CN115287694A - Iron-based phosphate electrocatalyst material and application - Google Patents
Iron-based phosphate electrocatalyst material and application Download PDFInfo
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- CN115287694A CN115287694A CN202210336709.3A CN202210336709A CN115287694A CN 115287694 A CN115287694 A CN 115287694A CN 202210336709 A CN202210336709 A CN 202210336709A CN 115287694 A CN115287694 A CN 115287694A
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 60
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 39
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 39
- 239000010452 phosphate Substances 0.000 title claims abstract description 39
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 32
- 239000000463 material Substances 0.000 title claims abstract description 26
- 239000002686 phosphate fertilizer Substances 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 230000000694 effects Effects 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 29
- 239000006228 supernatant Substances 0.000 claims description 29
- 239000000843 powder Substances 0.000 claims description 23
- 239000011259 mixed solution Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 11
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 238000000354 decomposition reaction Methods 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 abstract description 17
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 abstract 1
- 235000021317 phosphate Nutrition 0.000 description 29
- 229920006395 saturated elastomer Polymers 0.000 description 9
- 229910001463 metal phosphate Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000001075 voltammogram Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- ABKDZANKXKCXKG-UHFFFAOYSA-B P(=O)([O-])([O-])[O-].[W+4].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-].[W+4].[W+4] Chemical compound P(=O)([O-])([O-])[O-].[W+4].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-].[W+4].[W+4] ABKDZANKXKCXKG-UHFFFAOYSA-B 0.000 description 1
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 description 1
- 229910000161 silver phosphate Inorganic materials 0.000 description 1
- 229940019931 silver phosphate Drugs 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 229910000319 transition metal phosphate Inorganic materials 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- 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
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
-
- 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
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- 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
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Fertilizers (AREA)
Abstract
The invention discloses a preparation method and application of an iron-based phosphate electrocatalyst material. The electrocatalyst is prepared and synthesized by mainly using agricultural phosphate fertilizer and iron rust as main raw materials through a one-step hydrothermal method. The iron-based phosphate electrocatalytic material provided by the invention has lower overpotential of oxygen evolution reaction and good electrocatalytic activity. Experiments show that: by designing different preparation conditions, the iron-based phosphate electrocatalyst provided by the invention has the current density of 10mA cm ‑2 When the oxygen evolution reaction overpotential is as low as 267mV. In addition, the raw materials provided by the invention are extremely low in price, mild in preparation conditions and simple in operation, and are beneficial to large-scale production.
Description
Technical Field
The invention relates to the technical field of electrocatalyst materials, in particular to an iron-based phosphate electrocatalyst material and application thereof.
Background
The preparation of hydrogen and oxygen by decomposing water by using electric energy is one of important means for realizing carbon peak reaching and carbon neutralization, and can effectively promote green development of China and reduce carbon emission. The electrocatalyst can effectively reduce the reaction energy barrier of water decomposition and improve the reaction rate of electrolyzed water, so the development of the high-performance electrocatalyst becomes one of leading hot spots in the field of new energy sources at present. The whole process of water decomposition comprises a cathodic hydrogen evolution reaction and an anodic Oxygen Evolution Reaction (OER), wherein the OER reaction rate with four electrons is far lower than that with only two electrons, so that the whole reaction of water decomposition is realizedThe rate is determined by the rate of the OER reaction that occurs at the anode. Therefore, the development of high-performance OER electrocatalysts has become a key factor for increasing the rate of water decomposition. Due to the higher operating potential and the unique oxygen-based intermediate during the OER reaction, the surface of the catalyst is typically oxidized. In order to ensure long-term stability of OER catalysts, metal oxides or hydroxides have been the main subject of investigation for OER electrocatalysts. The study indicated that: noble metal oxides (e.g., ruO) 2 And IrO 2 ) Has excellent OER catalytic performance (low OER overpotential), but the scarcity and high cost severely limit the large-scale application.
And the transition metals such as Fe, co, ni and the like close to the noble metals in the periodic table of the elements have the outermost valence electron arrangement similar to that of the noble metals, so that Fe, co and Ni-based compounds are widely researched by domestic and foreign scholars and are intended to replace the existing noble metal-based catalysts. Among them, the transition metal phosphide has an OER catalytic performance superior to other metal compounds, such as: sodium phosphate, potassium phosphate, magnesium phosphate, tungsten phosphate, copper phosphate, silver phosphate and the like have proven to have good electrocatalytic properties and are used for catalyzing some esterification reactions and photo-oxidation reactions, but transition metal phosphates, particularly phosphate materials based on phosphoric acid Fe, co or Ni, are not reported to be used for electrocatalytic oxygen evolution reactions. In addition, most of the existing catalyst preparation raw materials are high-purity medicines purchased by companies such as alatin and the like, and the price is not high, so that the cost is not saved. Therefore, it is necessary to develop a lower-cost preparation method and expand the industrial application of the electrocatalyst.
Disclosure of Invention
The invention aims to provide preparation and application of an iron-based phosphate electrocatalyst material. The electrocatalyst has the advantages of extremely low raw material price, simple and feasible preparation method and long-term market application prospect. The prepared iron-based phosphate has reduced OER over potential and good electrocatalytic activity.
In order to realize the purpose, the invention adopts the following technical scheme:
the iron-based phosphate electrocatalytic material is synthesized by adopting a one-step hydrothermal method. The preparation method comprises the following steps: dissolving enough phosphate fertilizer in deionized water, taking supernatant of saturated phosphate fertilizer after precipitation, dropwise adding NaOH solution to adjust the pH value, adding ground iron rust powder into the solution, uniformly stirring, putting the mixed solution into a reaction kettle for hydrothermal reaction, taking precipitate for washing, and drying in vacuum to finally obtain the iron-based phosphate electro-catalytic material.
The method comprises the following specific key steps:
1) Preparing a phosphate fertilizer supernatant: weighing 5g of agricultural phosphate fertilizer, dissolving the agricultural phosphate fertilizer in 70mL of deionized water, fully stirring the mixture to enable the phosphate fertilizer to be dissolved in water in a saturated mode, taking 20-40 mL of saturated phosphate fertilizer supernatant after precipitation, dripping 1mol/L NaOH solution into the stirred supernatant, and adjusting the pH value to be 2-6.
2) Preparation of mixed solution: adding 0.1g of ground rust powder into the solution, wherein the mass ratio of the phosphate fertilizer supernatant to the rust is as follows: (200-400) 1, stirring for 10-15 min.
3) Preparation of iron-based phosphate powder samples: and putting the mixed solution into a reaction kettle for hydrothermal reaction at the temperature of 120-200 ℃ for 12-18 h, taking out the precipitate, washing the precipitate with deionized water for 3 times, and drying the precipitate in vacuum.
In the above technical solution, the pH value in step 1) is preferably 3 to 5, and more preferably 3.
In the above technical scheme, the mass ratio of the phosphate fertilizer supernatant to the rust in the step 2) is as follows: (200-400) 1, more preferably 300.
The iron-based phosphate electrocatalyst material prepared by the above method.
The electrocatalytic material is applied to electrocatalytic decomposition water-evolution oxygen reaction.
The present invention provides iron-based phosphate electrocatalyst materials. The iron-based phosphate prepared by utilizing the phosphate fertilizer and the rust has lower kinetic barrier of electrocatalytic oxygen evolution reaction and good electrocatalytic activity. The experimental result shows that the iron-based phosphate electrocatalyst provided by the invention has the current density of 10mA cm -2 When the potential is higher than the reference value, the OER overpotential is 267mV at the lowest level.
Compared with the conventional electrocatalyst, the invention has the following advantages: 1) The preparation cost is extremely low, and the raw materials are extremely easy to obtain; 2) The preparation process is simple; 3) The electrocatalytic performance of the sample is good.
The method provided by the invention can obtain the iron-based phosphate electrocatalyst material under mild conditions, has low price and simple and easily operated equipment, and can be used for large-scale production.
Drawings
FIG. 1 is an XRD pattern of the product prepared in example 1 of the instant invention;
FIG. 2 is an SEM photograph of a product of example 1 of the present invention;
FIG. 3 is a TEM image of a product prepared in example 1 of the present invention;
FIG. 4 is a plot of the Linear Scanning Voltammogram (LSV) of the products prepared in examples 1 to 8 of the present invention;
FIG. 5 is a graph of LSV at runs 1 and 1000 for the product of example 1 of the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention in conjunction with the following examples, but it will be understood that the description is intended to illustrate the features and advantages of the invention further and is not intended to limit the invention.
The invention provides a hydrothermal synthesis method of an iron-based phosphate electrocatalytic material, which comprises the following steps: the method comprises the steps of taking an agricultural phosphate fertilizer and rust as precursors, preparing the precursors through one-step hydrothermal reaction, and then washing and drying the precursors to obtain a final iron-based phosphate electrocatalytic material sample. The pH value of the supernatant in the scheme is the key of the scheme, and the mass ratio of the saturated phosphate fertilizer solution to the rust is also the important condition.
The iron-based phosphate electrocatalyst material prepared by the invention. The preparation method is characterized in that the iron-based phosphate material with the nanometer size is prepared through the hydrothermal reaction of the phosphate fertilizer supernatant and the iron rust powder, and the preparation process of the iron-based phosphate electrocatalyst material is optimized through the design of the pH value of a reaction liquid and the proportion of the phosphate fertilizer supernatant to the iron rust powder, so that the iron-based phosphate electrocatalyst material has a low OER reaction kinetic energy barrier and good electrocatalytic activity. The iron-based phosphate electrocatalyst provided by the invention has the current density of 10mA cm -2 When the potential is higher than the reference value, the OER overpotential is 267mV at the lowest level.
Compared with the prior art, the raw materials are low in price, the production cost is reduced, the method process is simple, and the industrial application is easy to realize. The electrocatalyst material prepared by the invention not only can be used for preparing oxygen by electrocatalytic decomposition of water, but also has great application potential in the aspects of metal-air batteries, fuel batteries and the like.
The agricultural phosphate fertilizer and NaOH adopted in the embodiment of the invention are purchased on a Taobao net, and the iron rust is collected from waste iron.
Example 1
In the embodiment, 5g of agricultural phosphate fertilizer is measured and dissolved in 70mL of deionized water, the mixture is fully stirred to enable the phosphate fertilizer to be dissolved in water in a saturated mode, 30mL of saturated phosphate fertilizer supernatant is obtained after precipitation, 1mol/L NaOH solution is dripped into the stirred supernatant, the pH value is adjusted to 3, 0.1g of ground rust powder is added into the solution, stirring is carried out for 10min, the mixed solution is placed into a reaction kettle to carry out hydrothermal reaction for 12h at 160 ℃, the mixed solution is taken out at room temperature and washed for 3 times, and vacuum drying is carried out for 6h at 50 ℃ to obtain iron-based metal phosphate powder.
As shown by line a in fig. 1, the XRD picture of the iron-based phosphate prepared by the practice of the present invention shows that the prepared iron-based phosphate has a crystal structure consistent with PDF card (# 45-1436).
As shown in fig. 2, which is an SEM picture of the iron-based phosphate prepared by the practice of the present invention, it is shown that the prepared iron-based phosphate exhibits a flaky morphology.
As shown in fig. 3, which is a TEM image of the iron matrix prepared in the practice of the present invention, the prepared iron matrix exhibited unclear lattice fringes, indicating low crystallinity.
As shown by line a in FIG. 4, the LSV curve for the iron base prepared in accordance with the practice of the present invention indicates a current density of 10mA cm -2 The OER overpotential is 267mV.
As shown in fig. 5, LSV curves for the 1 st and 1000 th runs of iron-based phosphate prepared in accordance with the practice of the present invention indicate that the sample has good electrocatalytic stability.
Example 2
In the embodiment, 5g of agricultural phosphate fertilizer is measured and dissolved in 70mL of deionized water, the mixture is fully stirred to enable the phosphate fertilizer to be dissolved in water in a saturated mode, 20mL of saturated phosphate fertilizer supernatant is obtained after precipitation, 1mol/L NaOH solution is dripped into the stirred supernatant, the pH value is adjusted to 3, 0.1g of ground rust powder is added into the solution, stirring is carried out for 10min, the mixed solution is placed into a reaction kettle to carry out hydrothermal reaction for 12h at 160 ℃, the mixed solution is taken out at room temperature and washed for 3 times, and vacuum drying is carried out for 6h at 50 ℃ to obtain iron-based metal phosphate powder.
As shown by line b in fig. 1, the XRD pattern of the iron-based phosphate prepared by the practice of the present invention shows that the prepared iron-based phosphate has a crystal structure consistent with PDF cards (# 45-1436).
The LSV curve for the iron base prepared in accordance with the practice of the present invention, as shown by line b in FIG. 4, shows at a current density of 10mA cm -2 Its OER overpotential was 285mV.
Example 3
In the embodiment, 5g of agricultural phosphate fertilizer is measured and dissolved in 70mL of deionized water, the mixture is fully stirred to enable the phosphate fertilizer to be dissolved in water in a saturated mode, 40mL of saturated phosphate fertilizer supernatant is obtained after precipitation, 1mol/L NaOH solution is dripped into the stirred supernatant, the pH value is adjusted to 3, 0.1g of ground rust powder is added into the solution, stirring is carried out for 10min, the mixed solution is placed into a reaction kettle to carry out hydrothermal reaction for 12h at 160 ℃, the mixed solution is taken out at room temperature and washed for 3 times, and vacuum drying is carried out for 6h at 50 ℃ to obtain iron-based metal phosphate powder.
Example 4
In the embodiment, 5g of agricultural phosphate fertilizer is measured and dissolved in 70mL of deionized water, the mixture is fully stirred to enable the phosphate fertilizer to be dissolved in water in a saturated mode, 50mL of saturated phosphate fertilizer supernatant is obtained after precipitation, 1mol/L NaOH solution is dripped into the stirred supernatant, the pH value is adjusted to 3, 0.1g of ground rust powder is added into the solution, stirring is carried out for 10min, the mixed solution is placed into a reaction kettle to carry out hydrothermal reaction for 12h at 160 ℃, the mixed solution is taken out at room temperature and washed for 3 times, and vacuum drying is carried out for 6h at 50 ℃ to obtain iron-based metal phosphate powder.
Example 5
In the embodiment, 5g of agricultural phosphate fertilizer is measured and dissolved in 70mL of deionized water, the agricultural phosphate fertilizer is fully stirred to be saturated and dissolved in the water, 30mL of supernatant of the saturated phosphate fertilizer is taken after precipitation, 1mol/L NaOH solution is dripped into the stirred supernatant, the pH value is adjusted to 2, 0.1g of ground rust powder is added into the solution, stirring is carried out for 10min, the mixed solution is put into a reaction kettle for hydrothermal reaction, reaction is carried out for 12h at 160 ℃, the mixed solution is taken out at room temperature, washed for 3 times and dried for 6h in vacuum at 50 ℃, and iron-based metal phosphate powder is obtained.
Example 6
In the embodiment, 5g of agricultural phosphate fertilizer is measured and dissolved in 70mL of deionized water, the mixture is fully stirred to enable the phosphate fertilizer to be dissolved in water in a saturated mode, 30mL of saturated phosphate fertilizer supernatant is obtained after precipitation, 1mol/L NaOH solution is dripped into the stirred supernatant, the pH value is adjusted to 4, 0.1g of ground rust powder is added into the solution, stirring is carried out for 10min, the mixed solution is placed into a reaction kettle to carry out hydrothermal reaction for 12h at 160 ℃, the mixed solution is taken out at room temperature and washed for 3 times, and vacuum drying is carried out for 6h at 50 ℃ to obtain iron-based metal phosphate powder.
Example 7
In the embodiment, 5g of agricultural phosphate fertilizer is measured and dissolved in 70mL of deionized water, the mixture is fully stirred to enable the phosphate fertilizer to be dissolved in water in a saturated mode, 30mL of saturated phosphate fertilizer supernatant is obtained after precipitation, 1mol/L NaOH solution is dripped into the stirred supernatant, the pH value is adjusted to 5, 0.1g of ground rust powder is added into the solution, stirring is carried out for 10min, the mixed solution is placed into a reaction kettle to carry out hydrothermal reaction for 12h at 160 ℃, the mixed solution is taken out at room temperature and washed for 3 times, and vacuum drying is carried out for 6h at 50 ℃ to obtain iron-based metal phosphate powder.
Example 8
In the embodiment, 5g of agricultural phosphate fertilizer is measured and dissolved in 70mL of deionized water, the mixture is fully stirred to enable the phosphate fertilizer to be dissolved in water in a saturated mode, 30mL of saturated phosphate fertilizer supernatant is obtained after precipitation, 1mol/L NaOH solution is dripped into the stirred supernatant, the pH value is adjusted to 6, 0.1g of ground rust powder is added into the solution, stirring is carried out for 10min, the mixed solution is placed into a reaction kettle to carry out hydrothermal reaction, the hydrothermal reaction is carried out for 12h at 160 ℃, the mixed solution is taken out at room temperature and washed for 3 times, and vacuum drying is carried out for 6h at 50 ℃ to obtain iron-based metal phosphate powder.
As shown by line c in fig. 4, is the hairLSV curve of the iron base prepared in the present invention, showing that the current density is 10mA cm -2 When the over-potential of OER is 339mV.
In the above examples, examples 1 to 8 disclose the preparation process of iron-based phosphate under different conditions, and the electrocatalysts prepared in examples 1 to 8 were subjected to electrolytic water catalysis tests to obtain the corresponding linear scanning voltammograms. As shown in FIG. 4, it can be found from the linear scanning voltammograms of comparative example 1 to example 4 that: the OER catalytic activity of the sample can be adjusted by different mass ratios of the phosphate fertilizer supernatant to the rust; comparing example 1, the linear scanning voltammograms of examples 5-8, it can be found that: the different pH values of the supernatant greatly influence the OER catalytic activity of the sample, and when the current density is 10mA cm -2 Example 1 achieved the lowest OER overpotential (267 mV) and the best catalytic activity.
The test conditions of the catalytic activity of the electrolyzed water are as follows: the electrocatalysis performance test is completed on CHI660E Chen Hua electrochemical workstation. The electrolytic cell was a home-made three-electrode cell, the operating temperature was kept at 25 ℃, the obtained sample powder 5mg was mixed into a solution containing 300. Mu.L of ethanol, 200. Mu.L of deionized water and 25. Mu.L of 5wt% of Nafion to form a slurry, and after ultrasonication for 30min, 5. Mu.L of the slurry was dropped on a glassy carbon electrode (area about 0.0707 cm) 2 ) The electrode is naturally dried to be used as a working electrode WE, the carbon rod is used as a counter electrode CE, and the saturated calomel solution is used as a reference electrode RE. The electrolyte was a 1M KOH solution with a pH of 13.97. The OER activity of the catalyst is measured by a linear voltammetry scanning method, the measurement range is-0V to-0.8V vs Hg/HgO, and the scanning speed is 5mV/s. The measurement potential vs reversible hydrogen electrode RHE is calculated by the following formula: e (RHE) =0.098+ 0.0591X 13.97. And the sample of the example 1 after LSV is continuously tested under the window voltage of-0V to-0.8V vs Hg/HgO for cyclic voltammogram, and the LSV is tested after 1000 cycles.
The preparation and application of the iron-based phosphate electrocatalyst material according to the present invention are described in detail above, and the principle and embodiments of the present invention are illustrated herein by using specific examples, which are only used to help understanding the method and the core concept of the present invention, and it should be noted that, for those skilled in the art, the present invention can be modified and controlled without departing from the principle of the present invention, and the modified and controlled are also within the protection scope of the claims.
Claims (10)
1. An iron-based phosphate electrocatalyst material is characterized in that agricultural phosphate fertilizer and rust are used as main raw materials, and the iron-based phosphate electrocatalyst is prepared by a one-step hydrothermal method and has good electrocatalytic activity.
2. The method of preparing an iron-based phosphate electrocatalyst material according to claim 1, comprising the steps of: dissolving enough agricultural phosphate fertilizer in deionized water, taking supernatant of saturated phosphate fertilizer after precipitation, dropwise adding NaOH solution to adjust pH value, adding ground rust powder into the solution, uniformly stirring, then putting the mixed solution into a reaction kettle for hydrothermal reaction, taking precipitate, washing with water, and vacuum drying.
3. The method of claim 2, wherein the concentration of the NaOH solution is 1mol/L and the pH of the reaction solution is 2-6.
4. The method for preparing the iron-based phosphate electrocatalyst material according to claim 2, wherein the mass ratio of the saturated phosphate fertilizer supernatant to the rust is: (200-400) 1.
5. The method of claim 2, wherein the hydrothermal reaction is carried out at a temperature of 120 to 200 ℃.
6. The method of claim 2, wherein the hydrothermal reaction is carried out for a period of 12 to 18 hours.
7. The method of claim 2, wherein the volume of the mixed solution is 70-80% of the volume of the reaction vessel.
8. The method of claim 2, wherein the vacuum drying temperature is 40-60 ℃.
9. An iron-based phosphate electrocatalyst prepared by the method of claims 2-8.
10. The method of preparing an iron-based phosphate electrocatalyst material according to claim 9, characterized in that the catalyst is prepared for application in oxygen evolution reactions for electrocatalytic decomposition of water.
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