CN111715248B - Cathode catalyst for hollow nano electrolyzed water and preparation method thereof - Google Patents
Cathode catalyst for hollow nano electrolyzed water and preparation method thereof Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000003054 catalyst Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- -1 potassium ferricyanide Chemical compound 0.000 claims abstract description 28
- 239000011259 mixed solution Substances 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 15
- 238000000137 annealing Methods 0.000 claims abstract description 13
- 229910021205 NaH2PO2 Inorganic materials 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 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 7
- 239000001509 sodium citrate Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims description 27
- 229910021641 deionized water Inorganic materials 0.000 claims description 27
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 10
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 10
- 235000011150 stannous chloride Nutrition 0.000 claims description 10
- 239000001119 stannous chloride Substances 0.000 claims description 10
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 150000001868 cobalt Chemical class 0.000 abstract description 10
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 40
- 238000003756 stirring Methods 0.000 description 14
- 229960000999 sodium citrate dihydrate Drugs 0.000 description 12
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 238000001291 vacuum drying Methods 0.000 description 10
- 229910052723 transition metal Inorganic materials 0.000 description 9
- 150000003624 transition metals Chemical class 0.000 description 9
- 238000005303 weighing Methods 0.000 description 8
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000010411 electrocatalyst Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229910003321 CoFe Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 2
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical group N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- 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
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Abstract
The invention provides a cathode catalyst for hollow nano electrolyzed water and a preparation method thereof, wherein the method comprises the following steps: step 1, adding potassium ferricyanide into a mixed solution of cobalt salt and sodium citrate, and standing, wherein the molar ratio of the cobalt salt to the potassium ferricyanide is (0.1-1): (0.2-0.5), separating the obtained product, and then sequentially washing and drying to obtain a prussian blue analog compound; step 2, according to (0.2-0.4): (1-2) mixing the Prussian-blue-like compound and NaH2PO2And carrying out annealing treatment under protective gas to obtain the cathode catalyst for the hollow nano-electrolyzed water. The method has the advantages of uniform reaction heating, simple and easy operation, easy control, low cost of used raw materials, easy obtainment of target products, hollow structure of the prepared catalyst, and excellent electrocatalytic activity and cathode reaction stability.
Description
Technical Field
The invention relates to the technical field of electrocatalysis, in particular to a cathode catalyst for hollow nano electrolyzed water and a preparation method thereof.
Background
Prussian Blue Analogue (PBA) was discovered as early as 1704 and is one of the oldest and simplest metal-organic framework compounds. Due to the wide application of the catalyst in the fields of gas adsorption, energy storage, catalysis, medicine carrying and the like, the catalyst is widely concerned and researched.
The prussian-like blue compound is a supramolecular structure formed by self-assembly connection of a transition metal central ion serving as a metal joint and a cyanide group ligand serving as an organic connector. The transition metal exists in two different positions adjacent to the carbon atom and the nitrogen atom, respectively, in the framework structure of the prussian blue, and the two positions can be occupied by different metal ions. These metal elements include transition metals such as iron, cobalt, nickel, zinc, and copper. Furthermore, a small amount of noble metal ions can be used to replace the transition metals in the transition metal ion positions in the framework structure, while still ensuring that the framework structure of the prussian blue-like is maintained.
The transition metal phosphide is also a catalyst widely used in hydrogen evolution, is a cathode catalyst for water electrolysis, and has performance even exceeding that of corresponding transition metals and alloys. The Prussian blue-like compound and the phosphorus source precursor can be used for preparing the transition metal phosphide electrocatalyst with excellent performance, such as CoFe-PBA, but the transition metal phosphide electrocatalyst synthesized by the existing method is 10mA/cm2The method has the disadvantage of high overpotential, so the synthesis of the method needs to be improved.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the cathode catalyst for the hollow nano-electrolyzed water and the preparation method thereof, the reaction is heated uniformly, the operation is simple and easy to control, the used raw materials are low in cost, the target product is easy to obtain, and the prepared catalyst is of a hollow structure and has excellent electrocatalytic activity and cathode reaction stability.
The invention is realized by the following technical scheme:
a preparation method of a cathode catalyst for hollow nano-electrolyzed water comprises the following steps:
Preferably, in the step 1, the molar ratio of the cobalt salt to the sodium citrate is (0.1-1): (0.5-2).
Preferably, the cobalt salt in step 1 is one or more of cobalt chloride, nitrate, sulfate and acetate.
Preferably, in the step 1, the mixed solution is added with potassium ferricyanide and then is kept stand for 20-48h.
Preferably, in the step 1, potassium ferricyanide is added into the mixed solution of cobalt salt, stannous chloride and sodium citrate and then the mixture is kept stand, wherein the molar ratio of the cobalt salt to the stannous chloride is (0.1-1): (0.1-1).
Preferably, in step 2, the annealing is performed at 200-500 ℃.
Preferably, in step 2, the annealing is performed for 1 to 3 hours.
Preferably, step 1 washes the isolated product with deionized water and absolute ethanol.
A cathode catalyst for hollow nano-electrolyzed water obtained by the method for preparing a cathode catalyst for hollow nano-electrolyzed water as set forth in any one of the above.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention relates to a preparation method of a cathode catalyst for hollow nano-electrolyzed water, which comprises the steps of firstly carrying out precipitation reaction on cobalt salt, sodium citrate and potassium ferricyanide to obtain a Prussian-blue-like compound, and then annealing the Prussian-blue-like compound and a phosphorus source precursor together to prepare the transition metal phosphide electrocatalyst with excellent performance. After annealing, the nano particles are mutually aggregated and tightly connected to form a large specific surface area, so that more electrochemical active sites and a larger contact area with electrolyte can be provided, and the catalytic performance is improved; the hollow structure can accelerate the transmission of electrons and ions and effectively relieve the problem of volume expansion caused by the circulation shuttle of the ions; so that the composite material shows high electrocatalytic activity, excellent HER performance of electrolyzed water and excellent stability.
Furthermore, the CoSnFe-PBA with the hollow structure has good appearance, is easy to regulate and control, has excellent electrocatalytic hydrogen production performance, and is added with Sn relative to PBA cubic nanometer materials2+By passing through NaH2PO2The hollow corner-cut polyhedron PBA obtained by annealing has larger specific surface area and exposes more active sites, so that the hollow corner-cut polyhedron PBA has more excellent electrocatalytic activity and excellent electrolyzed water HER performance.
Drawings
FIG. 1 is an XRD pattern of CoFe-PBA and CoSnFe-PBA prepared in example 1 of the present invention;
FIG. 2 is the XRD patterns of CoFeP-PBA and CoSnFeP-PBA prepared in example 1 of the present invention;
FIG. 3 is an SEM representation of CoFe-PBA prepared in example 1 of the present invention;
FIG. 4 is an SEM representation of CoSnFe-PBA prepared in example 1 of the present invention;
FIG. 5 is an SEM representation of CoFeP-PBA prepared in example 1 of the present invention;
FIG. 6 is a SEM representation of CoSnFeP-PBA prepared in example 1 of the invention;
FIG. 7 is the LSV curve of CoFe PBA, coSnFe PBA, coFeP-PBA and CoSnFeP-PBA prepared in example 1 of the present invention in 1M KOH electrolyte.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The invention discloses a preparation method of a cathode catalyst for hollow nano-electrolyzed water, which comprises two schemes, specifically comprising the following steps:
the first scheme is as follows:
weighing 0.1-1mmol of cobalt salt and 0.5-2mmol of sodium citrate dihydrate, wherein the cobalt metal salt can be one or more of cobalt chloride hexahydrate, nitrate, sulfate and acetate, and because the proportion is not required and the effects are the same, the following examples only take each pure substance, dissolving the pure substances in 10-30mL of deionized water, adding a potassium ferricyanide aqueous solution while stirring, uniformly mixing the potassium ferricyanide aqueous solution by dissolving 0.2-0.5mmol of potassium ferricyanide in 10-30mL of deionized water, continuously stirring for 5-30min to obtain a mixed solution, standing for 20-48h, centrifuging the product, washing the product with deionized water and absolute ethyl alcohol, drying in vacuum, and synthesizing a CoFe-PBA cube by a precipitation method.
Weighing 200-400mg CoFe-PBA cube, placing in a small crucible, and weighing 1-2g NaH2PO2Placing in a large crucible, placing a small crucible in the large crucible, introducing helium as protective gas, annealing at 200-500 deg.C for 1-3 hr, and reacting with NaH2PO2Etching of CoFe-PBA cubes, i.e. NaH2PO2Generating pH at high temperature3And phosphorizing the CoFe-PBA cube to obtain a hollow nano CoFe-PBA cube, namely the cathode catalyst for electrolyzing water.
The second scheme is as follows:
weighing 0.1-1mmol of cobalt metal salt, 0.1-1mmol of stannous chloride and 0.5-2mmol of sodium citrate dihydrate, wherein the cobalt metal salt can be one or more of cobalt chloride hexahydrate, nitrate, sulfate and acetate, dissolving the cobalt metal salt in 10-30mL of deionized water, adding a potassium ferricyanide aqueous solution while stirring, dissolving the potassium ferricyanide aqueous solution in 10-30mL of deionized water by 0.2-0.5mmol of potassium ferricyanide, uniformly mixing, continuously stirring for 5-30min to obtain a mixed solution, standing for 20-48h, centrifuging, washing and drying the product, and synthesizing to obtain the CoSnFe-PBA corner cut polyhedron by a precipitation method.
Weighing 200-400mg CoSnFe-PBA corner-cut polyhedron, placing in a small crucible, and weighing 1-2g NaH2PO2Placing into a large crucible, placing a small crucible into the large crucible, introducing helium gas as protective gas, annealing at 200-500 deg.C for 1-3 hr, and reacting with NaH2PO2Etching CoSnFe-PBA cubes, i.e. NaH2PO2Generating pH at high temperature3And phosphorizing the CoSnFe-PBA cube to obtain a hollow nano CoSnFe-PBA corner-cut polyhedron, namely the cathode catalyst for electrolyzing water.
The invention adopts an annealing method to chemically etch the CoFe-PBA cube and the CoSnFe-PBA corner-cut polyhedron structure to form the nanocube and the corner-cut polyhedron structure with hollow structures, and the structure is opposite to that without Sn2+The PBA cubic nanometer material is prepared by adding Sn2+And the hollow corner-cut polyhedron PBA obtained by annealing has larger specific surface area and exposes more active sites, so that the hollow corner-cut polyhedron PBA has more excellent electrocatalytic activity and excellent electrolyzed water HER performance.
The invention is illustrated in more detail below by means of specific examples:
example 1
Dissolving 142.758mg (0.6 mmol) of cobalt chloride hexahydrate and 264.69mg (0.9 mmol) of sodium citrate dihydrate in 20mL of deionized water to form a solution A, dissolving 0.4mmol of potassium ferricyanide in 20mL of deionized water to form a solution B, slowly pouring the solution A into the stirring solution B to obtain a mixed solution, standing for 48h, centrifuging, washing and vacuum-drying the product for 24h to obtain CoFe-PBA.
200mg of CoFe-PBA cubes were weighed into a small crucible, and 1g of NaH was weighed2PO2Placing the mixture into a large crucible, placing a small crucible into the large crucible, and reacting for 2 hours at 350 ℃ to obtain a hollow PBA cube.
Dissolving 95.172mg of cobalt chloride hexahydrate, 45.126mg of stannous chloride 0.2mmol and 264.69mg of sodium citrate dihydrate 0.9mmol in 20mL of deionized water to form a solution A, dissolving 0.4mmol of potassium ferricyanide in 20mL of deionized water to form a solution B, slowly pouring the solution A into the stirring solution B to obtain a mixed solution, standing for 48h, and centrifuging, washing and vacuum drying the product for 24h to obtain the CoSnFe-PBA.
200mg of CoSnFe-PBA corner-cut polyhedron is weighed and placed in a small crucible, and then 1g of NaH is weighed2PO2Placing the mixture into a large crucible, placing a small crucible into the large crucible, and reacting for 2 hours at 350 ℃ to obtain the hollow PBA corner-cut polyhedron.
FIG. 1 is XRD patterns of CoFe-PBA and CoSnFe-PBA, respectively, and it can be seen that diffraction peaks are shown at approximately 17.5, 24.8, 35.4 and 39.8, 43.7, 51.0, respectively, corresponding to (200), (220), (400), (420), (422) and (440) planes of CoFe PBA, respectively, indicating the formation of CoFe-PBA and CoSnFe-PBA.
Fig. 2 is XRD patterns of CoFeP-PBA and CoSnFeP-PBA, respectively, and it can be seen that diffraction peaks are shown at approximately 23.6, 32.0, 35.6 and 48.3, 56.7, respectively, corresponding to (101), (002), (102), (211) and (301) planes of CoFeP-PBA, respectively, indicating the formation of CoFeP-PBA and CoSnFeP-PBA.
FIGS. 3, 4, 5 and 6 are SEM characterization diagrams of CoFe-PBA, coSnFe-PBA, coFeP-PBA and CoSnFeP-PBA at 500nm magnification, respectively, and it can be seen that the synthesized CoFe-PBA has a solid cubic structure, and the CoSnFe-PBA has a solid corner-cutting polyhedral structure, and is uniform in size and distribution; the surface of the CoFeP-PBA and the CoSnFeP-PBA becomes rough after annealing treatment, but the shape is well maintained.
FIG. 7 is LSV curve diagrams of CoFe-PBA, coSnFe-PBA, coFeP-PBA and CoSnFeP-PBA, respectively, and it can be seen that the prepared CoSnFeP-PBA has good electrocatalytic hydrogen production performance in 1M KOH electrolyte as cathode anode carbon rod, and its HER performance is significantly improved and reaches 10mA/cm2The overpotential is approximately 62mV.
After the CoFeP-PBA and the CoSnFeP-PBA are subjected to several CV cycles, the LSV curve is almost the same as the initial curve, which indicates that the stability is good.
Example 2
Dissolving 0.1mmol of cobalt chloride hexahydrate and 0.5mmol of sodium citrate dihydrate in 20mL of deionized water to form a solution A, dissolving 0.3mmol of potassium ferricyanide in 20mL of deionized water to form a solution B, slowly pouring the solution A into the stirring solution B to obtain a mixed solution, standing for 20h, and centrifuging, washing and vacuum drying the product for 24h to obtain CoFe-PBA.
250mg of CoFe-PBA cubes are weighed into a small crucible, and then 2g of NaH are weighed2PO2Placing the mixture into a large crucible, placing a small crucible into the large crucible, and reacting for 1h at 200 ℃ to obtain a hollow PBA cube.
Dissolving 0.1mmol of cobalt chloride hexahydrate, 0.8mmol of stannous chloride and 0.5mmol of sodium citrate dihydrate in 20mL of deionized water to form a solution A, dissolving 0.3mmol of potassium ferricyanide in 20mL of deionized water to form a solution B, slowly pouring the solution A into the stirring solution B to obtain a mixed solution, standing for 20h, and centrifuging, washing and vacuum drying the product for 24h to obtain CoSnFe-PBA.
Weighing 250mg CoSnFe-PBA corner-cut polyhedron, placing in a small crucible, and weighing 2g NaH2PO2Placing the mixture into a large crucible, placing a small crucible into the large crucible, and reacting for 1h at 200 ℃ to obtain the hollow PBA corner-cut polyhedron.
Example 3
Dissolving 0.8mmol of cobalt nitrate hexahydrate and 2mmol of sodium citrate dihydrate in 20mL of deionized water to form a solution A, dissolving 0.2mmol of potassium ferricyanide in 20mL of deionized water to form a solution B, slowly pouring the solution A into the stirring solution B to obtain a mixed solution, standing for 40h, and centrifuging, washing and vacuum drying the product for 24h to obtain CoFe-PBA.
300mg of CoFe-PBA cubes were weighed into a small crucible, and 1.2g of NaH was weighed2PO2Placing the mixture into a large crucible, placing a small crucible into the large crucible, and reacting for 3 hours at 500 ℃ to obtain a hollow PBA cube.
Dissolving 0.8mmol of cobalt nitrate hexahydrate, 1mmol of stannous chloride and 2mmol of sodium citrate dihydrate in 20mL of deionized water to form a solution A, dissolving 0.2mmol of potassium ferricyanide in 20mL of deionized water to form a solution B, slowly pouring the solution A into the stirring solution B to obtain a mixed solution, standing for 40h, and centrifuging, washing and vacuum drying the product for 24h to obtain CoSnFe-PBA.
300mg of CoSnFe-PBA corner-cut polyhedron is weighed and placed in a small crucible, and then 1.2g of NaH is weighed2PO2Placing the mixture into a large crucible, placing a small crucible into the large crucible, and reacting for 3h at 500 ℃ to obtain the hollow PBA corner-cut polyhedron.
Example 4
Dissolving 0.3mmol of cobalt sulfate heptahydrate and 1.8mmol of sodium citrate dihydrate in 20mL of deionized water to form a solution A, dissolving 0.4mmol of potassium ferricyanide in 20mL of deionized water to form a solution B, slowly pouring the solution A into the stirring solution B to obtain a mixed solution, standing for 25h, and centrifuging, washing and vacuum drying the product for 24h to obtain CoFe-PBA.
400mg of CoFe-PBA cubes were weighed into a small crucible, and 1.8g of NaH was weighed2PO2Placing the mixture into a large crucible, placing a small crucible into the large crucible, and reacting for 2h at 250 ℃ to obtain a hollow PBA cube.
Dissolving 0.3mmol of cobalt sulfate heptahydrate, 0.1mmol of stannous chloride and 1.8mmol of sodium citrate dihydrate in 20mL of deionized water to form a solution A, dissolving 0.4mmol of potassium ferricyanide in 20mL of deionized water to form a solution B, slowly pouring the solution A into the stirring solution B to obtain a mixed solution, standing for 25h, and centrifuging, washing and vacuum drying the product for 24h to obtain CoSnFe-PBA.
400mg of CoSnFe-PBA corner-cut polyhedron is weighed and placed in a small crucible, and 1.8g of NaH is weighed2PO2Placing the mixture into a large crucible, placing a small crucible into the large crucible, and reacting for 2h at 250 ℃ to obtain the hollow PBA corner-cut polyhedron.
Example 5
Dissolving 1mmol of cobalt acetate and 1.2mmol of sodium citrate dihydrate in 20mL of deionized water to form a solution A, dissolving 0.1mmol of potassium ferricyanide in 20mL of deionized water to form a solution B, slowly pouring the solution A into the stirring solution B to obtain a mixed solution, standing for 30h, and centrifuging, washing and vacuum-drying the product for 24h to obtain CoFe-PBA.
350mg of CoFe-PBA cubes were weighed into a small crucible, and 1.6g of NaH was weighed2PO2Placing the mixture into a large crucible, placing a small crucible into the large crucible, and reacting for 2h at 450 ℃ to obtain a hollow PBA cube.
Dissolving 1mmol of cobalt acetate, 0.5mmol of stannous chloride and 1.2mmol of sodium citrate dihydrate in 20mL of deionized water to form a solution A, dissolving 0.1mmol of potassium ferricyanide in 20mL of deionized water to form a solution B, slowly pouring the solution A into the stirring solution B to obtain a mixed solution, standing for 30h, and centrifuging, washing and vacuum drying the product for 24h to obtain the CoSnFe-PBA.
350mg of CoSnFe-PBA corner-cut polyhedron is weighed and placed in a small crucible, and then 1.6g of NaH is weighed2PO2Placing the mixture into a large crucible, placing a small crucible into the large crucible, and reacting for 2 hours at 450 ℃ to obtain the hollow PBA corner-cut polyhedron.
Finally, it should be noted that: although the present invention has been described in detail with reference to the above embodiments, it should be understood by those skilled in the art that: modifications and equivalents may be made to the embodiments of the invention without departing from the spirit and scope of the invention, which is intended to be covered by the claims.
Claims (3)
1. A preparation method of a cathode catalyst for hollow nano-electrolyzed water is characterized by comprising the following steps:
step 1, adding potassium ferricyanide into a mixed solution of cobalt chloride, stannous chloride and sodium citrate, standing for 20-48h, wherein the molar ratio of the cobalt chloride to the potassium ferricyanide is (0.1-1): (0.2-0.5), separating the obtained product, and then sequentially washing and drying to obtain a prussian blue analog compound;
the molar ratio of the cobalt chloride to the sodium citrate is (0.1-1): (0.5-2), the molar ratio of the cobalt chloride to the stannous chloride is (0.1-1): (0.1-1);
step 2, according to (0.2-0.4): (1-2) Prussian-like blueCompound and NaH2PO2Annealing for 1-3h at 200-500 ℃ under protective gas to obtain the cathode catalyst for the hollow nano-electrolyzed water.
2. The method for preparing a cathode catalyst for hollow nano-electrolyzed water according to claim 1, wherein the separated product is washed with deionized water and absolute ethanol in step 1.
3. A cathode catalyst for hollow nano-electrolyzed water obtained by the method for producing a cathode catalyst for hollow nano-electrolyzed water according to any one of claims 1 to 2.
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| CN113388847B (en) * | 2021-07-06 | 2022-12-20 | 青岛科技大学 | Prussian blue analogue derived metal sulfide/nitrogen-doped carbon electrocatalyst and preparation method and application thereof |
| CN113584515A (en) * | 2021-09-09 | 2021-11-02 | 哈尔滨理工大学 | Based on CoxP/FeP electrode material as working electrode for electrocatalytic hydrogen evolution |
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