CN110152708B - Hollow open-pore structure iron series metal phosphide and preparation method and application thereof - Google Patents
Hollow open-pore structure iron series metal phosphide and preparation method and application thereof Download PDFInfo
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- CN110152708B CN110152708B CN201910446938.9A CN201910446938A CN110152708B CN 110152708 B CN110152708 B CN 110152708B CN 201910446938 A CN201910446938 A CN 201910446938A CN 110152708 B CN110152708 B CN 110152708B
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- 239000011148 porous material Substances 0.000 title claims abstract description 99
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 90
- 239000002184 metal Substances 0.000 title claims abstract description 90
- 150000002505 iron Chemical class 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 112
- 229920001690 polydopamine Polymers 0.000 claims abstract description 53
- 229910052742 iron Inorganic materials 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 32
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 31
- 239000002243 precursor Substances 0.000 claims abstract description 29
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 27
- 239000010411 electrocatalyst Substances 0.000 claims abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 110
- 239000000243 solution Substances 0.000 claims description 57
- 238000003756 stirring Methods 0.000 claims description 42
- 239000008367 deionised water Substances 0.000 claims description 39
- 229910021641 deionized water Inorganic materials 0.000 claims description 39
- 238000001035 drying Methods 0.000 claims description 34
- 238000005406 washing Methods 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000006185 dispersion Substances 0.000 claims description 20
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 17
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052573 porcelain Inorganic materials 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 10
- 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 9
- UCFIGPFUCRUDII-UHFFFAOYSA-N [Co](C#N)C#N.[K] Chemical compound [Co](C#N)C#N.[K] UCFIGPFUCRUDII-UHFFFAOYSA-N 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 9
- 229960003638 dopamine Drugs 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 9
- 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 description 9
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical group O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 238000011144 upstream manufacturing Methods 0.000 claims description 7
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical group O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 230000002431 foraging effect Effects 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 3
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 10
- 239000001257 hydrogen Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 abstract description 8
- 239000001301 oxygen Substances 0.000 abstract description 8
- 238000005336 cracking Methods 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000001228 spectrum Methods 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 230000002349 favourable effect Effects 0.000 description 4
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000005087 graphitization Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000010301 surface-oxidation reaction Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- AAMATCKFMHVIDO-UHFFFAOYSA-N azane;1h-pyrrole Chemical compound N.C=1C=CNC=1 AAMATCKFMHVIDO-UHFFFAOYSA-N 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- VAKIVKMUBMZANL-UHFFFAOYSA-N iron phosphide Chemical compound P.[Fe].[Fe].[Fe] VAKIVKMUBMZANL-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 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
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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Abstract
The invention discloses a preparation method of iron series metal phosphide with a hollow open pore structure, which comprises the following steps: (1) synthesis of Ni3[Co(CN)6]2·12H2O nano cubic precursor; (2) synthesis of hollow open-cell Ni3[Co(CN)6]2·12H2O nano cubic block; (3) synthetic polydopamine coated hollow open-cell Ni3[Co(CN)6]2·12H2O nano cubic block; (4) synthesis of metal ion coordinated polydopamine wrapped hollow open-cell Ni3[Co(CN)6]2·12H2O nano cubic block; (5) synthesizing the iron series metal phosphide with the hollow open pore structure. The invention skillfully uses the hollow open-pore Ni3[Co(CN)6]2·12H2The O nano cubic block is used as a precursor and a template, and further the iron-based metal phosphide electrocatalyst with a hollow open pore structure is obtained by covering poly-dopamine, introducing metal ions and adopting a high-temperature phosphorization strategy, so that the iron-based metal phosphide electrocatalyst with the hollow open pore structure not only shows excellent oxygen evolution and hydrogen evolution activities, but also has excellent full-water cracking electrocatalytic activity under a two-electrode system.
Description
Technical Field
The invention relates to the technical field of iron-based metal phosphide, in particular to iron-based metal phosphide with a hollow open pore structure, and a preparation method and application thereof.
Background
With the increasing consumption of fossil fuels, people pay more and more attention to the development of renewable novel clean energy sources such as solar energy, wind energy and the like. Due to the intermittent problem, the electrocatalysis energy conversion and storage of renewable novel clean energy sources such as solar energy, wind energy and the like are very important. At present, one of the most effective ways is to store the two energies in chemical bonds efficiently by electrocatalytic water splitting technology, and obtain hydrogen as a clean energy. However, water splitting does not occur easily thermodynamically, and the two half reactions involved in water splitting, the hydrogen evolution reaction and the oxygen evolution reaction, all have higher activation barriers. Suitable electrocatalysts are capable of significantly lowering the energy barrier and overpotential of these two half-reactions. At present, the noble metal Pt-based material is a high-efficiency hydrogen evolution catalyst, IrO2、RuO2Is a high-efficiency oxygen evolution catalyst. However, the scarcity and high cost of these precious metals greatly limit the large-scale, sustainable use of electrocatalytic technologies. Therefore, the development of a high-efficiency water cracking catalyst material with abundant reserves and low price is the urgent priority for the development of an electrocatalysis energy conversion technology at present.
Among many catalysts, iron-based metal phosphide is a water-splitting electrocatalyst with good comprehensive performance and wide application prospect. It can replace expensive and scarce noble metal-based catalysts and promote the commercial application of electrochemical water decomposition. However, the phosphide prepared by the traditional preparation method such as low-temperature phosphorization, liquid-phase hydrothermal method and the like has large size, catalytic sites are only positioned on the surface of the catalyst, so that the utilization rate of the active sites is low, and the conductivity of the single component of the prepared phosphide is poor. Therefore, how to further design a favorable mass transfer and load transfer channel on the basis of constructing a hollow structure, enrich the active sites of the channel, and improve the catalytic activity of the channel by utilizing the synergistic effect of multi-component iron-based metal phosphide, which becomes a difficulty that currently restricts the industrial application of the channel.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a hollow open pore structure iron series metal phosphide and a preparation method and application thereof. The invention skillfully uses the hollow open-pore Ni3[Co(CN)6]2·12H2The obtained product not only shows excellent oxygen evolution and hydrogen evolution activity, but also has excellent full water cracking electrocatalytic activity under a two-electrode system, and is closely related to the synergistic effect among the unique hollow open pore structure, favorable mass transfer and charge transfer channels, rich active sites and multi-component iron series metal phosphide.
The invention provides a preparation method of iron series metal phosphide with a hollow open pore structure, which comprises the following steps:
(1) synthesis of Ni3[Co(CN)6]2·12H2O nanometer cubic precursor
Dissolving nickel nitrate hexahydrate and trisodium citrate dihydrate in deionized water to obtain a solution A, and dissolving potassium cobalt cyanide in deionized water to obtain a solution B; adding the solution B into the solution A under the stirring state, continuously stirring, standing for aging, centrifugally washing and drying to obtain Ni3[Co(CN)6]2·12H2O nano cubic precursor;
(2) synthesis of hollow open-cell Ni3[Co(CN)6]2·12H2O nanometer cubic block
Mixing Ni3[Co(CN)6]2·12H2Dispersing the O nano cubic precursor in absolute ethyl alcohol to obtain a dispersion liquid C, and dissolving ammonia water in deionized water to obtain a solution D; adding the solution D into the dispersion liquid C under the stirring state, continuously stirring, centrifugally washing and drying to obtain hollow open-pore Ni3[Co(CN)6]2·12H2O nano cubic block;
(3) synthetic polydopamine coated hollow open-cell Ni3[Co(CN)6]2·12H2O nanometer cubic block
Opening the hollow Ni3[Co(CN)6]2·12H2Dispersing O nano cubic block in deionized water to form uniform dispersion, adding F-127, anhydrous ethanol, 1,3, 5-trimethylbenzene and dopamine, stirring, adding ammonia water, continuously stirring, centrifugally washing, and drying to obtain polydopamine-coated hollow open-pore Ni3[Co(CN)6]2·12H2O nano cubic block;
(4) synthesis of metal ion coordinated polydopamine wrapped hollow open-cell Ni3[Co(CN)6]2·12H2O nanometer cubic block
Wrapping the polydopamine with hollow open-pore Ni3[Co(CN)6]2·12H2Soaking the O nano cube in an iron metal salt solution, centrifuging and drying to obtain metal ion coordinated polydopamine-coated hollow open-cell Ni3[Co(CN)6]2·12H2O nano cubic block;
(5) synthesis of iron series metal phosphide with hollow open pore structure
Wrapping the metal ion coordinated polydopamine with hollow open-pore Ni3[Co(CN)6]2·12H2Placing the O nano cubic block into a porcelain boat to obtain a sample a, placing sodium hypophosphite into another porcelain boat to obtain a sample b, placing the sample b into the upstream of the air inlet of the tubular furnace, placing the sample a into the downstream of the air inlet of the tubular furnace, heating the tubular furnace to 300-450 ℃ in nitrogen atmosphere, calcining, and cooling the tubular furnace to room temperature to obtain the iron series metal phosphide with the hollow open pore structure.
Preferably, in (1), the molar ratio of nickel nitrate hexahydrate, trisodium citrate dihydrate and potassium cobalt cyanide is 1-10: 1.5-15: 0.67-6.7.
Preferably, in (2), Ni3[Co(CN)6]2·12H2Weight volume ratio of O nano cubic precursor to ammonia waterg: mL is 0.05-0.3: 12.5-75.
Preferably, in (3), the opening Ni is hollow3[Co(CN)6]2·12H2The weight ratio of the O nano cubic block to the dopamine is 0.025-0.2: 0.0125-0.1.
Preferably, in the centrifugal washing processes of (1), (2) and (3), washing is firstly carried out by deionized water, and then washing is carried out by absolute ethyl alcohol.
Preferably, in (4), the iron-based metal salt is at least one of a cobalt salt, an iron salt and a nickel salt;
preferably, the iron salt is ferric nitrate nonahydrate, preferably the nickel salt is nickel chloride hexahydrate, and further preferably, the iron-based metal salt comprises ferric nitrate nonahydrate, nickel chloride hexahydrate;
further preferably, the concentration of the iron-based metal salt is 0.02 to 0.06 mol/L.
Preferably, in (5), the metal ion-coordinated polydopamine wraps the hollow open-cell Ni3[Co(CN)6]2·12H2The mass ratio of the O nano cubic block to the sodium hypophosphite is 1: 10.
preferably, in (5), the temperature rising speed in the temperature rising process of the tube furnace is 1-10 ℃/min; preferably, the calcination time is 60-240 min.
The invention also provides the iron series metal phosphide with the hollow open pore structure, which is prepared by adopting the preparation method of the iron series metal phosphide with the hollow open pore structure.
The invention also provides application of the hollow open pore structure iron series metal phosphide in an electrocatalyst.
The invention firstly prepares Ni3[Co(CN)6]2·12H2O nano cubic precursor, then adopting ammonia water etching technology to etch Ni3[Co(CN)6]2·12H2Conversion of cubic O blocks to Ni3[Co(CN)6]2·12H2O hollow open-cell cubes; and then the iron series metal phosphide-based electrocatalyst with a hollow open pore structure is finally obtained by poly-dopamine coating, metal ion introduction and subsequent high-temperature phosphating process.
The invention skillfully uses the hollow open-pore Ni3[Co(CN)6]2·12H2The O cubic block is used as a precursor and a template, and then the iron series metal phosphide-based electrocatalyst with a hollow open pore structure is obtained through covering of polydopamine, introducing of metal ions and a high-temperature phosphating strategy. The obtained product not only shows excellent oxygen evolution and hydrogen evolution activities, but also has excellent full-water cracking electrocatalytic activity under a two-electrode system, which is closely related to the synergistic action among a unique hollow open pore structure, favorable mass transfer and charge transfer channels, rich active sites and multi-component iron-based metal phosphide.
Drawings
FIG. 1 is a flow chart of a hollow open-pore structure iron-based metal phosphide synthesized in example 5 of the present invention;
FIG. 2 shows the X-ray diffraction pattern of the iron-based metal phosphide having a hollow open pore structure synthesized in example 5 of the present invention, and FeP and Ni2XRD standard cards for P and NiCoP;
FIG. 3 is an XPS high resolution spectrum of Ni element in the hollow open pore structure iron-based metal phosphide synthesized in example 5 of the present invention;
FIG. 4 is an XPS high resolution spectrum of Co element in iron-based metal phosphide with a hollow open pore structure synthesized in example 5 of the present invention;
FIG. 5 is an XPS high resolution spectrum of Fe element in the hollow open pore structure iron-based metal phosphide synthesized in example 5 of the present invention;
FIG. 6 is an XPS high resolution spectrum of P element in iron-based metal phosphide with a hollow open pore structure synthesized in example 5 of the present invention;
FIG. 7 is an XPS high resolution spectrum of C element in iron-based metal phosphide with a hollow open pore structure synthesized in example 5 of the present invention;
FIG. 8 is an XPS high resolution spectrum of N element in iron-based metal phosphide with a hollow open pore structure synthesized in example 5 of the present invention;
FIG. 9 is a Raman spectrum of a hollow open-cell structured iron-based metal phosphide synthesized in example 5 of the present invention;
FIG. 10 is an SEM photograph of a hollow open-cell structured iron-based metal phosphide synthesized in example 5 of the present invention;
FIG. 11 is a TEM photograph of a hollow open-cell structured iron-based metal phosphide synthesized in example 5 of the present invention;
FIG. 12 is an HRTEM photograph of the exterior of a hollow open pore structure iron-based metal phosphide hollow cube shell synthesized in example 5 of the present invention;
FIG. 13 is an HRTEM photograph of the inside of a hollow open pore structure iron-based metal phosphide hollow cubic shell synthesized in example 5 of the present invention;
FIG. 14 is an oxygen evolution reaction curve of a hollow open pore structure iron-based metal phosphide synthesized in example 5 of the present invention;
FIG. 15 is a hydrogen evolution reaction curve of the hollow open pore structure iron-based metal phosphide synthesized in example 5 of the present invention;
FIG. 16 is an electrochemical curve of total water decomposition of the hollow open-pore structure iron-based metal phosphide synthesized in example 5 of the present invention.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
A preparation method of iron series metal phosphide with a hollow open pore structure comprises the following steps:
(1) synthesis of Ni3[Co(CN)6]2·12H2O nanometer cubic precursor
Dissolving nickel nitrate hexahydrate and trisodium citrate dihydrate in deionized water to obtain a solution A, and dissolving potassium cobalt cyanide in deionized water to obtain a solution B; adding the solution B into the solution A under the stirring state, continuously stirring, standing for aging, centrifugally washing and drying to obtain Ni3[Co(CN)6]2·12H2O nano cubic precursor;
(2) synthesis of hollow open-cell Ni3[Co(CN)6]2·12H2O nanometer cubic block
Mixing Ni3[Co(CN)6]2·12H2Dispersing the O nano cubic precursor in anhydrousDissolving ammonia water in deionized water to obtain a solution D; adding the solution D into the dispersion liquid C under the stirring state, continuously stirring, centrifugally washing and drying to obtain hollow open-pore Ni3[Co(CN)6]2·12H2O nano cubic block;
(3) synthetic polydopamine coated hollow open-cell Ni3[Co(CN)6]2·12H2O nanometer cubic block
Opening the hollow Ni3[Co(CN)6]2·12H2Dispersing O nano cubic block in deionized water to form uniform dispersion, adding F-127, anhydrous ethanol, 1,3, 5-trimethylbenzene and dopamine, stirring, adding ammonia water, continuously stirring, centrifugally washing, and drying to obtain polydopamine-coated hollow open-pore Ni3[Co(CN)6]2·12H2O nano cubic block;
(4) synthesis of metal ion coordinated polydopamine wrapped hollow open-cell Ni3[Co(CN)6]2·12H2O nanometer cubic block
Wrapping the polydopamine with hollow open-pore Ni3[Co(CN)6]2·12H2Soaking the O nano cube in an iron-based metal salt solution with the concentration of 0.02mol/L, centrifuging and drying to obtain metal ion coordination polydopamine-coated hollow open-cell Ni3[Co(CN)6]2·12H2O nano cubic block;
(5) synthesis of iron series metal phosphide with hollow open pore structure
Wrapping the metal ion coordinated polydopamine with hollow open-pore Ni3[Co(CN)6]2·12H2Placing the O nano cubic block into a porcelain boat to obtain a sample a, placing sodium hypophosphite into another porcelain boat to obtain a sample b, placing the sample b into the upstream of the air inlet of the tube furnace, placing the sample a into the downstream of the air inlet of the tube furnace, heating the tube furnace to 300 ℃ under the nitrogen atmosphere, calcining, and cooling the tube furnace to room temperature to obtain the iron-series metal phosphide with the hollow open pore structure.
Example 2
A preparation method of iron series metal phosphide with a hollow open pore structure comprises the following steps:
(1) synthesis of Ni3[Co(CN)6]2·12H2O nanometer cubic precursor
Dissolving nickel nitrate hexahydrate and trisodium citrate dihydrate in deionized water to obtain a solution A, and dissolving potassium cobalt cyanide in deionized water to obtain a solution B; adding the solution B into the solution A under the stirring state, continuously stirring, standing for aging, centrifugally washing and drying to obtain Ni3[Co(CN)6]2·12H2O nano cubic precursor;
(2) synthesis of hollow open-cell Ni3[Co(CN)6]2·12H2O nanometer cubic block
Mixing Ni3[Co(CN)6]2·12H2Dispersing the O nano cubic precursor in absolute ethyl alcohol to obtain a dispersion liquid C, and dissolving ammonia water in deionized water to obtain a solution D; adding the solution D into the dispersion liquid C under the stirring state, continuously stirring, centrifugally washing and drying to obtain hollow open-pore Ni3[Co(CN)6]2·12H2O nano cubic block;
(3) synthetic polydopamine coated hollow open-cell Ni3[Co(CN)6]2·12H2O nanometer cubic block
Opening the hollow Ni3[Co(CN)6]2·12H2Dispersing O nano cubic block in deionized water to form uniform dispersion, adding F-127, anhydrous ethanol, 1,3, 5-trimethylbenzene and dopamine, stirring, adding ammonia water, continuously stirring, centrifugally washing, and drying to obtain polydopamine-coated hollow open-pore Ni3[Co(CN)6]2·12H2O nano cubic block;
(4) synthesis of metal ion coordinated polydopamine wrapped hollow open-cell Ni3[Co(CN)6]2·12H2O nanometer cubic block
Wrapping the polydopamine with hollow open-pore Ni3[Co(CN)6]2·12H2Soaking in O nanometer cubic blockIn nickel chloride hexahydrate solution with the concentration of 0.06mol/L, centrifuging and drying to obtain metal ion coordination polydopamine-coated hollow open-pore Ni3[Co(CN)6]2·12H2O nano cubic block;
(5) synthesis of iron series metal phosphide with hollow open pore structure
Wrapping the metal ion coordinated polydopamine with hollow open-pore Ni3[Co(CN)6]2·12H2Placing the O nano cubic block into a porcelain boat to obtain a sample a, placing sodium hypophosphite into another porcelain boat to obtain a sample b, placing the sample b into the upstream of the air inlet of the tube furnace, placing the sample a into the downstream of the air inlet of the tube furnace, heating the tube furnace to 450 ℃ under the nitrogen atmosphere, calcining, and cooling the tube furnace to room temperature to obtain the iron-series metal phosphide with the hollow open pore structure.
Example 3
A preparation method of iron series metal phosphide with a hollow open pore structure comprises the following steps:
(1) synthesis of Ni3[Co(CN)6]2·12H2O nanometer cubic precursor
1mmol of nickel nitrate hexahydrate and 1.5mmol of trisodium citrate dihydrate are dissolved in 30mL of deionized water to form a uniform solution A;
dissolving 0.67mmol of potassium cobalt cyanide in 30mL of deionized water, and uniformly stirring to form a solution B;
dropwise adding the solution B into the solution A under the magnetic stirring state, continuously stirring for 2min, taking out magnetons, standing and aging for 6 days at room temperature, centrifuging, washing with deionized water for 3 times, washing with absolute ethanol for 2 times, finally placing in a blast drying oven, and drying at 50 ℃ for 6h to obtain Ni3[Co(CN)6]2·12H2O nano cubic precursor;
(2) synthesis of hollow open-cell Ni3[Co(CN)6]2·12H2O nanometer cubic block
0.05g of Ni3[Co(CN)6]2·12H2Dispersing the O nano cubic precursor in 25mL absolute ethyl alcohol to form uniform dispersion liquid C;
dissolving 12.5mL of ammonia water in 50mL of deionized water, and uniformly stirring to form a solution D;
dropwise adding the solution D into the dispersion C under magnetic stirring, continuously stirring for 10min, centrifuging, washing with deionized water for 3 times, washing with anhydrous ethanol for 2 times, placing in a forced air drying oven, and drying at 50 deg.C for 5h to obtain hollow open-cell Ni3[Co(CN)6]2·12H2O nano cubic block;
(3) synthetic polydopamine coated hollow open-cell Ni3[Co(CN)6]2·12H2O nanometer cubic block
The 0.025g of hollow open Ni3[Co(CN)6]2·12H2Dispersing cubic O blocks in 3mL of deionized water to form uniform dispersion, adding 0.05g F-127, 1.5mL of absolute ethyl alcohol, 0.2mL of 1,3, 5-trimethylbenzene and 0.0125g of dopamine, stirring for 15min, adding 0.19mL of ammonia water, continuously stirring for 1h, centrifugally washing with deionized water for 3 times, washing with absolute ethyl alcohol for 2 times, placing in a blast drying oven, and drying at 50 ℃ for 5h to obtain polydopamine-coated hollow open-cell Ni3[Co(CN)6]2·12H2O nano cubic block;
(4) synthesis of metal ion coordinated polydopamine wrapped hollow open-cell Ni3[Co(CN)6]2·12H2O nanometer cubic block
Uniformly mixing 10ml of 0.02mol/L ferric nitrate nonahydrate solution and 10ml of 0.02mol/L nickel chloride hexahydrate solution to obtain solution E, and coating 0.02g of polydopamine on hollow open-pore Ni3[Co(CN)6]2·12H2Soaking the O nano cube in the solution E for 8h, centrifuging, and drying at 50 ℃ for 5h to obtain metal ion coordinated polydopamine-coated hollow open-cell Ni3[Co(CN)6]2·12H2O nano cubic block;
(5) synthesis of iron series metal phosphide with hollow open pore structure
Coating 0.01g of metal ion coordinated polydopamine on hollow open-pore Ni3[Co(CN)6]2·12H2Putting O nano cubic block into porcelainAnd (3) carrying out boat setting to obtain a sample a, putting 0.1g of sodium hypophosphite into another porcelain boat to obtain a sample b, putting the sample b into the upstream of the air inlet of the tube furnace, putting the sample a into the downstream of the air inlet of the tube furnace, heating the tube furnace to 300 ℃ at the speed of 1 ℃/min under the nitrogen atmosphere, carrying out constant temperature calcination for 60min, and cooling the tube furnace to room temperature to obtain the hollow open pore structure iron series metal phosphide.
Example 4
A preparation method of iron series metal phosphide with a hollow open pore structure comprises the following steps:
(1) synthesis of Ni3[Co(CN)6]2·12H2O nanometer cubic precursor
Dissolving 10mmol of nickel nitrate hexahydrate and 15mmol of trisodium citrate dihydrate in 300mL of deionized water to form a uniform solution A;
dissolving 6.7mmol of potassium cobalt cyanide in 300mL of deionized water, and uniformly stirring to form a solution B;
dropwise adding the solution B into the solution A under the magnetic stirring state, continuously stirring for 10min, taking out magnetons, standing and aging at room temperature for 10 days, washing with deionized water for 6 times during centrifugation, washing with absolute ethyl alcohol for 5 times, finally placing in a blast drying oven, and drying at 80 ℃ for 12h to obtain Ni3[Co(CN)6]2·12H2O nano cubic precursor;
(2) synthesis of hollow open-cell Ni3[Co(CN)6]2·12H2O nanometer cubic block
0.3g of Ni3[Co(CN)6]2·12H2Dispersing the O nano cubic precursor in 150mL absolute ethyl alcohol to form uniform dispersion liquid C;
dissolving 75mL of ammonia water in 300mL of deionized water, and uniformly stirring to form a solution D;
dropwise adding the solution D into the dispersion C under magnetic stirring, continuously stirring for 30min, washing with deionized water for 6 times and anhydrous ethanol for 5 times during centrifugation, placing in a forced air drying oven, and drying at 80 deg.C for 12h to obtain hollow open-cell Ni3[Co(CN)6]2·12H2O nano cubic block;
(3) synthetic polydopamine coated hollow open-cell Ni3[Co(CN)6]2·12H2O nanometer cubic block
The 0.2g of hollow Ni3[Co(CN)6]2·12H2Dispersing cubic O blocks in 24mL deionized water to form uniform dispersion, adding 0.4g F-127, 12mL absolute ethyl alcohol, 1.6mL 1,3, 5-trimethylbenzene and 0.1g dopamine, stirring for 60min, adding 1.5mL ammonia water, continuing stirring for 4h, washing for 6 times with deionized water during centrifugation, washing for 5 times with absolute ethyl alcohol, placing in a blast drying oven, and drying at 80 ℃ for 12h to obtain polydopamine-coated hollow open-cell Ni3[Co(CN)6]2·12H2O nano cubic block;
(4) synthesis of metal ion coordinated polydopamine wrapped hollow open-cell Ni3[Co(CN)6]2·12H2O nanometer cubic block
Uniformly mixing 250ml of 0.06mol/L ferric nitrate nonahydrate solution and 0.06mol/L nickel chloride hexahydrate solution to obtain solution E, and coating 0.2g of polydopamine on hollow open-pore Ni3[Co(CN)6]2·12H2Soaking the O nano cube in the solution E for 24h, centrifuging, and drying at 80 ℃ for 12h to obtain metal ion coordinated polydopamine-coated hollow open-cell Ni3[Co(CN)6]2·12H2O nano cubic block;
(5) synthesis of iron series metal phosphide with hollow open pore structure
Wrapping 0.1g of metal ion coordinated polydopamine on hollow open-pore Ni3[Co(CN)6]2·12H2Placing the O nano cubic block into a porcelain boat to obtain a sample a, placing 1g of sodium hypophosphite into another porcelain boat to obtain a sample b, placing the sample b into the upstream of an air inlet of a tube furnace, placing the sample a into the downstream of the air inlet of the tube furnace, heating the tube furnace to 450 ℃ at the speed of 10 ℃/min under the nitrogen atmosphere, calcining at constant temperature for 240min, and cooling the tube furnace to room temperature to obtain the iron series metal phosphide with the hollow open pore structure.
Example 5
A preparation method of iron series metal phosphide with a hollow open pore structure comprises the following steps:
(1) synthesis of Ni3[Co(CN)6]2·12H2O nanometer cubic precursor
Dissolving 6mmol of nickel nitrate hexahydrate and 9mmol of trisodium citrate dihydrate in 200mL of deionized water to form a uniform solution A;
dissolving 4mmol of potassium cobalt cyanide in 200mL of deionized water, and uniformly stirring to form a solution B;
dropwise adding the solution B into the solution A under the magnetic stirring state, continuously stirring for 5min, taking out magnetons, standing and aging at room temperature for 7 days, washing with deionized water for 5 times during centrifugation, washing with absolute ethyl alcohol for 3 times, finally placing in a blast drying oven, and drying at 60 ℃ for 8h to obtain Ni3[Co(CN)6]2·12H2O nano cubic precursor;
(2) synthesis of hollow open-cell Ni3[Co(CN)6]2·12H2O nanometer cubic block
0.1g of Ni3[Co(CN)6]2·12H2Dispersing the O nano cubic precursor in 50mL of absolute ethanol to form a uniform dispersion liquid C;
dissolving 25mL of ammonia water in 100mL of deionized water, and uniformly stirring to form a solution D;
dropwise adding the solution D into the dispersion C under magnetic stirring, continuously stirring for 20min, washing with deionized water for 5 times and absolute ethyl alcohol for 3 times during centrifugation, placing in a forced air drying oven, and drying at 60 deg.C for 8h to obtain hollow open-cell Ni3[Co(CN)6]2·12H2O nano cubic block;
(3) synthetic polydopamine coated hollow open-cell Ni3[Co(CN)6]2·12H2O nanometer cubic block
The 0.05g of hollow Ni3[Co(CN)6]2·12H2Dispersing cubic O block in 6mL deionized water to obtain uniform dispersion, adding 0.1g F-127, 3mL anhydrous ethanol, 0.4mL 1,3, 5-trimethylbenzene, and 0.025g dopamine, stirring for 30min, adding 0.37Continuously stirring 5mL ammonia water for 2h, washing with deionized water for 5 times during centrifugation, washing with anhydrous ethanol for 3 times, placing in a blast drying oven, and drying at 60 deg.C for 8h to obtain polydopamine-coated hollow open-cell Ni3[Co(CN)6]2·12H2O nano cubic block;
(4) synthesis of metal ion coordinated polydopamine wrapped hollow open-cell Ni3[Co(CN)6]2·12H2O nanometer cubic block
Uniformly mixing 20ml of 0.05mol/L ferric nitrate nonahydrate solution and 20ml of 0.05mol/L nickel chloride hexahydrate solution to obtain solution E, and coating 0.03g of polydopamine on hollow open-pore Ni3[Co(CN)6]2·12H2Soaking the O nano cube in the solution E for 12h, centrifuging, and drying at 60 ℃ for 8h to obtain metal ion coordinated polydopamine-coated hollow open-cell Ni3[Co(CN)6]2·12H2O nano cubic block;
(5) synthesis of iron series metal phosphide with hollow open pore structure
Wrapping 0.03g of metal ion coordinated polydopamine on hollow open-pore Ni3[Co(CN)6]2·12H2Placing the O nano cubic block into a porcelain boat to obtain a sample a, placing 0.3g of sodium hypophosphite into another porcelain boat to obtain a sample b, placing the sample b into the upstream of an air inlet of a tube furnace, placing the sample a into the downstream of the air inlet of the tube furnace, heating the tube furnace to 400 ℃ at the speed of 3 ℃/min under the nitrogen atmosphere, calcining at constant temperature for 120min, and cooling the tube furnace to room temperature to obtain the iron series metal phosphide with the hollow open pore structure.
FIG. 1 is a flow chart of a hollow open-pore structure iron-based metal phosphide synthesized in example 5 of the present invention; as shown in the figure, we first prepared a Ni3[Co(CN)6]2·12H2O nano cubic block, then adopting ammonia water etching technology to etch Ni3[Co(CN)6]2·12H2Conversion of cubic O blocks to Ni3[Co(CN)6]2·12H2O hollow open-cell cubes; further through polydopamine coating and metal ion introduction, and after the polydopamine coating and the metal ion introduction are assistedAnd (3) continuing the high-temperature phosphating process to finally obtain the iron metal phosphide with the hollow open pore structure.
FIG. 2 shows the X-ray diffraction pattern of the iron-based metal phosphide having a hollow open pore structure synthesized in example 5 of the present invention, and FeP and Ni2XRD standard cards for P and NiCoP. The XRD standard card of FeP is ICDD00-003-2The XRD standard card of P is ICDD 00-003-. Wherein, the characteristic peak of ICDD 00-003-. As can be seen from FIG. 1, the obtained product contains three phases, i.e., FeP and Ni2P and NiCoP, demonstrating that the electrocatalyst synthesized in example 5 of the invention is iron based metal phosphide.
FIG. 3 is an XPS high resolution spectrum of Ni element in the hollow open pore structure iron-based metal phosphide synthesized in example 5 of the present invention. In FIG. 3, two peaks appear at 852.8eV and 856.3eV, where the peak with the binding energy at 852.8eV should be Ni for nickel phosphide in metal phosphideδ+While the peak with the binding energy at 856.3eV is nickel in the oxidized state, due to surface oxidation of the sample when exposed to air.
FIG. 4 is an XPS high resolution spectrum of Co element in the hollow open pore structure iron-based metal phosphide synthesized in example 5 of the present invention. In FIG. 4, the peak at a binding energy of 778.4eV corresponds to Co 2p as a Co species in NiCoP3/2The peak at the binding energy of 781.3eV corresponds to cobalt in the oxidized state, while the peak at 782.4eV is the satellite peak for cobalt oxide.
FIG. 5 is an XPS high resolution spectrum of Fe element in example 5 of the present invention. In FIG. 5, three peaks at 706.5eV, 710.8eV, and 713.9eV can be observed, with the peak at 706.5eV corresponding to the Fe species in the iron phosphide and the peak at 710.8eV corresponding to the Fe species2+Fe 2p of3/2The peak at 713.9eV corresponds to Fe3+。
FIG. 6 is an XPS high resolution spectrum of P element in example 5 of the present invention. The peak with binding energy at 129.7eV in FIG. 6 corresponds to P in the metal phosphideδ-This peak occurs relative to elemental phosphorus (130eV)A negative shift occurs and therefore carries a negative charge. The peak of the binding energy at 134eV is phosphorus in an oxidized state due to surface oxidation caused by contact with air.
FIG. 7 is an XPS high resolution spectrum of element C in example 5 of the present invention. In FIG. 7, the peaks of the binding energies at 284.8eV, 285.6eV and 286.5eV are sp2Hybridized carbon, sp3Hybridized carbon, sp3Characteristic peaks of hybridized carbon-nitrogen. The C species mainly come from the carbonization of cyano-group and polydopamine in the reaction precursor in the high-temperature phosphorization process, which shows that the obtained electrocatalyst not only contains iron metal phosphide, but also contains a large amount of carbon, and thus, the improvement of the conductivity and the catalytic activity of the electrocatalyst can be guaranteed.
FIG. 8 is an XPS high resolution spectrum of N element in example 5 of the present invention. The peaks with binding energies at 398.2eV, 399.6eV and 401.3eV are characteristic peaks for pyridine nitrogen, pyrrole nitrogen and quaternary nitrogen, respectively. The presence of the nitrogen peak can be attributed to the cyano group and polydopamine in the reaction precursor, indicating that the carbon component in the electrocatalyst contains a significant amount of nitrogen element, i.e., the formation of nitrogen-doped carbon.
FIG. 9 shows a Raman spectrum of a hollow open-pore structure iron-based metal phosphide synthesized in example 5 of the present invention. It is clear from FIG. 9 that the distances between 1350 and 1580cm-1There are two distinct peaks corresponding to the D and G bands of the material, respectively. In general, the D peak represents a lattice defect of a carbon atom, and the G peak represents a carbon atom sp2Hybrid in-plane stretching vibration. Wherein, the ratio of the peak intensity of the D peak to the peak intensity of the G peak (I)D/IG) The carbon material is an important parameter for representing the graphitization degree of the carbon material, and the smaller the ratio is, the higher the graphitization degree of the carbon material is. According to calculation, the synthesized iron series metal phosphide with the hollow open pore structure has the structure ID/IGAbout 0.96, indicating a higher degree of graphitization of the carbon in the catalyst.
FIG. 10 is an SEM photograph of the hollow open-pore structure iron-based metal phosphide synthesized in example 5 of the present invention. From the figure it can be seen that the morphology of the electrocatalyst is cubic structures, approximately 230nm in size, and careful observation reveals that pore structures appear at the apex of each cube, the appearance of which can provide advantageous mass and charge transfer channels for the active sites inside the cube.
FIG. 11 is a TEM image of a hollow open-pore structure iron-based metal phosphide synthesized in example 5 of the present invention. As can be seen, the catalyst was a hollow cubic structure and the pore structure was clearly visible at the vertices of the cubic blocks, which is consistent with the analysis results of SEM.
FIG. 12 is an HRTEM photograph of the exterior of a hollow open-structured iron-based metal phosphide hollow cube shell synthesized in example 5 of the present invention. As can be seen, the outer portion of the hollow cubic shell contains two clear lattice fringes, and the lattice fringe spacing is estimated to be 0.204nm and 0.246nm, respectively, corresponding to Ni2P and FeP, indicating that the exterior of the hollow cube shell consists primarily of Ni2P and FeP.
FIG. 13 is an HRTEM photograph of the inside of a hollow open pore structure iron-based metal phosphide hollow cubic shell synthesized in example 5 of the present invention. As can be seen, the interior of the hollow cubic shell contains two clear lattice fringes, wherein the crystal planes with interplanar spacing of 0.201nm correspond to NiCoP, and the crystal planes with interplanar spacing of 0.204nm correspond to Ni2P, indicating that the interior of the hollow cube shell is composed primarily of Ni2P and NiCoP.
FIG. 14 is an oxygen evolution reaction curve of the hollow open pore structure iron-based metal phosphide synthesized in example 5 of the present invention. According to the calculation, the current density reaches 10mA/cm2Only 252mV of overpotential is needed, which shows that the prepared iron series metal phosphide with the hollow open pore structure has excellent oxygen evolution activity.
FIG. 15 is a hydrogen evolution reaction curve of the hollow open pore structure iron-based metal phosphide synthesized in example 5 of the present invention. According to calculation, the electrocatalyst only needs 119mV of overpotential to enable the current density of the hydrogen evolution reaction to reach 10mA/cm2The result shows that the prepared iron series metal phosphide with the hollow open pore structure has excellent hydrogen evolution activity.
FIG. 16 is an electrochemical curve of total water decomposition of the hollow open-pore structure iron-based metal phosphide synthesized in example 5 of the present invention. From FIG. 16, it can be observedTo that, the current density reaches 10mA/cm2When the catalyst is used, only 1.63V of voltage is needed, and excellent full-water-splitting electrocatalytic activity is shown, which is closely related to the unique hollow open-pore structure, favorable mass and charge transfer channels, abundant active sites and the synergistic action among multi-component iron-based metal phosphide.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (9)
1. The preparation method of the iron series metal phosphide with the hollow open pore structure is characterized by comprising the following steps of:
(1) synthesis of Ni3[Co(CN)6]2•12H2O nanometer cubic precursor
Dissolving nickel nitrate hexahydrate and trisodium citrate dihydrate in deionized water to obtain a solution A, and dissolving potassium cobalt cyanide in deionized water to obtain a solution B; adding the solution B into the solution A under the stirring state, continuously stirring, standing for aging, centrifugally washing and drying to obtain Ni3[Co(CN)6]2•12H2O nano cubic precursor;
(2) synthesis of hollow open-cell Ni3[Co(CN)6]2•12H2O nanometer cubic block
Adding the Ni3[Co(CN)6]2•12H2Dispersing the O nano cubic precursor in absolute ethyl alcohol to obtain a dispersion liquid C, and dissolving ammonia water in deionized water to obtain a solution D; adding the solution D into the dispersion liquid C under the stirring state, continuously stirring, centrifugally washing and drying to obtain hollow open-pore Ni3[Co(CN)6]2•12H2O nano cubic block;
(3) synthetic polydopamine coated hollow open-cell Ni3[Co(CN)6]2•12H2O nanometer cubic block
Opening the hollow Ni3[Co(CN)6]2•12H2Dispersing O nano cubic block in deionized water to form dispersion, adding F-127, absolute ethyl alcohol, 1,3, 5-trimethylbenzene and dopamine, stirring, adding ammonia water, continuously stirring, centrifugally washing, and drying to obtain polydopamine-coated hollow open-pore Ni3[Co(CN)6]2•12H2O nano cubic block;
(4) synthesis of metal ion coordinated polydopamine wrapped hollow open-cell Ni3[Co(CN)6]2•12H2O nanometer cubic block
Wrapping the polydopamine with hollow open-pore Ni3[Co(CN)6]2•12H2Soaking the O nano cube in an iron metal salt solution, centrifuging and drying to obtain metal ion coordinated polydopamine-coated hollow open-cell Ni3[Co(CN)6]2•12H2O nano cubic block; the iron-based metal salt is at least one of cobalt salt, iron salt and nickel salt; the iron salt is ferric nitrate nonahydrate, and the nickel salt is nickel chloride hexahydrate; the concentration of the iron metal salt is 0.02-0.06mol/L
(5) Synthesis of iron series metal phosphide with hollow open pore structure
Wrapping the metal ion coordinated polydopamine with hollow open-pore Ni3[Co(CN)6]2•12H2Placing the O nano cubic block into a porcelain boat to obtain a sample a, placing sodium hypophosphite into another porcelain boat to obtain a sample b, placing the sample b into the upstream of the air inlet of the tubular furnace, placing the sample a into the downstream of the air inlet of the tubular furnace, heating the tubular furnace to 300-450 ℃ in nitrogen atmosphere, calcining, and cooling the tubular furnace to room temperature to obtain the iron series metal phosphide with the hollow open pore structure.
2. The method for preparing hollow open-pore structure iron-based metal phosphide as claimed in claim 1, wherein in (1), the molar ratio of nickel nitrate hexahydrate, trisodium citrate dihydrate and potassium cobalt cyanide is 1-10: 1.5-15: 0.67-6.7.
3. The method for producing a hollow open-porous structured iron-based metal phosphide as claimed in claim 1, wherein in (2), Ni3[Co(CN)6]2•12H2The weight volume ratio g of the O nano cubic precursor to the ammonia water is as follows: mL is 0.05-0.3: 12.5-75.
4. The method for producing hollow open-structured iron-based metal phosphide as claimed in claim 1, wherein in (3), hollow open-structured Ni3[Co(CN)6]2•12H2The weight ratio of the O nano cubic block to the dopamine is 0.025-0.2: 0.0125-0.1.
5. The method for preparing iron-based metal phosphide with a hollow open pore structure according to claim 1, wherein in the centrifugal washing steps (1), (2) and (3), washing with deionized water is first performed, and then washing with absolute ethyl alcohol is performed.
6. The method for preparing iron-based metal phosphide with hollow open pore structure according to claim 1, wherein in (5), metal ion-coordinated polydopamine is used for wrapping hollow open pore Ni3[Co(CN)6]2•12H2The mass ratio of the O nano cubic block to the sodium hypophosphite is 1: 10.
7. the method for preparing the iron-based metal phosphide with a hollow open-cell structure according to claim 1, wherein in (5), the temperature rise rate in the temperature rise process of the tube furnace is 1-10 ℃/min; the calcination time is 60-240 min.
8. A hollow open-pore structure iron-based metal phosphide, characterized by being produced by the method for producing a hollow open-pore structure iron-based metal phosphide according to any one of claims 1 to 7.
9. Use of the hollow open-porous structured iron-based metal phosphide of claim 8 in an electrocatalyst.
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