energy sources to replace fossil energies. Hydrogen is receiving wide attention as a clean and efficient energy source. The electrolysis of water to produce hydrogen is considered a very promising approach to produce hydrogen due to its environmental friendliness and high efficiency. However, its excessive energy consumption limits its wide industrial application. The proper electrocatalyst can reduce the activation energy of water decomposition reaction and accelerate reaction kinetics, thereby improving the efficiency of preparing hydrogen by electrolyzing water and reducing energy consumption.
Electrolyzed water consists essentially of two half-reactions: a cathodic hydrogen evolution reaction and an anodic oxygen evolution reaction. Compared with the hydrogen evolution reaction, the multi-electron reaction step of the oxygen evolution reaction causes slower kinetics, so that the development of the high-activity oxygen evolution electrocatalyst has important significance for preparing hydrogen by electrolyzing water. Meanwhile, if the prepared electro-catalyst has double functions, namely, the electro-catalyst can efficiently catalyze and separate hydrogen and oxygen, and great contribution is made to reducing the production cost and simplifying the production process.
At present, the hydrogen evolution catalyst and the oxygen evolution catalyst with the most excellent electrocatalytic performance are Pt-based compounds and Ir-based compounds respectively. However, the noble metals are expensive and have low reserves, which limits large-scale industrial application. Transition metals have the characteristics of low cost, abundant reserves and excellent electrocatalytic performance, and are currently being researched and used in a large number. Therefore, it is necessary to prepare a highly active hydrogen and oxygen evolution water electrolysis catalyst using a transition metal system.
Disclosure of Invention
It is a first object of the present invention to provide a novel Co-Mo-P-O electrocatalyst.
The second purpose of the invention is to provide a preparation method of the Co-Mo-P-O electrocatalyst.
The third purpose of the invention is to provide the application of the Co-Mo-P-O electrocatalyst, which is used for realizing high-performance electrolytic water hydrogen evolution reaction, electrolytic water oxygen evolution reaction and complete electrolytic water reaction.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a Co-Mo-P-O electrocatalyst which is an amorphous nanoparticle thin film comprising four elements of Co, Mo, P, O supported on an electrically conductive substrate.
In the Co-Mo-P-O electrocatalyst, Co, Mo, P and O are uniformly distributed in the whole film, and the surface of the film is highly rough. The Co-Mo-P-O electrocatalyst has a highly rough surface, a large electrochemical active area and excellent conductivity.
Preferably, the conductive substrate is nickel foam, nickel sheet or ITO glass, and the conductive substrate herein may be any conductive substrate as would be readily understood by a worker skilled in the art.
In a second aspect, the present invention provides a method for preparing a Co-Mo-P-O electrocatalyst, comprising the steps of:
1) preparing an electrolyte aqueous solution containing cobalt sulfate, sodium molybdate, sodium hypophosphite and sodium citrate;
2) in a three-electrode electrochemical system, a conductive substrate is used as a working electrode, and a constant potential is applied to the working electrode for electrochemical deposition, so that the Co-Mo-P-O electrocatalyst is obtained.
The following is detailed for each step:
step 1): preparing an electrolyte aqueous solution containing cobalt sulfate, sodium molybdate, sodium hypophosphite and sodium citrate.
Preferably, the concentration of each component in the electrolyte aqueous solution is: 0.15mol/L cobalt sulfate, 0.05mol/L sodium molybdate, 0.05mol/L-0.6mol/L sodium hypophosphite and 0.15mol/L sodium citrate.
Step 2): in a three-electrode electrochemical system, a conductive substrate is used as a working electrode, and a constant potential is applied to the working electrode for electrochemical deposition, so that the Co-Mo-P-O electrocatalyst is obtained.
Preferably, the conductive substrate is any conductive substrate such as nickel foam, nickel sheet or ITO glass.
Preferably, in the three-electrode electrochemical system, a platinum sheet is used as a counter electrode, and a Saturated Calomel Electrode (SCE) is used as a reference electrode.
Preferably, the constant potential is-2.0V (relative to a saturated calomel electrode). Those skilled in the art will appreciate that the potential values will vary from reference electrode to reference electrode. The potential values are different, the electrodeposition rate is different, and the appearance is also changed; the Co-Mo-P-O electrocatalyst with limited performance and structure is obtained only under the conditions that a reference electrode is a saturated calomel electrode and the constant potential is-2.0V.
Preferably, the electrochemical deposition is carried out at room temperature, with continuous stirring by a magnetic stirrer at a stirring speed of 200-; preferably 300 rpm.
Preferably, the deposition time is 5 minutes. The deposition time is too long, the deposited film is easy to fall off, the invention obtains 5 minutes as the optimal time in the research process, and the electrocatalyst deposited on the foamed nickel begins to fall off after more than 5 minutes.
In a third aspect, the present invention provides the use of the above Co-Mo-P-O electrocatalyst in the hydrogen evolution reaction by electrolysis of water, the oxygen evolution reaction by electrolysis of water and in the complete electrolysis of water.
Specifically, the application of the Co-Mo-P-O electrocatalyst in the hydrogen evolution reaction by electrolysis water, the oxygen evolution reaction by electrolysis water and the complete electrolysis water comprises the following aspects:
1) the Co-Mo-P-O electrocatalyst is used as a cathode for the hydrogen evolution reaction by electrolysis with the current density of 10mA/cm 2 The overpotential was only 97 mV.
2) The Co-Mo-P-O electrocatalyst is used as an anode for the electrolytic water oxygen evolution reaction, and the current density is 10mA/cm 2 The overpotential at this time was only 260.4 mV.
3) The Co-Mo-P-O electrocatalyst is respectively used as an anode and a cathode for complete water electrolysis reaction, and the current density is 10mA/cm 2 The voltage at time is only 1.62V.
The tests carried out in the examples of the invention with respect to the above applications are as follows:
applications 1) and 2) were carried out in 1mol/L KOH aqueous solution, with Co-Mo-P-O electrocatalyst as the working electrode and graphite rod and mercury/mercury oxide electrode as the counter and reference electrodes, respectively. Before the test is started, nitrogen is introduced into the electrolyte for 30 minutes, and the nitrogen is continuously introduced into the electrolyte at a flow rate of 20mL/min until the test is finished. The test was carried out at room temperature with a constant stirring rate of 200 rpm. The hydrogen evolution reaction and oxygen evolution performance of the Co-Mo-P-O electrocatalyst by water electrolysis were tested in the range of-0.27 to 1.60V (relative to the reversible hydrogen electrode) by linear sweep voltammetry.
Application 3) Co-Mo-P-O electrocatalyst is used as anode and cathode respectively, and complete electrolytic water reaction is carried out in 1mol/L KOH aqueous solution. Before the test is started, nitrogen is introduced into the electrolyte for 30 minutes, and the nitrogen is continuously introduced into the electrolyte at a flow rate of 20mL/min until the test is finished. The test was carried out at room temperature with a constant stirring rate of 200 rpm. The complete water electrolysis performance of the Co-Mo-P-O electrocatalyst was tested by linear sweep voltammetry in the range of 1.23-1.70V.
The invention has the following beneficial effects:
the Co-Mo-P-O electrocatalyst has the advantages that: the amorphous Co-Mo-P-O electrocatalyst supported on the conductive substrate has a highly rough surface, a large electrochemical active area and excellent conductivity; the electrodeposition method for preparing the Co-Mo-P-O electrocatalyst has the advantages of simple process, high repeatability and low cost; the Co-Mo-P-O electrocatalyst of the invention can be used as a bifunctional catalyst for the hydrogen evolution reaction by electrolysis and the oxygen evolution reaction by electrolysis, so that the Co-Mo-P-O electrocatalyst can be simultaneously used as a cathode and an anode for completely electrolyzing water. When the Co-Mo-P-O electrocatalyst of the invention is used for catalyzing electrolysis water hydrogen evolution reaction, the low overpotential of water hydrogen evolution by electrocatalysis decomposition is shown, and the current density is 10mA/cm 2 The required overpotential of this is only 97 mV; when the Co-Mo-P-O electrocatalyst of the invention is used for catalyzing water electrolysis and oxygen evolution, the current density is 10mA/cm 2 The required overpotential is only 260.4 mV; when the Co-Mo-P-O electrocatalyst of the invention is used as a cathode and an anode for completely electrolyzing water, the Co-Mo-P-O electrocatalyst shows better performance than the similar catalysts, has low overpotential and good stability, and has the current density of 10mA/cm 2 Only 1.57V of applied voltage is needed. The novel Co-Mo-P-O electrocatalyst provided by the invention has the advantages of simple preparation method, high repeatability, low cost and extremely high catalytic activity, and can be widely applied to industrial production of hydrogen production by water electrolysis.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is an SEM image of a Co-Mo-P-O electrocatalyst according to example 5 of the invention.
FIG. 2 is an EDX energy spectrum of a Co-Mo-P-O electrocatalyst according to example 5 of the present invention.
FIG. 3a is a TEM image of a Co-Mo-P-O electrocatalyst according to example 5 of the present invention.
FIG. 3b is a Mapping diagram of Co element in Co-Mo-P-O electrocatalyst according to example 5 of the present invention.
FIG. 3c is a Mapping diagram of Mo element in Co-Mo-P-O electrocatalyst according to example 5 of the present invention.
FIG. 3d is a Mapping chart of P element in Co-Mo-P-O electrocatalyst according to example 5 of the present invention.
FIG. 3e is a Mapping diagram of the O element in the Co-Mo-P-O electrocatalyst according to example 5 of the present invention.
FIG. 4 is an XRD pattern of a Co-Mo-P-O electrocatalyst according to example 5 of the invention.
FIG. 5 is a graph showing the hydrogen evolution performance of Co-Mo-P-O electrocatalyst for electrolyzed water in example 6 according to the present invention.
FIG. 6 is a graph showing the hydrogen evolution performance of Co-Mo-P-O electrocatalyst for electrolyzed water according to example 7 of the present invention.
FIG. 7 is a graph showing the performance of the Co-Mo-P-O electrocatalyst for electrolyzed water oxygen evolution in accordance with example 8 of the present invention.
FIG. 8 is a graph of the complete electrolyzed water response performance of the Co-Mo-P-O electrocatalyst according to example 9 of the present invention.
Detailed Description
In order to make the technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
Example 1
The nickel sheet of 2cm x 2cm was sequentially placed in acetone, ethanol and 1M hydrochloric acid for ultrasonic cleaning for 15min, then rinsed with a large amount of deionized water and blown dry with nitrogen. Preparing an electrolyte containing the following components: 0.15mol/L CoSO 4 、0.05mol/L NaMoO 4 、0.6mol/L NaH 2 PO 2 、0.15M Na 3 C 6 H 5 O 7 . In a three-electrode electrochemical system, cleaned nickel sheets, platinum sheets and saturated calomel electrodes are respectively used as a working electrode, a counter electrode and a reference electrode. The potential of-2V (relative to the saturated calomel electrode) was applied to the working electrode through an electrochemical workstation at room temperature, and the potential was deposited for 5 min. During the deposition, the reaction system was stirred by a magnetic stirrer at 300 rpm. Electric powerAnd after the chemical deposition is finished, taking out the nickel sheet, washing the nickel sheet by using a large amount of deionized water, and drying the nickel sheet by using nitrogen to obtain the Co-Mo-P-O electrocatalyst.
Example 2
The nickel sheet of 2cm x 2cm was sequentially placed in acetone, ethanol and 1M hydrochloric acid for ultrasonic cleaning for 15min, then rinsed with a large amount of deionized water and blown dry with nitrogen. Preparing an electrolyte containing the following components: 0.15mol/L CoSO 4 、0.05mol/L NaMoO 4 、0.5mol/L NaH 2 PO 2 、0.15M Na 3 C 6 H 5 O 7 . In a three-electrode electrochemical system, cleaned nickel sheets, platinum sheets and saturated calomel electrodes are respectively used as a working electrode, a counter electrode and a reference electrode. The potential of-2V (relative to the saturated calomel electrode) was applied to the working electrode through an electrochemical workstation at room temperature, and the potential was deposited for 5 min. During the deposition, the reaction system was stirred by a magnetic stirrer at 300 rpm. And after the electrochemical deposition is finished, taking out the nickel sheet, washing the nickel sheet by using a large amount of deionized water, and drying the nickel sheet by using nitrogen to obtain the Co-Mo-P-O electrocatalyst.
Example 3
The nickel sheet of 2cm x 2cm was sequentially placed in acetone, ethanol and 1M hydrochloric acid for ultrasonic cleaning for 15min, then rinsed with a large amount of deionized water and blown dry with nitrogen. Preparing an electrolyte containing the following components: 0.15mol/L CoSO 4 、0.05mol/L NaMoO 4 、0.3mol/L NaH 2 PO 2 、0.15M Na 3 C 6 H 5 O 7 . In a three-electrode electrochemical system, cleaned nickel sheets, platinum sheets and saturated calomel electrodes are respectively used as a working electrode, a counter electrode and a reference electrode. The potential of-2V (relative to the saturated calomel electrode) was applied to the working electrode through an electrochemical workstation at room temperature, and the potential was deposited for 5 min. During the deposition, the reaction system was stirred by a magnetic stirrer at 300 rpm. And after the electrochemical deposition is finished, taking out the nickel sheet, washing the nickel sheet by using a large amount of deionized water, and drying the nickel sheet by using nitrogen to obtain the Co-Mo-P-O electrocatalyst.
Example 4
Putting nickel sheets of 2cm multiplied by 2cm in sequence on the glassUltrasonic cleaning in ketone, ethanol and 1M hydrochloric acid for 15min, rinsing with a large amount of deionized water and blowing with nitrogen. Preparing an electrolyte containing the following components: 0.15mol/L CoSO 4 、0.05mol/L NaMoO 4 、0.05mol/L NaH 2 PO 2 、0.15M Na 3 C 6 H 5 O 7 . In a three-electrode electrochemical system, cleaned nickel sheets, platinum sheets and saturated calomel electrodes are respectively used as a working electrode, a counter electrode and a reference electrode. The potential of-2V (relative to the saturated calomel electrode) was applied to the working electrode through an electrochemical workstation at room temperature, and the potential was deposited for 5 min. During the deposition, the reaction system was stirred by a magnetic stirrer at 300 rpm. And after the electrochemical deposition is finished, taking out the nickel sheet, washing the nickel sheet by using a large amount of deionized water, and drying the nickel sheet by using nitrogen to obtain the Co-Mo-P-O electrocatalyst.
Example 5
The foamed nickel of 2cm x 2cm is sequentially placed in acetone, ethanol and 1M hydrochloric acid for ultrasonic cleaning for 15min, and then is washed by a large amount of deionized water and dried by nitrogen. Preparing an electrolyte containing the following components: 0.15mol/L CoSO 4 、0.05mol/L NaMoO 4 、0.5mol/L NaH 2 PO 2 、0.15M Na 3 C 6 H 5 O 7 . In a three-electrode electrochemical system, cleaned foamed nickel, a platinum sheet and a saturated calomel electrode are respectively used as a working electrode, a counter electrode and a reference electrode. The potential of-2V (relative to the saturated calomel electrode) was applied to the working electrode through an electrochemical workstation at room temperature, and the potential was deposited for 5 min. During the deposition, the reaction system was stirred by a magnetic stirrer at 300 rpm. And after the electrochemical deposition is finished, taking out the foamed nickel, washing the foamed nickel by using a large amount of deionized water, and drying the foamed nickel by using nitrogen to obtain the Co-Mo-P-O electrocatalyst.
The Co-Mo-P-O electrocatalyst prepared in example 5 was characterized by a variety of means. The morphology of the Co-Mo-P-O electrocatalyst is shown in the SEM picture of FIG. 1. FIG. 2 is an EDX spectrum of a Co-Mo-P-O electrocatalyst, which shows that the Co-Mo-P-O electrocatalyst is composed of four elements of Co, Mo, P and O, wherein Cu and C are from the substrate used in the spectrum characterization. Fig. 3 a-3 e are TEM images and corresponding Mapping images of Co-Mo-P-O electrocatalyst, wherein fig. 3 a-is TEM image of Co-Mo-P-O particle, fig. 3b, 3c, 3d, and 3e are distribution diagrams of Co, Mo, P, and O elements, respectively, and it can be seen that the four elements of Co, Mo, P, and O are uniformly distributed in the whole particle. FIG. 4 is an XRD pattern of the Co-Mo-P-O electrocatalyst, and it can be seen that no other peaks except the Ni base peak appear in the XRD pattern of the Co-Mo-P-O electrocatalyst, indicating that the Co-Mo-P-O electrocatalyst has an amorphous structure.
Example 6
The Co-Mo-P-O electrocatalyst of example 2 was used as a working electrode, a graphite rod and a mercury/mercury oxide electrode were used as a counter electrode and a reference electrode, respectively, and the performance of hydrogen evolution by electrolysis of water of the Co-Mo-P-O electrocatalyst of example 2 was tested in a 1mol/L KOH aqueous solution using an electrochemical three-electrode system. Before the test is started, nitrogen is introduced into the electrolyte for 30 minutes, and the nitrogen is continuously introduced into the electrolyte at a flow rate of 20mL/min until the test is finished. The test was carried out at room temperature with a constant stirring rate of 200 rpm. The Co-Mo-P-O electrocatalyst of example 2 was tested for its hydrogen evolution performance by water electrolysis using linear sweep voltammetry in the range-0.23-0V (versus reversible hydrogen electrode) and the results are shown in fig. 5. The current density reaches 10mA/cm 2 When the overpotential is as low as 121.9mV, the catalyst has excellent hydrogen evolution catalytic activity.
Example 7
The Co-Mo-P-O electrocatalyst of example 5 was tested for its performance in hydrogen evolution by electrolysis in 1mol/L KOH aqueous solution using a three-electrode electrochemical system with the Co-Mo-P-O electrocatalyst of example 5 as the working electrode, the graphite rod and the mercury/mercury oxide electrode as the counter electrode and the reference electrode, respectively. Before the test is started, nitrogen is introduced into the electrolyte for 30 minutes, and the flow of the nitrogen at 20mL/min is kept introduced into the electrolyte until the test is finished. The test was carried out at room temperature with a constant stirring rate of 200 rpm. The Co-Mo-P-O electrocatalyst of example 5 was tested for its hydrogen evolution performance by water electrolysis using linear sweep voltammetry in the range-0.27-0V (versus reversible hydrogen electrode) and the results are shown in fig. 6. The current density reaches 10mA/cm 2 When the overpotential is as low as 97mV, which is lower than that of the substrate of example 6The Co-Mo-P-O electrocatalyst with the same electrodeposition conditions proves that the foamed nickel conductive substrate is more favorable for reducing the overpotential of the electrolytic water hydrogen evolution reaction compared with a nickel sheet conductive substrate, because the three-dimensional framework structure of the foamed nickel is more favorable for exposing more active sites.
Example 8
The Co-Mo-P-O electrocatalyst of example 5 was tested for its electrolyzed water oxygen evolution performance in a 1mol/L KOH aqueous solution using a three-electrode electrochemical system with the Co-Mo-P-O electrocatalyst of example 5 as the working electrode and the graphite rod and the mercury/mercury oxide electrode as the counter electrode and the reference electrode, respectively. Before the test is started, nitrogen is introduced into the electrolyte for 30 minutes, and the nitrogen is continuously introduced into the electrolyte at a flow rate of 20mL/min until the test is finished. The test was performed at room temperature with a constant stirring rate of 200 rpm. The Co-Mo-P-O electrocatalyst of example 5 was tested for electrolyzed water oxygen evolution performance in the range of 1.12-1.60V (versus reversible hydrogen electrode) using linear sweep voltammetry, and the results are shown in fig. 7. The current density reaches 10mA/cm 2 When the overpotential is as low as 260.4mV, the catalyst has excellent oxygen evolution catalytic activity.
Example 9
The Co-Mo-P-O electrocatalyst of example 5 was used as anode and cathode, respectively, and subjected to complete electrolytic water reaction in 1mol/L KOH aqueous solution using an electrochemical two-electrode system. Before the test is started, nitrogen is introduced into the electrolyte for 30 minutes, and the flow of the nitrogen at 20mL/min is kept introduced into the electrolyte until the test is finished. The test was performed at room temperature with a constant stirring rate of 200 rpm. The complete water electrolysis performance of the Co-Mo-P-O electrocatalyst was tested by linear sweep voltammetry at a voltage range of 1.23-1.70V, and the results are shown in fig. 8. The current density reaches 10mA/cm 2 When the required supply voltage is as low as 1.62V, the dual-function catalyst has excellent complete electrolytic water catalytic activity.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (9)
1. A Co-Mo-P-O electrocatalyst used for electrolytic water hydrogen evolution reaction or electrolytic water oxygen evolution reaction or complete electrolytic water is characterized in that the Co-Mo-P-O electrocatalyst is an amorphous nanoparticle film loaded on a conductive substrate and comprising four elements of Co, Mo, P and O; in the Co-Mo-P-O electrocatalyst, Co, Mo, P and O are uniformly distributed in the whole film, and the surface of the film is highly rough;
the preparation method of the Co-Mo-P-O electrocatalyst comprises the following steps:
1) preparing an electrolyte aqueous solution containing cobalt sulfate, sodium molybdate, sodium hypophosphite and sodium citrate;
2) in a three-electrode electrochemical system, a conductive substrate is used as a working electrode, and a constant potential is applied to the working electrode for electrochemical deposition, so that the Co-Mo-P-O electrocatalyst is obtained.
2. The Co-Mo-P-O electrocatalyst according to claim 1, wherein the electrically conductive substrate is foamed nickel, nickel sheet or ITO glass.
3. The Co-Mo-P-O electrocatalyst according to claim 1, wherein the concentration of each component in the aqueous electrolyte solution is: 0.15 mol/L cobalt sulfate, 0.05 mol/L sodium molybdate, 0.05 mol/L-0.6 mol/L sodium hypophosphite and 0.15 mol/L sodium citrate.
4. The Co-Mo-P-O electrocatalyst according to claim 1, wherein in said three-electrode electrochemical system a platinum sheet is used as counter electrode and a saturated calomel electrode is used as reference electrode.
5. The Co-Mo-P-O electrocatalyst according to claim 1, characterized in that the constant potential is-2.0V.
6. The Co-Mo-P-O electrocatalyst according to claim 1, characterized in that the electrochemical deposition is performed at room temperature with continuous stirring by a magnetic stirrer at a stirring speed of 200-500 rpm.
7. The Co-Mo-P-O electrocatalyst according to claim 1, wherein the electrochemical deposition time is 5 minutes.
8. Use of a Co-Mo-P-O electrocatalyst according to any one of claims 1-2 in hydrogen evolution reactions by electrolysis, oxygen evolution reactions by electrolysis and complete electrolysis of water.
9. The use according to claim 8, characterized by the following aspects:
1) the Co-Mo-P-O electrocatalyst is used as a cathode for the electrolytic water hydrogen evolution reaction;
2) the Co-Mo-P-O electrocatalyst is used as an anode for the electrolytic water oxygen evolution reaction;
3) the Co-Mo-P-O electrocatalyst is used as an anode and a cathode respectively for complete water electrolysis reaction.
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