CN115364879A - Preparation method and application of cobalt phosphide nanosheet array three-function catalyst - Google Patents
Preparation method and application of cobalt phosphide nanosheet array three-function catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 40
- 239000010941 cobalt Substances 0.000 title claims abstract description 40
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000002135 nanosheet Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000243 solution Substances 0.000 claims abstract description 33
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 24
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000012298 atmosphere Substances 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 239000003792 electrolyte Substances 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- 239000002585 base Substances 0.000 claims abstract description 6
- 150000001868 cobalt Chemical class 0.000 claims abstract description 6
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims abstract description 6
- 239000002841 Lewis acid Substances 0.000 claims abstract description 5
- 239000002879 Lewis base Substances 0.000 claims abstract description 5
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 5
- 230000003993 interaction Effects 0.000 claims abstract description 5
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 5
- 239000003446 ligand Substances 0.000 claims abstract description 5
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- 239000013256 coordination polymer Substances 0.000 claims abstract description 4
- 229920001795 coordination polymer Polymers 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 150000007527 lewis bases Chemical class 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 229910001463 metal phosphate Inorganic materials 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract 1
- 238000004220 aggregation Methods 0.000 abstract 1
- -1 melamine lewis base Chemical class 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- 238000001075 voltammogram Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 238000000970 chrono-amperometry Methods 0.000 description 1
- 229910000152 cobalt phosphate Inorganic materials 0.000 description 1
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000002498 deadly effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012353 t test Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 1
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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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
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B01J35/33—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/08—Other phosphides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The invention relates to a preparation method and application of a cobalt phosphide nanosheet array three-function catalyst, and the preparation method comprises the following steps: aminotrimethylene phosphonic Acid (ATMP) was added to a hot aqueous solution of fully dissolved melamine to form a supramolecular gel precursor. Then, adding cobalt salt into the supermolecule gel precursor solution to react to obtain a pink product; and further placing the product in a tubular furnace, and calcining at high temperature in a protective gas atmosphere to obtain the cobalt phosphide nanosheet array three-function catalyst. The invention provides a simple 'Lewis acid-base interaction' strategy, i.e. LewisAcid ATMP as proton donor and melamine lewis base as proton donor. The combination of ATMP and melamine through hydrogen bond greatly weakens Co 2+ And the strong chelating ability of ATMP. In the high-temperature calcination process, the carbon-rich melamine ligand enables the cobalt-organic phosphorus coordination polymer to be placed in a strong reducing atmosphere, so that the purpose of in-situ phosphorization is achieved, the formation and aggregation of metal phosphate particles are avoided, and the preparation method is simple and efficient. Meanwhile, the prepared cobalt phosphide is in a nanosheet array, the specific surface is high, the contact area of the electrolyte and the cobalt phosphide is larger, more active sites participate in catalysis, excellent three-function characteristics are shown, and the overpotential of ORR, OER and HER is effectively reduced.
Description
Technical Field
The invention belongs to the technical field of new energy materials, and particularly relates to a preparation method and application of a cobalt phosphide nanosheet array three-function catalyst.
Background
The increasing global demand for environmentally friendly and low cost renewable storage has driven the emergence of the most advanced electrocatalysts for metal-air batteries, fuel cells and water electrolysers. In order to reduce costs and simplify the system in industrial applications, it is technically crucial to develop homologous catalysts with multifunctional activity in OER, ORR and HER that such ideal catalysts should also work at lower overpotentials, beyond the benchmark noble metal/metal oxide. In recent years, transition Metal Phosphides (TMPs), in particular cobalt phosphides (CoP), have attracted attention for their hydrogenase-like catalytic mechanism and suitable gibbs free energy for hydrogen adsorption. How to simplify the preparation process of CoP is an important component of industrial application of CoP.
The current methods for CoP synthesis often require additional inorganic phosphorus sources (e.g., naH) 2 PO 2 And NH 4 H 2 PO 2 ) High-boiling organic solvents (e.g. tri-n-octylphosphine or tri-n-octylphosphine oxide) or use H 2 As a reducing agent to reduce metal phosphates, the former inevitably produces large amounts of toxic, deadly pH 3 A gas. The latter is due to the very strong bond energy of the phosphorus-oxygen bond, H 2 In the process of reducing metal phosphate, metal particles are easily generated, and the adsorption of gas is influenced, so that the catalytic efficiency is influenced. In order to solve the problems in the prior art, the invention provides a preparation method and application of a cobalt phosphide nanosheet array three-function catalyst, the method is simple, the cost is low, the efficiency is high, and the prepared cobalt phosphide nanosheet array material shows thatExcellent three-functional characteristics, effectively reduces the overpotential of ORR, OER and HER.
Aminotrimethylene phosphonic Acid (ATMP) contains a carbon species and a phosphate group that can provide a source of phosphorus in situ to produce metal heteroatom-free doped carbon for a variety of uses. In addition, ATMP containing rich phosphate functionality also exhibits good compatibility with transition metal ions (Co) 2+ 、Ni 2+ Etc.) and a proton base, etc. We propose a simple "Lewis acid-base interaction" strategy to prepare nitrogen-coordinated cobalt phosphide (N-CoP/NC) on nitrogen-doped carbon substrates. ATMP provides protons as lewis acid and melamine accepts protons as lewis base. The melamine and the ATMP are combined through hydrogen bonds, and the chelating capacity of the cobalt and the ATMP is greatly weakened. Meanwhile, the introduction of the carbon-rich alkaline ligand enables the organic cobalt phosphate complex to be placed in a strong reducing atmosphere in the high-temperature calcination process, so that the purpose of in-situ phosphating is achieved. In the present invention, our synthetic scheme greatly simplifies the synthesis of the common CoP-based hybrid because it does not require additional hybrid carbon sources to be obtained by multi-step reactions and does not require the use of strong reducing agents or high boiling organic solvents as phosphorus sources. Meanwhile, the prepared cobalt phosphide is in a nanosheet array, the specific surface is high, the contact area of the electrolyte and the cobalt phosphide is larger, and more active sites participate in catalysis. In addition, the method can also be used for synthesizing other Transition Metal Phosphide (TMP) based hybrid structures. The unique and novel structure endows the N-CoP/NC hybrid material with excellent electrocatalytic performance on ORR, OER and HER.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the cobalt phosphide nanosheet array three-function catalyst which is simple in preparation method, low in cost and high in efficiency, the specific surface of the material is improved, the contact area of an electrolyte and the material is larger, more active sites participate in catalysis are provided, excellent three-function characteristics are shown, and the overpotentials of ORR, OER and HER are effectively reduced.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a cobalt phosphide nanosheet array three-function catalyst comprises the following steps:
the method comprises the following steps: dissolving melamine in deionized water at a certain temperature until a transparent solution is formed;
step two: adding a certain amount of ATMP into the solution and stirring for a certain time, and forming a supramolecular gel precursor when the mixture is naturally cooled to room temperature;
step three: mixing Co (NO) 3 ) 2 ·6H 2 Adding O into the supermolecule gel precursor solution obtained in the step two, continuously stirring for a certain time, centrifuging and drying to obtain a pink product;
step four: and (4) placing the pink product formed in the third step into a tubular furnace, and calcining at high temperature in a protective gas atmosphere to obtain the cobalt phosphide nanosheet array three-function catalyst.
Further, in the first step, the molar volume of the melamine is in the range of 0.2-0.3 mol/L, and the temperature is between 80-100 ℃.
Further, in the second step, the mass concentration of the ATMP aqueous solution is 50wt.% to 75wt.%, and the volume range of the added ATMP is 0.8mL to 1.0mL.
Further, in the second step, the stirring time is 3-5min;
further, in step three, the cobalt salt may be Co (NO) 3 ) 2 ·6H 2 O、CoCl 2 And Co (C) 2 H 3 O 2 ) 2 The molar weight of the added cobalt salt is 1-2 mmol.
Further, in the third step, the stirring time is 3-10min.
Further, in the fourth step, the protective atmosphere may be one of nitrogen and argon.
Furthermore, in the fourth step, the calcining temperature is 900-950 ℃, the heating rate is 3-5 ℃/min, and the heat preservation time is 2-3 h.
A simple 'Lewis acid-base interaction' strategy is provided, and Lewis acid ATMP is used as a substrateThe sub-donor, the lewis base melamine, acts as a proton donor. The combination of ATMP and melamine through hydrogen bond greatly weakens Co 2+ And the strong chelating ability of ATMP. In the high-temperature calcination process, the carbon-rich melamine ligand enables the cobalt-organic phosphorus coordination polymer to be placed in a strong reducing atmosphere so as to achieve the purpose of in-situ phosphorization.
The cobalt phosphide with the nanosheet array structure is prepared by the preparation method, the surface appearance is uniform and regular, and the thickness of the nanosheet array is uniform.
The application of the three-function catalyst of the cobalt phosphide nanosheet array is used for reaction of ORR (organic oxygen radical) and OER (organic oxygen radical) in alkaline electrolyte and HER (organic hydrogen radical) in acidic electrolyte, so that the overpotential of the ORR, OER and HER is effectively reduced. ORR reaction in 0.1MKOH, an initial potential equivalent to commercial 20% Pt/C (0.910V vs. RHE), and a diffusion limiting current superior to 20% Pt/C (6.280 mA cm -2 ) And exhibits excellent methanol tolerance and stability.
Compared with the prior art, the technical scheme provided by the invention has the following remarkable effects:
the three-function catalyst of the cobalt phosphide nanosheet array is easy to purchase, cheap and easy to obtain as raw materials, and is convenient for large-scale production.
In the preparation process of the cobalt phosphide nanosheet array three-function catalyst, a simple 'Lewis acid-base interaction' strategy is provided, lewis acid ATMP is used as a proton donor, and Lewis base melamine is used as a proton donor. ATMP and melamine are combined through hydrogen bonds, and Co is greatly weakened 2+ And the strong chelating ability of ATMP. In the high-temperature calcination process, the carbon-rich melamine ligand enables the cobalt-organic phosphorus coordination polymer to be placed in a strong reducing atmosphere so as to achieve the purpose of in-situ phosphorization, and the preparation method is simple and efficient.
The three-function catalyst of the cobalt phosphide nanosheet array, disclosed by the invention, has excellent three-function characteristics, and effectively reduces the overpotential of ORR, OER and HER. ORR reaction in 0.1M KOH, an initial potential (0.910V vs. RHE) equivalent to commercial 20% Pt/C was obtained,And a diffusion limit current (6.280 mA cm) of better than 20% Pt/C -2 ) And exhibits excellent methanol tolerance and stability.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
FIG. 1 is an X-ray diffraction pattern of CoP/NC obtained according to example 1 of the present invention.
FIG. 2 is a scanning electron micrograph of catalysts (NCP, HNCP and CoP/NC) obtained in example 1 according to the present invention.
FIG. 3 is a plot of (A) Linear sweep voltammograms, (B) Linear sweep voltammograms, (C) methanol tolerance, and (D) stability of the catalysts (NCP, HNCP, and CoP/NC) and 20% commercial Pt-modified rotating disk electrode (RRDE) obtained in example 1 according to the present invention in 0.1M KOH.
FIG. 4 is a graph of (A) oxygen evolution linear sweep voltammograms and (B) stability of CoP/NC and 20% commercial Pt-modified rotating disk electrode (RRDE) obtained in example 1 according to the invention in 1.0M KOH.
FIG. 5 is a graph of CoP/NC obtained according to example 1 of the present invention and a 20% commercial Pt modified rotating disk electrode (RRDE) at 0.5M H 2 SO 4 Hydrogen evolution linear sweep voltammograms (a) and stability profiles (B) in solution.
Detailed Description
For a further understanding of the present invention, reference will now be made to the following detailed description taken in conjunction with the accompanying drawings and examples.
Example 1:
the method comprises the following steps: dissolving 0.2mol/L melamine in deionized water at 80 ℃ until a transparent solution is formed, and recording the solution as solution A;
step two: adding 0.8mL of ATMP with the mass concentration of 50wt.% into the solution A, stirring for 3min, and forming a supramolecular gel precursor which is marked as a solution B when the mixture is naturally cooled to room temperature;
step three: mixing Co (NO) 3 ) 2 ·6H 2 O is added to the B solution and thenContinuously stirring for 5min, centrifuging, and drying to obtain pink product C;
step four: and (3) placing the C in a tubular furnace, heating from room temperature to 900 ℃ at the heating rate of 3 ℃/min under the atmosphere of nitrogen protection gas, and calcining for 2h to obtain the cobalt phosphide nanosheet array three-function catalyst.
Example 2:
the method comprises the following steps: dissolving 0.3mol/L melamine in deionized water at 80 ℃ until a transparent solution is formed, and recording the solution as solution A;
step two: adding 0.8mL of ATMP with the mass concentration of 60wt.% into the solution A, stirring for 3min, and forming a supramolecular gel precursor which is marked as a solution B when the mixture is naturally cooled to room temperature;
step three: 1mmol of Co (NO) 3 ) 2 ·6H 2 Adding O into the solution B, continuously stirring for 3min, centrifuging, and drying to obtain a pink product which is marked as C;
step four: and (3) placing the C in a tubular furnace, heating from room temperature to 900 ℃ at the heating rate of 4 ℃/min under the atmosphere of nitrogen protection gas, and calcining for 2h to obtain the cobalt phosphide nanosheet array three-function catalyst.
Example 3:
the method comprises the following steps: dissolving 0.3mol/L melamine in deionized water at 90 ℃ until a transparent solution is formed, and marking as a solution A;
step two: adding 0.8mL of ATMP with the mass concentration of 60wt.% into the solution A, stirring for 5min, and forming a supramolecular gel precursor when the mixture is naturally cooled to room temperature, wherein the supramolecular gel precursor is marked as solution B;
step three: 2mmol of CoCl 2 Adding the mixture into the solution B, continuously stirring for 8min, centrifuging and drying to obtain a pink product which is marked as C;
step four: and (3) placing the C in a tubular furnace, heating the C from room temperature to 925 ℃ at the heating rate of 4 ℃/min under the atmosphere of nitrogen protection gas, and calcining the C for 2 hours at a high temperature to obtain the cobalt phosphide nanosheet array three-functional catalyst.
Example 4:
the method comprises the following steps: dissolving 0.3mol/L melamine in deionized water at 100 ℃ until a transparent solution is formed, and marking as a solution A;
step two: adding 1.0mL of ATMP with the mass concentration of 75wt.% into the solution A, stirring for 5min, and forming a supramolecular gel precursor which is marked as a solution B when the mixture is naturally cooled to room temperature;
step three: 2mmo Co (C) 2 H 3 O 2 ) 2 Adding the mixture into the solution B, continuously stirring for 10min, centrifuging and drying to obtain a pink product which is marked as C;
step four: and (3) placing the C in a tubular furnace, heating the C from room temperature to 950 ℃ at the heating rate of 3 ℃/min under the atmosphere of nitrogen protection gas, and calcining the C for 3 hours at the high temperature to obtain the cobalt phosphide nanosheet array three-functional catalyst.
FIG. 1 is an X-ray diffraction pattern of CoP/NC obtained in example 1 according to the present invention, and it can be seen from FIG. 1 that a series of diffraction peaks for N-CoP/NC can be indexed as CoP phase (JCPDS No. 29-0497).
FIG. 2 is a scanning electron micrograph of catalysts (NCP, HNCP and CoP/NC) obtained in example 1 according to the present invention. Figure 2A shows that NCP (product after ATMP pyrolysis) exhibits a curled flake morphology with some particle aggregates at the flake edges. After adding ATMP to melamine, HNCP showed a two-dimensional sheet morphology with irregular dimensions, as shown in fig. 2B. Interestingly, when Co is used 2+ After addition, as shown in FIG. 2C, the morphology of N-CoP/NC presents a uniform nanosheet array, with the width of the nanosheet being about 200nm.
FIG. 3 is a graph of (A) Linear sweep voltammograms, (B) Linear sweep voltammograms, (C) methanol tolerance and (D) stability of the catalysts (NCP, HNCP and CoP/NC) and 20% commercial Pt-modified rotating disk electrode (RRDE) obtained in example 1 according to the present invention in 0.1M KOH solution. As shown in FIG. 3A, in N2 (dotted line) and O 2 (solid line) saturated electrolyte at 10mV s -1 The scanning rate of (c) performs CVs. Compared with the initial potentials of NCP (0.812V) and HNCP (0.865V), the initial potential of the N-CoP/NC catalyst (Eonset = 0.908V) is more positive, and the cathode current is higher, and is equivalent to commercial Pt/C (0.911V). LSV testing was performed on all catalysts at 1600rpm and the results are shown in FIG. 3B. Half of N-CoP/NCWave potential (0.824V) and diffusion limiting current density (6.280 mA cm) -2 ) The ratio of (1) to NCP (0.664V, 2.226mA cm) -2 ) And HNCP (0.802V, 3.764mA cm -2 ) High. Currently, the catalysts used in Direct Methanol Fuel Cells (DMFC) are predominantly platinum-based noble metal catalysts. However, carbon monoxide (CO), an anodic oxidation product of methanol, is liable to poison the catalyst, which is a major problem facing researchers at present. Therefore, DMFC must take into account the methanol resistance of the catalyst. The methanol resistance of N-CoP/NC and Pt/C was measured by chronoamperometry (i-t). As shown in FIG. 3C, the current density of the Pt/C electrode immediately decreased by about 20% after adding 3.0M methanol to 10.0mL of 0.1M KOH electrolyte for 600 seconds. In sharp contrast, methanol did not significantly affect N-CoP/NC, and the current density decreased by about 5%. The results show that N-CoP/NC has excellent methanol permeation resistance. The catalyst stability was further evaluated with i-t. As shown in FIG. 3D, the CoP nanocomposite electrode is at O 2 The current density was only lost by about 5% and the Pt/C was lost by about 16% for 500 minutes in saturated 0.1M KOH electrolyte, indicating that the N-CoP/NC nanocomposite electrode had good stability in alkaline media. CoP has an N-doped core-shell structure and stable C, N, P chemical bonds, which are responsible for its excellent methanol resistance and long-term stability.
FIG. 4 is a graph of (A) oxygen evolution linear sweep voltammogram and (B) stability of CoP/NC and 20% commercial Pt modified rotating disk electrode (RRDE) obtained in example 1 according to the invention in 1.0M KOH solution. As shown in FIG. 4A, N-CoP/NC only needs 153mV to realize 10mA cm -2 The current density of (2) is superior to that of NCP (179 mV), HNCP (176 mV), pt/C (1.68 mV), and IrO2/C (1.56 mV). After the long-term stability test, after 500 minutes of operation, fig. 4B shows significant stability, it is evident that there is almost no overpotential decay, indicating significant stability. Meanwhile, the LSV curves (4B inset) almost overlapped before and after the N-CoP/NC continuous operation for 500 minutes also show excellent stability.
FIG. 5 shows CoP/NC and 20% commercial Pt modified rotating disk electrode (RRDE) H at 0.5M obtained according to example 1 of the present invention 2 SO 4 Linear sweep voltammogram for hydrogen evolution (A) in solutionAnd (B) stability profile. N-CoP/NC requires 160mV overpotential to drive 10mA cm -2 The current density of (2) was, although lower than Pt/C (70 mV), better than NCP and HNCP (FIG. 5A). The i-t test proves that the N-CoP/NC is at 0.5 MH 2 SO 4 There was significant stability in solution over 500 minutes of continuous operation (fig. 5B). Furthermore, after 500 minutes of continuous operation, the attenuation of overpotential and current density was negligible (FIG. 5B inset), indicating that N-CoP/NC has superior stability.
Those of ordinary skill in the art will understand that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (11)
1. A preparation method of a cobalt phosphide nanosheet array three-function catalyst is characterized by comprising the following steps:
the method comprises the following steps: dissolving melamine in deionized water at a certain temperature until a transparent solution is formed;
step two: adding a certain amount of aminotrimethylene phosphonic Acid (ATMP) into the solution, stirring for a certain time, and forming a supramolecular gel precursor when the mixture is naturally cooled to room temperature;
step three: adding cobalt salt into the supermolecule gel precursor solution obtained in the step two, continuously stirring for a certain time, centrifuging, and drying to obtain a pink product;
step four: and (4) placing the pink product formed in the third step into a tubular furnace, and calcining at high temperature in a protective gas atmosphere to obtain the cobalt phosphide nanosheet array three-function catalyst.
2. The preparation method of the cobalt phosphide nanosheet array trifunctional catalyst according to claim 1, wherein the preparation method comprises the following steps: in the first step, the molar volume range of the melamine is 0.2-0.3 mol/L, and the temperature is between 80-100 ℃.
3. The preparation method of the cobalt phosphide nanosheet array trifunctional catalyst according to claim 1, wherein the preparation method comprises the following steps: in the second step, the mass concentration of the ATMP aqueous solution is 50wt.% to 75wt.%, and the volume range of the added ATMP is 0.8mL to 1.0mL.
4. The preparation method of the cobalt phosphide nanosheet array trifunctional catalyst according to claim 1, wherein the preparation method comprises the following steps: in the second step, the stirring time is 3-5min.
5. The preparation method of the cobalt phosphide nanosheet array trifunctional catalyst according to claim 1, wherein the preparation method comprises the following steps: in step three, the cobalt salt may be Co (NO) 3 ) 2 ·6H 2 O、CoCl 2 And Co (C) 2 H 3 O 2 ) 2 The molar weight of the added cobalt salt is 1-2 mmol.
6. The preparation method of the cobalt phosphide nanosheet array trifunctional catalyst according to claim 1, wherein the preparation method comprises the following steps: in the third step, the stirring time is 3-10min.
7. The preparation method of the cobalt phosphide nanosheet array trifunctional catalyst according to claim 1, wherein the preparation method comprises the following steps: in the fourth step, the protective atmosphere may be one of nitrogen and argon.
8. The preparation method of the cobalt phosphide nanosheet array trifunctional catalyst according to claim 1, wherein the preparation method comprises the following steps: in the fourth step, the calcining temperature is 900-950 ℃, the heating rate is 3-5 ℃/min, and the heat preservation time is 2-3 h.
9. The cobalt phosphide nano-scale as defined in claim 1A simple 'Lewis acid-base interaction' strategy is provided, lewis acid ATMP is used as a proton donor, and Lewis base melamine is used as the proton donor. The combination of ATMP and melamine through hydrogen bond greatly weakens Co 2+ And the strong chelating ability of ATMP. In the high-temperature calcination process, the carbon-rich melamine ligand enables the cobalt-organic phosphorus coordination polymer to be placed in a strong reducing atmosphere, so that the purpose of in-situ phosphorization is achieved.
10. A cobalt phosphide nanosheet array trifunctional catalyst, characterized in that the cobalt phosphide nanosheet array trifunctional catalyst is prepared by the preparation method of any one of claims 1 to 7.
11. The application of the cobalt phosphide nanosheet array trifunctional catalyst prepared by the preparation method of any one of claims 1 to 7 is characterized in that the cobalt phosphide nanosheet array trifunctional catalyst is used for oxygen reduction and oxygen evolution in alkaline electrolyte and hydrogen evolution reaction in acidic electrolyte.
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| KR20210154674A (en) * | 2020-06-12 | 2021-12-21 | 고려대학교 산학협력단 | Manufacturing method of electrocatalysts based on cobalt phosphide whth crystalline-amorphous hybrid phase and electrocatalysts based on cobalt phosphide whth crystalline-amorphous hybrid phase prepared by the same |
| CN114481204A (en) * | 2022-01-26 | 2022-05-13 | 青岛科技大学 | Preparation of cobalt phosphide-supported noble metal nano material |
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| KR20210154674A (en) * | 2020-06-12 | 2021-12-21 | 고려대학교 산학협력단 | Manufacturing method of electrocatalysts based on cobalt phosphide whth crystalline-amorphous hybrid phase and electrocatalysts based on cobalt phosphide whth crystalline-amorphous hybrid phase prepared by the same |
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