CN110586148A - Preparation method of self-supporting flower-shaped nickel phosphide/ferrous phosphate heterostructure full-electrolysis hydro-electric catalyst - Google Patents
Preparation method of self-supporting flower-shaped nickel phosphide/ferrous phosphate heterostructure full-electrolysis hydro-electric catalyst Download PDFInfo
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- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 63
- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229940116007 ferrous phosphate Drugs 0.000 title claims abstract description 18
- 229910000155 iron(II) phosphate Inorganic materials 0.000 title claims abstract description 18
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 title claims abstract description 18
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 title claims abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 318
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 129
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000006260 foam Substances 0.000 claims abstract description 40
- 238000004140 cleaning Methods 0.000 claims abstract description 32
- 238000001035 drying Methods 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 62
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 56
- 229910052757 nitrogen Inorganic materials 0.000 claims description 31
- MQYRLAZBVBHGDU-UHFFFAOYSA-J iron(2+) nickel(2+) dicarbonate Chemical compound C([O-])([O-])=O.[Ni+2].[Fe+2].C([O-])([O-])=O MQYRLAZBVBHGDU-UHFFFAOYSA-J 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 20
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 19
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 18
- AYTGUZPQPXGYFS-UHFFFAOYSA-N urea nitrate Chemical compound NC(N)=O.O[N+]([O-])=O AYTGUZPQPXGYFS-UHFFFAOYSA-N 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000007664 blowing Methods 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 238000007605 air drying Methods 0.000 claims 1
- 238000007599 discharging Methods 0.000 claims 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims 1
- 238000004321 preservation Methods 0.000 claims 1
- 238000004506 ultrasonic cleaning Methods 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 25
- 239000001301 oxygen Substances 0.000 abstract description 25
- 229910052760 oxygen Inorganic materials 0.000 abstract description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 22
- 239000010411 electrocatalyst Substances 0.000 abstract description 19
- 230000001588 bifunctional effect Effects 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 4
- 238000003411 electrode reaction Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 20
- 238000006460 hydrolysis reaction Methods 0.000 description 15
- 230000007062 hydrolysis Effects 0.000 description 9
- 238000002484 cyclic voltammetry Methods 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- -1 transition metal selenides Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- YGHCWPXPAHSSNA-UHFFFAOYSA-N nickel subsulfide Chemical compound [Ni].[Ni]=S.[Ni]=S YGHCWPXPAHSSNA-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- QHASIAZYSXZCGO-UHFFFAOYSA-N selanylidenenickel Chemical compound [Se]=[Ni] QHASIAZYSXZCGO-UHFFFAOYSA-N 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B01J35/30—
-
- B01J35/33—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
A preparation method of a self-supporting flower-shaped nickel phosphide/ferrous phosphate heterostructure full-electrolysis water-electricity catalyst belongs to the field of new energy materials, and particularly relates to a Ni-based catalyst2P/Fe(PO3)2A preparation method of a heterostructure full-electrolysis water catalyst. The invention aims to solve the problems of large electrode reaction overpotential and slow reaction kinetic process of the traditional bifunctional electrocatalyst for catalyzing HER and OER simultaneously. The preparation method comprises the following steps: firstly, cleaning foam nickel; secondly, preparing a solution; thirdly, carrying out hydrothermal treatment; fourthly, cleaning and drying; and fifthly, phosphating. The advantages are that: when used as a working electrode, the current density is 10mA cm‑2When it is over oxygen evolutionThe potential is lower than 250mV, and when the current density is-10 mA cm‑2When the hydrogen evolution overpotential is lower than 110 mV; the method is mainly used for preparing the self-supporting flower-shaped nickel phosphide/ferrous phosphate heterostructure full-electrolysis hydro-electric catalyst.
Description
Technical Field
The invention belongs to the field of new energy materials, and particularly relates to Ni2P/Fe(PO3)2A preparation method of a heterostructure full-electrolysis water catalyst.
Background
The main energy sources used in the world are fossil fuels, including coal, oil, and natural gas, among others. With the consumption of fossil fuels, the search for alternative energy sources is urgent. Hydrogen is widely regarded as a future fuel, water can be decomposed to produce hydrogen, the only by-product is oxygen, and oxygen plays an important role in industry, and hydrogen produced by electrolyzing water accounts for 3.9% of the total hydrogen supply in the world. Due to the huge power consumption, the research on the low-pressure electrolysis water has important significance.
The current major problem in hydrogen production by water electrolysis is high energy consumption due to the two half reactions of water decomposition, both HER (hydrogen evolution) and OER (oxygen evolution), requiring a reduction in the activation energy barrier to achieve a fast kinetic process. With the increasingly intensive research, higher demands are being made on electrocatalysts having high efficiency and long life. Pt and noble metal oxides (RuO)2And IrO2) Is a common commercial catalyst and has unique advantages. However, due to their scarcity and high cost, they are not well suited for large scale practical application to the decomposition of water. Under such circumstances, the development of high-activity, economical high-activity, highly-active electrocatalysts is a current research focus. It would be highly desirable to design a bifunctional electrocatalyst capable of catalyzing both HER and OER because it simplifies the operating system and reduces the overall cost of the equipment. To date, a series of transition metal selenides, oxides, chalcogenides, borides, and phosphides have been used as symmetric bifunctional catalysts for bulk water decomposition, such as NiSe, CoMnO, Ni3S2、Co9S8@MoS2Carbon Nanofibers (CNFs), Co2B. CoP and Ni2And P. Conductive self-supporting materials such as nickel foam, copper foam, titanium sheet and the likeThe advantages of strong binding force, difficult falling off in the reaction process, small contact resistance and the like are also favored. Of these non-noble metal catalysts, transition metal phosphides have been theoretically calculated and experimentally proved to be better bifunctional catalysts. However, the existing material still has the problem that the electrode reaction overpotential is large (when the current density is 10mA cm)-2In the time, the oxygen evolution overpotential is generally 300mV), the reaction kinetic process is slow, and the like. Much work remains to be done in developing high performance bifunctional electrocatalysts.
Disclosure of Invention
The invention aims to solve the problems of large overpotential of electrode reaction and slow reaction kinetics process of the traditional bifunctional electrocatalyst for catalyzing HER and OER simultaneously, and provides a preparation method of a self-supporting flower-shaped nickel phosphide/ferrous phosphate heterostructure full-electrolysis electrocatalyst.
A preparation method of a self-supporting flower-shaped nickel phosphide/ferrous phosphate heterostructure full-electrolysis hydro-electric catalyst is specifically completed according to the following steps:
firstly, cleaning foamed nickel: sequentially adopting acetone, ethanol and deionized water to ultrasonically clean the foamed nickel, and then drying to obtain clean foamed nickel;
secondly, preparing a solution: dissolving ferric nitrate and urea in deionized water, and uniformly stirring to obtain a ferric nitrate-urea solution;
thirdly, hydrothermal treatment: placing the ferric nitrate-urea solution into a reaction kettle, obliquely soaking clean foamed nickel into the ferric nitrate-urea solution, and placing the reaction kettle into an air-blowing drying oven for heating reaction to obtain reacted foamed nickel;
fourthly, cleaning and drying: taking out the reacted foam nickel, firstly ultrasonically cleaning the foam nickel by using deionized water, and then drying the foam nickel in a vacuum drying oven to obtain the foam nickel for growing the nickel-based basic nickel-iron carbonate;
fifthly, phosphating treatment: sodium hypophosphite is taken as a phosphorus source, foamed nickel and sodium hypophosphite for growing the nickel-based basic nickel-iron carbonate are respectively placed in a tubular furnace, nitrogen is taken as protective gas, the air in the tubular furnace is discharged by utilizing the nitrogen, and phosphorization is carried out in the nitrogen atmosphereTreating to obtain self-supporting flower-shaped Ni2P/Fe(PO3)2A heterostructure full-electrolysis hydro-catalyst.
The invention has the advantages that: firstly, the self-supporting flower-shaped Ni prepared by the invention2P/Fe(PO3)2When the heterostructure full-electrolysis water catalyst is used as a working electrode, the current density is 10mA cm-2When the current density is-10 mA cm, the oxygen evolution overpotential is lower than 250mV-2When the hydrogen evolution overpotential is lower than 110mV, the current density is 10mA cm-2When the voltage is 1.56V, the total hydrolysis voltage is high; secondly, the self-supporting flower-shaped Ni prepared by the invention2P/Fe(PO3)2The heterostructure full-electrolysis water catalyst grows a great deal of Ni on the surface of the foamed nickel2P/Fe(PO3)2The nanoflower has a unique heterostructure which exposes more active sites, so that more electrolyzed water active centers are provided, the catalytic activity is high, and the problem of slow reaction kinetics is effectively solved; thirdly, the invention self-supporting flower-shaped Ni2P/Fe(PO3)2The preparation process of the heterostructure full-electrolysis water catalyst is simple, the price of raw materials is low, and the repeatability is good.
Drawings
FIG. 1 is a scanning electron microscope photomicrograph of the foamed nickel of the growing nickel-based basic nickel oxycarbonate obtained in step four of example 1;
FIG. 2 is a high power scanning electron microscope image of the foamed nickel of the growing nickel-based basic nickel oxycarbonate obtained in step four of example 1;
FIG. 3 shows self-supporting flower-like Ni prepared in example 12P/Fe(PO3)2Macroscopic scanning electron micrographs of the heterostructure full hydrolysis hydrocatalyst;
FIG. 4 shows self-supporting flower-like Ni prepared in example 12P/Fe(PO3)2High power scanning electron micrographs of heterostructure full hydrolysis hydrocatalysts;
FIG. 5 is an X-ray diffraction pattern in which A represents the self-supporting flower-like Ni of the electrode prepared in example 12P/Fe(PO3)2An X-ray diffraction spectrum of the heterostructure full-hydrolysis electrocatalyst; b represents Ni2P's standard card; c represents Fe (PO)3)2The standard card of (1);
FIG. 6 shows self-supporting flower-like Ni prepared in example 12P/Fe(PO3)2Transmission electron microscopy of the heterostructure full hydrolysis electrocatalyst;
FIG. 7 is a graph of oxygen evolution performance, wherein ● represents the self-supporting flower-like Ni prepared in example 12P/Fe(PO3)2Oxygen evolution performance profile of heterostructure full-electrolysis electrocatalyst as working electrode, a-gravy representing self-supporting flower-like Ni prepared with example 22P/Fe(PO3)2Graph of oxygen evolution performance of heterostructure full-electrolysis electrocatalyst as working electrode, t.X represents self-supporting flower-like Ni prepared in example 32P/Fe(PO3)2An oxygen evolution performance curve chart when the heterostructure full electrolysis water catalyst is used as a working electrode, wherein ■ shows the oxygen evolution performance curve chart when clean foamed nickel is respectively used as the working electrode;
FIG. 8 is a graph of hydrogen evolution performance, in whichShows the self-supporting flower-like Ni prepared in example 12P/Fe(PO3)2Hydrogen evolution Performance of the heterostructure Total hydrolysis Hydrocatalyst as a working electrode, shown in solid-solid form in the self-supporting flower-like Ni prepared in example 22P/Fe(PO3)2Graph of hydrogen evolution performance for heterostructure full-electrolysis electrocatalyst as working electrode, t.X represents the self-supporting flower-like Ni prepared in example 32P/Fe(PO3)2A hydrogen evolution performance curve chart when the heterostructure full electrolysis water catalyst is used as a working electrode, wherein ■ shows the hydrogen evolution performance curve chart when clean foamed nickel is respectively used as the working electrode;
FIG. 9 shows self-supporting flower-like Ni prepared in example 12P/Fe(PO3)2A full-hydrolysis performance curve when the heterostructure full-hydrolysis electrocatalyst is used as a working electrode;
FIG. 10 shows self-supporting flower-like Ni prepared in example 12P/Fe(PO3)2Heterostructure full electrolysis water catalyst as working electrodeA time evolution stability curve, wherein a represents the curve at the 1 st cycle of cyclic voltammetry and B represents the curve at the 3000 th cycle of cyclic voltammetry;
FIG. 11 shows self-supporting flower-like Ni prepared in example 12P/Fe(PO3)2I-t curve of heterostructure full electrolysis water catalyst as working electrode;
FIG. 12 shows self-supporting flower-like Ni prepared in example 12P/Fe(PO3)2When the heterostructure full-electrolysis water catalyst is used as a working electrode, a hydrogen evolution stability curve is shown, wherein A represents a curve of a 1 st circle of cyclic voltammetry, and B represents a curve of a 3000 th circle of cyclic voltammetry;
FIG. 13 shows self-supporting flower-like Ni prepared in example 12P/Fe(PO3)2I-t curve of heterostructure full-electrolysis electrocatalyst as working electrode.
Detailed Description
The first embodiment is as follows: the embodiment is a preparation method of a self-supporting flower-shaped nickel phosphide/ferrous phosphate heterostructure full-electrolysis hydro-electric catalyst, which is specifically completed according to the following steps:
firstly, cleaning foamed nickel: sequentially adopting acetone, ethanol and deionized water to ultrasonically clean the foamed nickel, and then drying to obtain clean foamed nickel;
secondly, preparing a solution: dissolving ferric nitrate and urea in deionized water, and uniformly stirring to obtain a ferric nitrate-urea solution;
thirdly, hydrothermal treatment: placing the ferric nitrate-urea solution into a reaction kettle, obliquely soaking clean foamed nickel into the ferric nitrate-urea solution, and placing the reaction kettle into an air-blowing drying oven for heating reaction to obtain reacted foamed nickel;
fourthly, cleaning and drying: taking out the reacted foam nickel, firstly ultrasonically cleaning the foam nickel by using deionized water, and then drying the foam nickel in a vacuum drying oven to obtain the foam nickel for growing the nickel-based basic nickel-iron carbonate;
fifthly, phosphating treatment: sodium hypophosphite is used as a phosphorus source, and foamed nickel and sodium hypophosphite for growing nickel-based basic nickel-iron carbonate are respectively placed inIn the tubular furnace, nitrogen is used as protective gas, the air in the tubular furnace is discharged by the nitrogen, and the phosphorization treatment is carried out in the nitrogen atmosphere to obtain the self-supporting flower-shaped Ni2P/Fe(PO3)2A heterostructure full-electrolysis hydro-catalyst.
The second embodiment is as follows: the present embodiment differs from the first embodiment in that: firstly, ultrasonically cleaning the foamed nickel in acetone for 5-30 min, then ultrasonically cleaning in ethanol for 5-30 min, finally ultrasonically cleaning in deionized water for 5-30 min, and then drying to obtain clean foamed nickel. The rest is the same as the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: in the second step, the molar ratio of the ferric nitrate to the urea is 1-10: 8-12; the volume ratio of the ferric nitrate to the deionized water is (1-10) mmol (10-100) mL. The others are the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is as follows: and step three, placing the reaction kettle into a blast drying oven, and preserving the heat for 2-10 hours at the temperature of 40-120 ℃ to obtain the reacted foamed nickel. The others are the same as the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: and in the fourth step, the reacted foam nickel is taken out, is firstly ultrasonically cleaned by deionized water, and is then placed in a vacuum drying oven to be dried for 5 to 60 hours at the temperature of 60 ℃ to obtain the foam nickel for growing the nickel-based basic nickel-iron carbonate. The rest is the same as the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is as follows: and in the fifth step, the mass ratio of the foamed nickel and the sodium hypophosphite for growing the nickel-based basic nickel-iron carbonate is (1-3): 1. The rest is the same as the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: and fifthly, sequentially placing sodium hypophosphite and foamed nickel for growing the nickel-based basic nickel-iron carbonate in the tubular furnace along the flowing direction of the nitrogen, wherein the interval between the sodium hypophosphite and the foamed nickel for growing the nickel-based basic nickel-iron carbonate is 1-20 cm, and introducing the nitrogen into the tubular furnace at the flow rate of 10-100 mL/min to discharge the air in the tubular furnace. The rest is the same as the first to sixth embodiments.
The specific implementation mode is eight: the difference between this embodiment and one of the first to seventh embodiments is: in the fifth step, the specific process of the phosphating treatment under the nitrogen atmosphere is as follows: under the nitrogen atmosphere, the temperature in the tubular furnace is firstly increased to 250-650 ℃ from the room temperature at the heating rate of 1-10 ℃/min, then the temperature is kept for 30-300 min under the conditions of the nitrogen atmosphere and the temperature of 250-650 ℃, and then the tubular furnace is cooled to the room temperature along with the furnace. The rest is the same as the first to seventh embodiments.
The invention is not limited to the above embodiments, and one or a combination of several embodiments may also achieve the object of the invention.
The following tests were carried out to confirm the effects of the present invention
Example 1: a preparation method of a self-supporting flower-shaped nickel phosphide/ferrous phosphate heterostructure full-electrolysis hydro-electric catalyst is specifically completed according to the following steps:
firstly, cleaning foamed nickel: cutting foam Nickel (NF) into a rectangular shape with the length, width and height of 4cm multiplied by 2cm multiplied by 0.05cm, firstly ultrasonically cleaning in acetone for 15min, then ultrasonically cleaning in ethanol for 10min, finally ultrasonically cleaning in deionized water for 5min, and then drying to obtain clean foam nickel;
secondly, preparing a solution: dissolving 3mmol of ferric nitrate and 10mmol of urea in 40mL of deionized water, and uniformly stirring to obtain a ferric nitrate-urea solution;
thirdly, hydrothermal treatment: placing the ferric nitrate-urea solution into a reaction kettle, obliquely soaking clean foamed nickel into the ferric nitrate-urea solution, placing the reaction kettle into an air-blowing drying oven, and preserving heat for 10 hours at the temperature of 120 ℃ to obtain reacted foamed nickel;
fourthly, cleaning and drying: taking out the reacted foam nickel, firstly ultrasonically cleaning the foam nickel by using deionized water for 5min, then placing the foam nickel in a vacuum drying oven, and drying the foam nickel at the temperature of 60 ℃ for 6h to obtain the foam nickel for growing the nickel-based basic nickel-iron carbonate, wherein the mass of the foam nickel for growing the nickel-based basic nickel-iron carbonate is known to be 1.2754g by weighing;
fifthly, phosphating treatment: placing the foamed nickel growing the nickel-based basic nickel-iron carbonate obtained in the fourth step and 1g of sodium hypophosphite in a tubular furnace in sequence along the flowing direction of nitrogen, wherein the interval between the sodium hypophosphite and the foamed nickel growing the nickel-based basic nickel-iron carbonate is 10cm, using nitrogen as protective gas, introducing the nitrogen into the tubular furnace at the gas flow rate of 25mL/min, introducing the nitrogen for 60min, adjusting the gas flow rate of the nitrogen to 15mL/min, raising the temperature in the tubular furnace from room temperature to 300 ℃ at the temperature raising rate of 2 ℃/min under the condition that the gas flow rate of the nitrogen is 15mL/min and the temperature is 300 ℃, then preserving the heat for 30min under the conditions that the gas flow rate of the nitrogen is 15mL/min and the temperature is 300 ℃, and then cooling the tubular furnace to the room temperature to obtain the self-supporting flower-shaped Ni2P/Fe(PO3)2A heterostructure full-electrolysis hydro-catalyst.
For the foamed nickel obtained in step four of example 1 and the self-supporting flower-like Ni prepared in example 12P/Fe(PO3)2Scanning the heterostructure full-electrolysis water catalyst by an electron microscope, wherein the electron microscope is shown in figures 1-4, and figure 1 is a low-power scanning electron microscope image of the foamed nickel of the nickel-based basic nickel iron carbonate obtained in the fourth step of the example 1; FIG. 2 is a high power scanning electron microscope image of the foamed nickel of the growing nickel-based basic nickel oxycarbonate obtained in step four of example 1; FIG. 3 shows self-supporting flower-like Ni prepared in example 12P/Fe(PO3)2Macroscopic scanning electron micrographs of the heterostructure full hydrolysis hydrocatalyst; FIG. 4 shows self-supporting flower-like Ni prepared in example 12P/Fe(PO3)2High power scanning electron micrographs of heterostructure full hydrolysis hydrocatalysts; as can be seen from fig. 1 and 2, the foamed nickel of the growing nickel-based basic nickel iron carbonate obtained in the fourth step of example 1 shows a flower-like morphology; it can be seen from FIGS. 3 and 4 that the self-supporting flower-like Ni obtained after phosphating2P/Fe(PO3)2The heterogeneous structure full-electrolysis water catalyst can still keep the original structureHas a shape.
FIG. 5 is an X-ray diffraction pattern in which A represents the self-supporting flower-like Ni of the electrode prepared in example 12P/Fe(PO3)2An X-ray diffraction spectrum of the heterostructure full-hydrolysis electrocatalyst; b represents Ni2P's standard card; c represents Fe (PO)3)2The standard card of (1); from FIG. 5, it can be seen that the self-supporting flower-like Ni of the electrode prepared in example 12P/Fe(PO3)2Diffraction peaks of heterostructure full-electrolysis water catalyst can be matched with Ni2P and Fe (PO3)2Corresponds to the standard card of (1).
FIG. 6 shows self-supporting flower-like Ni prepared in example 12P/Fe(PO3)2Transmission electron microscopy of the heterostructure full hydrolysis electrocatalyst; from FIG. 6, Ni can be seen2P and Fe (PO)3)2The lattice of (2) is identical to XRD.
Example 2: a preparation method of a self-supporting flower-shaped nickel phosphide/ferrous phosphate heterostructure full-electrolysis hydro-electric catalyst is specifically completed according to the following steps:
firstly, cleaning foamed nickel: cutting foam Nickel (NF) into a rectangular shape with the length, width and height of 4cm multiplied by 2cm multiplied by 0.05cm, firstly ultrasonically cleaning in acetone for 15min, then ultrasonically cleaning in ethanol for 10min, finally ultrasonically cleaning in deionized water for 5min, and then drying to obtain clean foam nickel;
secondly, preparing a solution: dissolving 3mmol of ferric nitrate and 10mmol of urea in 40mL of deionized water, and uniformly stirring to obtain a ferric nitrate-urea solution;
thirdly, hydrothermal treatment: placing the ferric nitrate-urea solution into a reaction kettle, obliquely soaking clean foamed nickel into the ferric nitrate-urea solution, placing the reaction kettle into an air-blowing drying oven, and preserving heat for 10 hours at the temperature of 120 ℃ to obtain reacted foamed nickel;
fourthly, cleaning and drying: taking out the reacted foam nickel, firstly ultrasonically cleaning the foam nickel by using deionized water for 5min, then placing the foam nickel in a vacuum drying oven, and drying the foam nickel at the temperature of 60 ℃ for 6h to obtain the foam nickel with the mass of 1.2693g for growing the nickel-based basic nickel-iron carbonate;
fifth, phosphorizationAnd (3) treatment: placing the foamed nickel growing the nickel-based basic nickel-iron carbonate obtained in the fourth step and 1g of sodium hypophosphite in a tubular furnace in sequence along the flowing direction of nitrogen, wherein the interval between the sodium hypophosphite and the foamed nickel growing the nickel-based basic nickel-iron carbonate is 10cm, using nitrogen as protective gas, introducing the nitrogen into the tubular furnace at the gas flow rate of 25mL/min, introducing the nitrogen for 60min, adjusting the gas flow rate of the nitrogen to 15mL/min, raising the temperature in the tubular furnace from room temperature to 250 ℃ at the temperature raising rate of 2 ℃/min under the condition that the gas flow rate of the nitrogen is 15mL/min, then preserving the heat for 30min under the conditions that the gas flow rate of the nitrogen is 15mL/min and the temperature is 250 ℃, and then cooling the tubular furnace to the room temperature to obtain the self-supporting flower-shaped Ni2P/Fe(PO3)2A heterostructure full-electrolysis hydro-catalyst.
Example 3: a preparation method of a self-supporting flower-shaped nickel phosphide/ferrous phosphate heterostructure full-electrolysis hydro-electric catalyst is specifically completed according to the following steps:
firstly, cleaning foamed nickel: cutting foam Nickel (NF) into a rectangular shape with the length, width and height of 4cm multiplied by 2cm multiplied by 0.05cm, firstly ultrasonically cleaning in acetone for 15min, then ultrasonically cleaning in ethanol for 10min, finally ultrasonically cleaning in deionized water for 5min, and then drying to obtain clean foam nickel;
secondly, preparing a solution: dissolving 3mmol of ferric nitrate and 10mmol of urea in 40mL of deionized water, and uniformly stirring to obtain a ferric nitrate-urea solution;
thirdly, hydrothermal treatment: placing the ferric nitrate-urea solution into a reaction kettle, obliquely soaking clean foamed nickel into the ferric nitrate-urea solution, placing the reaction kettle into an air-blowing drying oven, and preserving heat for 10 hours at the temperature of 120 ℃ to obtain reacted foamed nickel;
fourthly, cleaning and drying: taking out the reacted foam nickel, firstly ultrasonically cleaning the foam nickel by using deionized water for 5min, then placing the foam nickel in a vacuum drying oven, and drying the foam nickel at the temperature of 60 ℃ for 6h to obtain the foam nickel with the mass of 1.2754g for growing the nickel-based basic nickel-iron carbonate;
fifthly, phosphating treatment: taking sodium hypophosphite as a phosphorus source, and carrying out the step four to obtain the growth nickel base along the flowing direction of nitrogenSequentially placing foamed nickel of basic nickel-iron carbonate and 1g of sodium hypophosphite in a tubular furnace, setting the interval between the sodium hypophosphite and the foamed nickel for growing the nickel-based basic nickel-iron carbonate to be 10cm, taking nitrogen as protective gas, introducing the nitrogen into the tubular furnace at the gas flow rate of 25mL/min, introducing the nitrogen for 60min, regulating the gas flow rate of the nitrogen to be 15mL/min, heating the temperature in the tubular furnace from room temperature to 350 ℃ at the heating rate of 2 ℃/min under the condition that the gas flow rate of the nitrogen is regulated to be 15mL/min, then preserving the temperature for 30min under the conditions that the gas flow rate of the nitrogen is regulated to be 15mL/min and the temperature is 350 ℃, and then cooling the tubular furnace to the room temperature to obtain the self-supporting flower-shaped Ni2P/Fe(PO3)2A heterostructure full-electrolysis hydro-catalyst.
Self-supporting flower-like Ni prepared as in examples 1-32P/Fe(PO3)2The heterostructure full electrolysis water catalyst and the clean foam nickel are respectively used as working electrodes, and oxygen evolution hydrogen evolution full water performance test is carried out in KOH aqueous solution with the concentration of 1mol/mL, as shown in figures 7 to 9, figure 7 is an oxygen evolution performance curve graph, and ● in the figure shows self-supporting flower-shaped Ni prepared by example 12P/Fe(PO3)2Oxygen evolution performance profile of heterostructure full-electrolysis electrocatalyst as working electrode, a-gravy representing self-supporting flower-like Ni prepared with example 22P/Fe(PO3)2Graph of oxygen evolution performance of heterostructure full-electrolysis electrocatalyst as working electrode, t.X represents self-supporting flower-like Ni prepared in example 32P/Fe(PO3)2An oxygen evolution performance curve chart when the heterostructure full electrolysis water catalyst is used as a working electrode, wherein ■ shows the oxygen evolution performance curve chart when clean foamed nickel is respectively used as the working electrode; FIG. 8 is a graph of hydrogen evolution performance, in whichShows the self-supporting flower-like Ni prepared in example 12P/Fe(PO3)2Hydrogen evolution Performance of the heterostructure Total hydrolysis Hydrocatalyst as a working electrode, shown in solid-solid form in the self-supporting flower-like Ni prepared in example 22P/Fe(PO3)2Hydrogen evolution when heterostructure full electrolysis hydro-electric catalyst is used as working electrodePerformance Chart, t, represents the self-supporting flower-like Ni prepared in example 32P/Fe(PO3)2A hydrogen evolution performance curve chart when the heterostructure full electrolysis water catalyst is used as a working electrode, wherein ■ shows the hydrogen evolution performance curve chart when clean foamed nickel is respectively used as the working electrode; FIG. 9 shows self-supporting flower-like Ni prepared in example 12P/Fe(PO3)2A full-hydrolysis performance curve when the heterostructure full-hydrolysis electrocatalyst is used as a working electrode; as can be seen from FIGS. 7 to 9, the self-supporting flower-like Ni prepared in example 12P/Fe(PO3)2When the heterostructure full-electrolysis water catalyst is used as a working electrode, the current density is 10mA cm-2When the current density is-10 mA cm, the oxygen evolution overpotential is 230mV-2When the current density is 10mA cm, the hydrogen evolution overpotential is 84mV-2The total water overpotential was 1.56V. As can be seen from FIGS. 7 and 8, the self-supporting flower-like Ni prepared in example 22P/Fe(PO3)2When the heterostructure full-electrolysis water catalyst is used as a working electrode, the current density is 10mA cm-2When the current density is-10 mA cm, the oxygen evolution overpotential is 240mV-2When the reaction is carried out, the overpotential for hydrogen evolution is 100 mV. As can be seen from FIGS. 7 and 8, the self-supporting flower-like Ni prepared in example 32P/Fe(PO3)2When the heterostructure full-electrolysis water catalyst is used as a working electrode, the current density is 10mA cm-2When the current density is-10 mA.m, the oxygen evolution overpotential is 250mV-2When the hydrogen evolution overpotential is 110 mV; thus the self-supporting flower-like Ni prepared by the invention2P/Fe(PO3)2The heterostructure full-electrolysis water catalyst has excellent catalytic performance.
Self-supporting flower-like Ni prepared as in example 12P/Fe(PO3)2Heterostructure full electrolysis water catalyst as working electrode, oxygen evolution and hydrogen evolution stability test is carried out in KOH aqueous solution with concentration of 1mol/mL, as shown in FIGS. 10-13, FIG. 10 is self-supporting flower-shaped Ni prepared in example 12P/Fe(PO3)2The oxygen evolution stability curve of the heterostructure full-electrolysis hydro-catalyst used as a working electrode is shown in the figure, A represents the 1 st circle of cyclic voltammetryB represents the curve of the 3000 th cycle of cyclic voltammetry, and comparing the previous and subsequent curves shows that good oxygen evolution stability can be maintained after 3000 cycles, FIG. 11 is a graph of the self-supporting flower-like Ni prepared in example 12P/Fe(PO3)2The I-t curve of the heterostructure full-electrolysis water catalyst as a working electrode can be known from fig. 11, the current density is still kept above 99% after 24h of oxygen evolution electrolysis, and the electrode stability is proved to be good; FIG. 12 shows self-supporting flower-like Ni prepared in example 12P/Fe(PO3)2When the heterostructure full-electrolysis hydro-catalyst is used as a working electrode, the hydrogen evolution stability curve is shown in the figure, wherein A represents the curve of the 1 st circle of cyclic voltammetry, B represents the curve of the 3000 th circle of cyclic voltammetry, and the curves before and after comparison show that the good hydrogen evolution stability curve can be maintained after 3000 cycles, and FIG. 13 is the self-supporting flower-shaped Ni prepared in example 12P/Fe(PO3)2The I-t curve of the heterostructure full-electrolysis water catalyst used as a working electrode can be known from fig. 11, the current density is still kept above 99% after 24h of oxygen evolution electrolysis, and the electrode stability is proved to be good; as can be seen from FIGS. 10-13, the self-supporting flower-like Ni prepared in example 12P/Fe(PO3)2The heterostructure full-electrolysis water catalyst keeps good stability.
Combining examples 1-3, it can be seen that the self-supporting flower-like Ni prepared by the present invention2P/Fe(PO3)2The specific surface area of the heterostructure full-electrolysis water catalyst is increased, active sites are increased, the catalytic activity is improved, the preparation process is simple, and the heterostructure full-electrolysis water catalyst is suitable for large-scale production.
Claims (8)
1. A preparation method of a self-supporting flower-shaped nickel phosphide/ferrous phosphate heterostructure full-electrolysis hydro-electric catalyst is characterized by comprising the following steps:
firstly, cleaning foamed nickel: sequentially adopting acetone, ethanol and deionized water to ultrasonically clean the foamed nickel, and then drying to obtain clean foamed nickel;
secondly, preparing a solution: dissolving ferric nitrate and urea in deionized water, and uniformly stirring to obtain a ferric nitrate-urea solution;
thirdly, hydrothermal treatment: placing the ferric nitrate-urea solution into a reaction kettle, obliquely soaking clean foamed nickel into the ferric nitrate-urea solution, and placing the reaction kettle into an air-blowing drying oven for heating reaction to obtain reacted foamed nickel;
fourthly, cleaning and drying: taking out the reacted foam nickel, firstly ultrasonically cleaning the foam nickel by using deionized water, and then drying the foam nickel in a vacuum drying oven to obtain the foam nickel for growing the nickel-based basic nickel-iron carbonate;
fifthly, phosphating treatment: taking sodium hypophosphite as a phosphorus source, respectively placing foamed nickel and sodium hypophosphite for growing nickel-based basic nickel-iron carbonate in a tubular furnace, taking nitrogen as protective gas, discharging air in the tubular furnace by utilizing the nitrogen, and carrying out phosphating treatment in a nitrogen atmosphere to obtain self-supporting flower-shaped Ni2P/Fe(PO3)2A heterostructure full-electrolysis hydro-catalyst.
2. The preparation method of the self-supporting flower-shaped nickel phosphide/ferrous phosphate heterostructure full-electrolysis hydro-electric catalyst according to claim 1, characterized in that in the first step, the foamed nickel is firstly ultrasonically cleaned in acetone for 5min to 30min, then ultrasonically cleaned in ethanol for 5min to 30min, finally ultrasonically cleaned in deionized water for 5min to 30min, and then dried to obtain clean foamed nickel.
3. The preparation method of the self-supporting flower-shaped nickel phosphide/ferrous phosphate heterostructure full-electrolysis hydro-catalyst according to claim 1, wherein the molar ratio of the ferric nitrate to the urea in the second step is 1-10: 8-12; the volume ratio of the ferric nitrate to the deionized water is (1-10) mmol (10-100) mL.
4. The preparation method of the self-supporting flower-shaped nickel phosphide/ferrous phosphate heterostructure full-electrolysis hydro-electric catalyst according to claim 1, which is characterized in that in the third step, a reaction kettle is placed in a forced air drying oven, and heat preservation is carried out at the temperature of 40-120 ℃ for 2-10 h, so that the reacted foamed nickel is obtained.
5. The preparation method of the self-supporting flower-shaped nickel phosphide/ferrous phosphate heterostructure full-electrolysis hydro-electric catalyst according to claim 1, characterized in that in the fourth step, the foamed nickel after reaction is taken out, firstly, deionized water is used for ultrasonic cleaning for 5min to 10min, then, the foamed nickel is placed in a vacuum drying oven and dried for 5h to 60h at the temperature of 60 ℃, and the foamed nickel with the grown nickel-based basic nickel carbonate is obtained.
6. The preparation method of the self-supporting flower-shaped nickel phosphide/ferrous phosphate heterostructure full-electrolysis hydro-electric catalyst according to claim 1, wherein the mass ratio of the foamed nickel and the sodium hypophosphite of the nickel-based basic nickel iron carbonate growing in the step five is (1-3): 1.
7. The method for preparing the self-supporting flower-shaped nickel phosphide/ferrous phosphate heterostructure full-electrolysis hydro-electric catalyst according to claim 6, wherein in the fifth step, sodium hypophosphite and foamed nickel growing nickel-based basic nickel iron carbonate are sequentially placed in a tubular furnace along the flowing direction of nitrogen, the distance between the sodium hypophosphite and the foamed nickel growing nickel-based basic nickel iron carbonate is 1 cm-20 cm, and nitrogen is introduced into the tubular furnace at the flow rate of 10 mL/min-100 mL/min to discharge air in the tubular furnace.
8. The preparation method of the self-supporting flower-shaped nickel phosphide/ferrous phosphate heterostructure full-electrolysis hydro-electric catalyst according to claim 6 or 7, which is characterized in that the specific process of carrying out the phosphating treatment in the nitrogen atmosphere in the fifth step is as follows: under the nitrogen atmosphere, the temperature in the tubular furnace is firstly increased to 250-650 ℃ from the room temperature at the heating rate of 1-10 ℃/min, then the temperature is kept for 30-300 min under the conditions of the nitrogen atmosphere and the temperature of 250-650 ℃, and then the tubular furnace is cooled to the room temperature along with the furnace.
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Application publication date: 20191220 |