CN113388847A - Prussian blue analogue derived metal sulfide/nitrogen-doped carbon electrocatalyst and preparation method and application thereof - Google Patents
Prussian blue analogue derived metal sulfide/nitrogen-doped carbon electrocatalyst and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 22
- 229910052976 metal sulfide Inorganic materials 0.000 title claims abstract description 17
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229910052960 marcasite Inorganic materials 0.000 claims abstract description 84
- 229910052683 pyrite Inorganic materials 0.000 claims abstract description 84
- 239000003054 catalyst Substances 0.000 claims abstract description 48
- -1 cobalt iron Prussian blue analogue Chemical class 0.000 claims abstract description 27
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 12
- 238000005530 etching Methods 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 238000005303 weighing Methods 0.000 claims description 32
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 229910020598 Co Fe Inorganic materials 0.000 claims description 15
- 229910002519 Co-Fe Inorganic materials 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 229910001868 water Inorganic materials 0.000 claims description 14
- 235000019441 ethanol Nutrition 0.000 claims description 13
- 230000007935 neutral effect Effects 0.000 claims description 11
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 11
- FQMNUIZEFUVPNU-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co] FQMNUIZEFUVPNU-UHFFFAOYSA-N 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 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 6
- 239000001509 sodium citrate Substances 0.000 claims description 6
- 239000002105 nanoparticle Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 2
- 238000005486 sulfidation Methods 0.000 claims 1
- 229910000510 noble metal Inorganic materials 0.000 abstract description 15
- 238000004073 vulcanization Methods 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 239000002114 nanocomposite Substances 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract 2
- 238000013329 compounding Methods 0.000 abstract 1
- 239000011148 porous material Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 15
- 239000004744 fabric Substances 0.000 description 11
- 150000001721 carbon Chemical class 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000001075 voltammogram Methods 0.000 description 9
- 239000003575 carbonaceous material Substances 0.000 description 7
- 229910052723 transition metal Inorganic materials 0.000 description 7
- 230000007774 longterm Effects 0.000 description 5
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- NJFMNPFATSYWHB-UHFFFAOYSA-N ac1l9hgr Chemical compound [Fe].[Fe] NJFMNPFATSYWHB-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 229960003351 prussian blue Drugs 0.000 description 2
- 239000013225 prussian blue Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000012353 t test Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910017108 Fe—Fe Inorganic materials 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 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
- 229910052748 manganese Inorganic materials 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000013354 porous framework Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
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- 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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/069—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of at least one single element and at least one compound; consisting of two or more compounds
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- 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 Prussian blue analogue derived metal sulfide/nitrogen-doped carbon electrocatalyst, a preparation method and application thereof. The invention takes cobalt iron Prussian blue analogue as a template, and prepares the non-noble metal sulfide cubic cage-shaped nano composite catalyst by ammonia water etching and gas phase vulcanization. The catalyst has CoS2‑FeS2The nitrogen-doped carbon heterostructure is in a cubic pore structure, has high porosity and good conductivity, and has excellent hydrogen evolution and oxygen evolution electrocatalytic activity in an alkaline medium. The excellent catalytic performance is mainly due to the enhanced conductivity of nitrogen-doped carbon; CoS2‑FeS2N doped carbon heterojunctionThe electronic structure of a heterogeneous interface is changed, the conductivity of the heterogeneous interface is improved, and the conduction of electrons is facilitated; the compounding of the nitrogen-doped carbon matrix increases the stability of the catalyst, promotes the effective transfer of electrons between the metal sulfide and the carbon matrix, and greatly improves the electrocatalytic performance of the material.
Description
The technical field is as follows:
the invention belongs to the field of new energy material technology and electrochemical catalysis, and particularly relates to a Prussian blue analogue-derived metal sulfide/nitrogen-doped carbon electrocatalyst; also relates to a preparation method of the catalyst and the application of the catalyst in the anodic oxygen evolution reaction of electrolyzed water, the cathodic hydrogen evolution reaction of electrolyzed water and the electrocatalysis in full-electrolysis water.
Background art:
the Hydrogen Evolution Reaction (HER) and the Oxygen Evolution Reaction (OER) are key electrode processes of the electrolytic water technology, but both processes suffer from slow kinetics. The catalyst for HER is Pt and its alloy, and the catalyst for OER is IrO2And RuO2However, these precious metals are rare in nature, so it is important to develop a new type of high-efficiency and low-cost electrocatalyst, of which carbon-based non-precious metal catalysts are one of the most likely to replace the above precious metals, and this has attracted much attention.
Prussian blue and analogues thereof are a class of porous crystalline materials, which themselves have high stability and high porosity and are commonly used in high efficiency catalytic and separation processes. The cobalt iron prussian blue analogue is prepared by reacting cobalt nitrate hexahydrate with potassium ferricyanide, can be used as a sacrificial template to prepare a non-noble metal compound-porous carbon composite material by a high-temperature calcination method, and can adjust electronic properties and surface polarity by doping heteroatom so as to improve the electrochemical catalytic activity of the composite material. Currently, N, S, B, P, etc. are the more commonly used doping atoms that can be substituted for some of the sp in the graphite lattice2The carbon atoms are hybridized, the electronic characteristics of the carbon material are changed, and the catalytic activity and the stability of the carbon material are further improved. Although the Prussian blue analogue is taken as a precursor to prepare the porous carbon nano material to achieve certain performance at present, the cobalt-iron Prussian blue analogue is taken as a template and the precursor, ammonia etching and gas phase vulcanization are carried out to prepare the non-noble metal/carbon material cubic nano compound with the metal sulfide/nitrogen-doped carbon heterostructure and the HER and OER double-function electrocatalytic catalyst thereofThe performance study has not been reported in the literature.
The invention takes cobalt iron Prussian blue analogue as a template, and prepares the non-noble metal sulfide cubic cage-shaped nano carbon compound by ammonia etching and gas phase vulcanization. Due to the porous framework structure of the cobalt iron Prussian blue analogue, the non-noble metal sulfide/nitrogen-doped carbon material obtained by ammonia etching and gas phase vulcanization inherits the cubic porous structure. The resulting CoS2-FeS2the/NC catalyst has high porosity, good conductivity and catalytic activity, effectively reduces the overpotential of OER and HER, and shows excellent long-term stability. The method has important theoretical and practical significance for developing non-noble metal sulfide heteroatom doped carbon composite electro-catalysts and energy conversion and storage devices.
The invention content is as follows:
in view of the deficiencies of the prior art and the need for research and application in the art, it is an object of the present invention to provide a prussian blue analog derived metal sulfide/nitrogen doped carbon electrocatalyst; namely, CoS is obtained by taking a cobalt-iron Prussian blue analogue as a template and carrying out ammonia etching and gas phase vulcanization on the cobalt-iron Prussian blue analogue2-FeS2A nitrogen-doped carbon catalyst; wherein the cobalt iron Prussian blue analogue is marked as CoFe-PBA, CoS2-FeS2N-doped carbon catalyst is described as CoS2-FeS2/NC；
The second purpose of the invention is to provide a preparation method of a Prussian blue analogue derived metal sulfide/nitrogen doped carbon electrocatalyst, which comprises the following steps:
(a) preparation of CoFe-PBA
Weighing 860mg Co (NO)3)2·6H2Dissolving O and 1.32g of sodium citrate in 100mL of deionized water, and marking as a solution A; weighing 658mg of potassium ferricyanide and dissolving the potassium ferricyanide into another 100mL of deionized water, and marking as a solution B; adding the solution B into the solution A under the condition of stirring, stirring for three minutes, standing for 10 hours, centrifuging to collect a sample, washing with ionized water and absolute ethyl alcohol for three times respectively, and drying at 50 ℃ for 12 hours;
(b)CoS2-FeS2preparation of/NC
Dispersing 20mg of Co-Fe PBA in 50mL of ethanol, adding the Co-Fe PBA into 50mL of 25% ammonia water solution, stirring and reacting for 10min, centrifugally collecting a sample, washing the sample with deionized water until the solution is nearly neutral, and drying the sample at 60 ℃ for 24h to obtain a cobalt-iron nano-framework which is marked as CoFe-NFs; weighing 20mg of CoFe-NFs in a magnetic boat, placing the magnetic boat in the lower end of a tube furnace, weighing 200-400 mg of sulfur powder in the magnetic boat, placing the magnetic boat in the upper end of the tube furnace, heating to 200-500 ℃ at the speed of 2 ℃/min, and vulcanizing in a nitrogen atmosphere for 1-5 hours to obtain the catalyst CoS2-FeS2/NC；
The metal sulfide/nitrogen-doped carbon electrocatalyst is of a hollow nano cubic cage structure, elements are uniformly distributed on the edges of a cube, and the average particle size of nano cubic cage units of the catalyst is 100-200 nm; metal sulfide CoS2-FeS2The average grain diameter of the nano-particles is 5-30nm, and the nano-particles are uniformly embedded on the nitrogen-doped carbon nano-chip.
The invention also aims to provide the catalytic application of the Prussian blue analogue derived metal sulfide/nitrogen-doped carbon electrocatalyst in the electrolysis of water cathode HER and anode OER.
The invention takes cobalt iron Prussian blue analogue as a template, prepares the non-noble metal sulfide cubic cage-shaped nano composite electrocatalyst by ammonia etching and gas phase vulcanization; the heterostructure not only improves the conductivity of the catalyst and increases active sites, but also effectively reduces overpotentials of HER and OER, and shows excellent long-term stability.
Compared with the prior art, the invention has the following main advantages and beneficial effects:
1) the bifunctional electrocatalyst is a non-noble metal composite material, and the used raw materials are easy to purchase, rich in resources, low in price, easy to operate and convenient for large-scale production;
2) the bifunctional electrocatalyst is a non-noble metal sulfide/nitrogen-doped carbon material, has better OER and HER catalytic activities, and has remarkable advantages compared with the unilateral OER or HER activities of non-noble metal/nonmetal catalysts reported in the current research;
3) according to the inventionDual function electrocatalyst and commercial RuO2Compared with the catalyst, the stability of the catalyst is obviously improved, and the catalyst can keep good catalytic activity in long-term use of an electrolytic water technology.
Description of the drawings:
FIG. 1 shows CoFe-PBA (A) obtained in example 1, CoFe-NFs (B) obtained in example 1, and CoS obtained in example 12-FeS2Scanning Electron microscopy of/NC (C) and CoS obtained in example 12-FeS2(NC) (D) transmission electron microscope image.
FIG. 2 depicts the CoS obtained in example 12-FeS2XRD pattern of/NC catalyst.
FIG. 3 depicts the CoS obtained in example 12-FeS2NC, FeS from comparative example 12NC and commercial RuO2The OER linear sweep voltammograms of the carbon cloths were modified separately.
FIG. 4 shows the CoS obtained in example 12-FeS2Comparative example 1 FeS/NC2NC NiS from comparative example 22-FeS2MnS-FeS obtained by/NC and comparative example 32OER linear sweep voltammogram of/NC modified carbon cloth.
FIG. 5 depicts the CoS obtained in example 12-FeS2The OER constant voltage i-t (left) of the/NC modified carbon cloth and the linear sweep voltammetry curve (right) before and after 1500 cycles of cyclic voltammetry are tested.
FIG. 6 depicts the CoS obtained in example 12-FeS2NC, FeS from comparative example 12HER linear sweep voltammograms for the modified carbon cloths of/NC and commercial Pt/C, respectively.
FIG. 7 shows the CoS obtained in example 12-FeS2Comparative example 1 FeS/NC2NC NiS from comparative example 22-FeS2MnS-FeS obtained by/NC and comparative example 32HER linear sweep voltammogram of/NC modified carbon cloth.
FIG. 8 shows the CoS obtained in example 12-FeS2A full-hydrolysis linear scanning voltammogram carried out by the/NC non-noble metal electrocatalyst modified carbon cloth.
FIG. 9 depicts the CoS obtained in example 12-FeS2The carbon cloth modified by NC non-noble metal electrocatalyst is distributed at 1.61VConstant voltage i-t test pattern.
The specific implementation mode is as follows:
for a further understanding of the invention, reference will now be made to the following examples and drawings, which are not intended to limit the invention in any way.
Example 1:
(a) preparation of CoFe-PBA
Weighing 860mg Co (NO)3)2·6H2Dissolving O and 1.32g of sodium citrate in 100mL of deionized water, and marking as a solution A; weighing 658mg of potassium ferricyanide, and dissolving the weighed potassium ferricyanide in another 100mL of deionized water to obtain a solution B; adding the solution B into the solution A under the condition of stirring, stirring for three minutes, standing for 10 hours, centrifuging to collect a sample, washing with deionized water and absolute ethyl alcohol for three times respectively, and drying at 50 ℃ for 12 hours;
(b)CoS2-FeS2preparation of/NC
Dispersing 20mg of Co-Fe PBA in 50mL of ethanol, adding the Co-Fe PBA into 50mL of 25% ammonia water solution, stirring and reacting for 10min, centrifugally collecting a sample, washing the sample with deionized water until the solution is nearly neutral, and drying the sample at 60 ℃ for 24h to obtain a cobalt-iron nano-framework CoFe-NFs;
weighing 20mg of CoFe-NFs, placing the CoFe-NFs in a magnetic boat, placing the magnetic boat at the lower end of a tube furnace, weighing 300mg of sulfur powder, placing the magnetic boat at the upper end of the tube furnace, heating to 400 ℃ at a heating rate of 2 ℃/min, and vulcanizing in a nitrogen atmosphere for 4 hours to obtain the catalyst CoS2-FeS2/NC；
Example 2:
(a) preparation of CoFe-PBA
Prepared according to the method and conditions of step (a) in example 1;
(b)CoS2-FeS2preparation of/NC
Dispersing 20mg of Co-Fe PBA in 50mL of ethanol, adding the Co-Fe PBA into 50mL of 25% ammonia water solution, stirring and reacting for 10min, centrifugally collecting a sample, washing the sample with deionized water until the solution is nearly neutral, and drying the sample at 60 ℃ for 24h to obtain a cobalt-iron nano-framework CoFe-NFs;
20mg of the CoFe-NFs was weighed inPlacing a magnetic boat at the lower end of the tube furnace, weighing 300mg of sulfur powder, placing the sulfur powder at the upper end of the tube furnace in the magnetic boat, heating to 200 ℃ at a heating rate of 2 ℃/min, and vulcanizing in a nitrogen atmosphere for 4 hours to obtain the catalyst CoS2-FeS2/NC；
Example 3:
(a) preparation of CoFe-PBA
Prepared according to the method and conditions of step (a) in example 1;
(b)CoS2-FeS2preparation of/NC
Dispersing 20mg of Co-Fe PBA in 50mL of ethanol, adding the Co-Fe PBA into 50mL of 25% ammonia water solution, stirring and reacting for 10min, centrifugally collecting a sample, washing the sample with deionized water until the solution is nearly neutral, and drying the sample at 60 ℃ for 24h to obtain a cobalt-iron nano-framework CoFe-NFs;
weighing 20mg of CoFe-NFs, placing the CoFe-NFs in a magnetic boat, placing the magnetic boat at the lower end of a tube furnace, weighing 300mg of sulfur powder, placing the magnetic boat at the upper end of the tube furnace, heating to 300 ℃ at a heating rate of 2 ℃/min, and keeping vulcanization in a nitrogen atmosphere for 4 hours to obtain the catalyst CoS2-FeS2/NC；
Example 4:
(a) preparation of CoFe-PBA
Prepared according to the method and conditions of step (a) in example 1;
(b)CoS2-FeS2preparation of/NC
Dispersing 20mg of Co-Fe PBA in 50mL of ethanol, adding the Co-Fe PBA into 50mL of 25% ammonia water solution, stirring and reacting for 10min, centrifugally collecting a sample, washing the sample with deionized water until the solution is nearly neutral, and drying the sample at 60 ℃ for 24h to obtain a cobalt-iron nano-framework CoFe-NFs;
weighing 20mg of CoFe-NFs, placing the CoFe-NFs in a magnetic boat, placing the magnetic boat at the lower end of a tube furnace, weighing 300mg of sulfur powder, placing the magnetic boat at the upper end of the tube furnace, heating to 500 ℃ at a heating rate of 2 ℃/min, and vulcanizing in a nitrogen atmosphere for 4 hours to obtain the catalyst CoS2-FeS2/NC；
Example 5:
(a) preparation of CoFe-PBA
Prepared according to the method and conditions of step (a) in example 1;
(b)CoS2-FeS2preparation of/NC
Dispersing 20mg of Co-Fe PBA in 50mL of ethanol, adding the Co-Fe PBA into 50mL of 25% ammonia water solution, stirring and reacting for 10min, centrifugally collecting a sample, washing the sample with deionized water until the solution is nearly neutral, and drying the sample at 60 ℃ for 24h to obtain a cobalt-iron nano-framework CoFe-NFs;
weighing 20mg of CoFe-NFs, placing the CoFe-NFs in a magnetic boat, placing the magnetic boat at the lower end of a tube furnace, weighing 200mg of sulfur powder, placing the magnetic boat at the upper end of the tube furnace, heating to 400 ℃ at a heating rate of 2 ℃/min, and vulcanizing in a nitrogen atmosphere for 4 hours to obtain the catalyst CoS2-FeS2/NC；
Example 6:
(a) preparation of CoFe-PBA
Prepared according to the method and conditions of step (a) in example 1;
(b)CoS2-FeS2preparation of/NC
Dispersing 20mg of Co-Fe PBA in 50mL of ethanol, adding the Co-Fe PBA into 50mL of 25% ammonia water solution, stirring and reacting for 10min, centrifugally collecting a sample, washing the sample with deionized water until the solution is nearly neutral, and drying the sample at 60 ℃ for 24h to obtain a cobalt-iron nano-framework CoFe-NFs;
weighing 20mg of CoFe-NFs, placing the CoFe-NFs in a magnetic boat, placing the magnetic boat at the lower end of a tube furnace, weighing 250mg of sulfur powder, placing the magnetic boat at the upper end of the tube furnace, heating to 400 ℃ at a heating rate of 2 ℃/min, and vulcanizing in a nitrogen atmosphere for 4 hours to obtain the catalyst CoS2-FeS2/NC；
Comparative example 1:
(a) preparation of FeFe-PB
1.2g Fe (NO) are weighed out3)3·6H2Dissolving O and 1.32g of sodium citrate in 100mL of deionized water, and marking as a solution A; weighing 658mg of potassium ferricyanide, and dissolving the weighed potassium ferricyanide in another 100mL of deionized water to obtain a solution B; adding the solution B into the solution A under the condition of stirring, stirring for three minutes, standing for 10 hours, and then centrifugally collectingThe samples were collected, then washed three times with deionized water and absolute ethanol each, and dried at 50 ℃ for 12 h.
(b)FeS2Preparation of/NC
Dispersing 20mg of Fe-Fe PB in 50mL of ethanol, adding the ethanol into 50mL of 25% ammonia water solution, stirring and reacting for 10min, centrifuging to collect a sample, washing the sample with deionized water until the solution is nearly neutral, and drying the sample at 60 ℃ for 24h to obtain an iron-iron nano framework; weighing 20mg of the iron-iron nano frame, placing the iron-iron nano frame in a magnetic boat, placing the iron-iron nano frame at the lower end of a tube furnace, weighing 300mg of sulfur powder, placing the sulfur powder in the magnetic boat, placing the sulfur powder at the upper end of the tube furnace, heating to 400 ℃ at a heating rate of 2 ℃/min, and keeping vulcanization for 4 hours in a nitrogen atmosphere to obtain the catalyst FeS2/NC；
Comparative example 2:
(a) preparation of NiFe-PBA
Weighing 870mg Ni (NO)3)2·6H2Dissolving O and 1.32g of sodium citrate in 100mL of deionized water, and marking as a solution A; weighing 658mg of potassium ferricyanide, and dissolving the weighed potassium ferricyanide in another 100mL of deionized water to obtain a solution B; adding the solution B into the solution A under the condition of stirring, stirring for three minutes, standing for 10 hours, centrifuging to collect a sample, washing with deionized water and absolute ethyl alcohol for three times respectively, and drying at 50 ℃ for 12 hours;
(b)NiS2-FeS2preparation of/NC
Dispersing 20mg of NiFe PBA in 50mL of ethanol, adding the mixture into 50mL of 25% ammonia water solution, stirring and reacting for 10min, centrifugally collecting a sample, washing the sample with deionized water until the solution is nearly neutral, and drying the sample at 60 ℃ for 24h to obtain the nickel-iron nano-frame NiFe-NFs;
weighing 20mg of NiFe-NFs, placing the NiFe-NFs in a magnetic boat, placing the magnetic boat at the lower end of a tube furnace, weighing 300mg of sulfur powder, placing the magnetic boat at the upper end of the tube furnace, heating to 400 ℃ at a heating rate of 2 ℃/min, and vulcanizing in a nitrogen atmosphere for 4 hours to obtain the catalyst NiS2-FeS2/NC；
Comparative example 3:
(a) preparation of MnFe-PBA
Weighing 500mg MnSO4·H2O and 1.32g lemonDissolving sodium citrate in 100mL of deionized water, and marking as a solution A; weighing 658mg of potassium ferricyanide, and dissolving the weighed potassium ferricyanide in another 100mL of deionized water to obtain a solution B; adding the solution B into the solution A under the condition of stirring, stirring for three minutes, standing for 10 hours, centrifuging to collect a sample, washing with deionized water and absolute ethyl alcohol for three times respectively, and drying at 50 ℃ for 12 hours;
(b)MnS-FeS2preparation of/NC
Dispersing 20mg of MnFe PBA in 50mL of ethanol, adding the ethanol into 50mL of 25% ammonia water solution, stirring and reacting for 10min, centrifuging to collect a sample, washing the sample with deionized water until the solution is nearly neutral, and drying the sample at 60 ℃ for 24h to obtain a nickel-iron nano-framework MnFe-NFs;
weighing 20mg of NiFe-NFs, placing the NiFe-NFs in a magnetic boat, placing the NiFe-NFs in the lower end of a tube furnace, weighing 300mg of sulfur powder, placing the sulfur powder in the magnetic boat, placing the sulfur powder in the upper end of the tube furnace, heating to 400 ℃ at a heating rate of 2 ℃/min, and vulcanizing for 4 hours in a nitrogen atmosphere to obtain the catalyst MnS-FeS2/NC；
FIG. 1 shows CoFe-PBA, CoFe-NFs and CoS obtained in example 1(A), example 1(B) and example 1(C), respectively2-FeS2Scanning Electron microscopy of/NC and CoS obtained in example 12-FeS2(NC) (D) transmission electron microscope image. As can be seen from FIG. A, the crystal grains of CoFe-PBA appear as regular cubes, and CoFe-PBA has a good crystal form. As can be seen from FIG. B, the edges of the cubes of the ammonia etched CoFe-PBA were destroyed, but the cube skeleton was substantially maintained. Panel C and D show that the material retains a cubic structure after gas phase vulcanization, where panel D shows CoS2-FeS2Uniformly distributed on the surface of the cube, presenting a hollow cage-like structure, which may be the result of gradual migration of internal components to the external surface during high temperature vulcanization.
FIG. 2 depicts the CoS obtained in example 12-FeS2XRD pattern of/NC catalyst. By comparison with a standard card, the main component of the sample after vulcanization was found to be CoS2And FeS2Corresponding to standard cards JCPDS41-1471 and JCPDS 42-1340 respectively. Indicating that CoFe-PBA is converted into nitrogen-doped carbon-loaded transition metal for vulcanization after ammonia etching and vulcanizationSubstance CoS2-FeS2The heterostructure is beneficial to regulation and control of an electronic structure, and the electrocatalytic performance of the catalyst is improved.
The electrocatalysis performance test adopts a saturated Ag/AgCl electrode as a reference electrode, a Pt electrode as a counter electrode, the sweep rate is 5mV/s, the electrolyte is 1M KOH, and the electrolyte needs to be subjected to N before the OER catalysis performance test2And (5) saturation treatment.
FIG. 3 depicts the CoS obtained in example 12-FeS2NC, FeS from comparative example 12NC and commercial RuO2The OER linear sweep voltammograms of the carbon cloths were modified separately. As can be seen from the figure, the current density reached 10mA/cm2Of CoS2-FeS2The presence of the/NC heterostructure has the lowest overpotential, indicating the transition metal sulfide CoS2-FeS2The existence of the catalyst plays a role in synergistically promoting the OER performance of the catalyst, further increases the active sites of the carbon material, improves the surface property of the catalyst, and ensures that CoS2-FeS2The electrochemical activity of the/NC is better than that of single-phase metal sulfide FeS2/NC。
FIG. 4 shows the CoS obtained in example 12-FeS2Comparative example 1 FeS/NC2NC NiS from comparative example 22-FeS2MnS-FeS obtained by/NC and comparative example 32OER linear sweep voltammogram of/NC modified carbon cloth. Considering transition metal cobalt sulfide and FeS2When the catalyst is matched as an OER catalyst, the performance is greatly improved, and other transition metal sulfides and FeS are examined2Catalytic performance in the formation of heterostructures, respectively synthesizing NiS2-FeS2(iii) NC and MnS-FeS2(ii)/NC sulfides of two transition metals Mn and Ni, as shown in FIG. 4, comparing four catalysts NiS2-FeS2/NC，MnS-FeS2/NC，CoS2-FeS2/NC，FeS2OER performance of/NC in 1M KOH solution environment, it can be seen that sulfide of transition metal Co still shows the best catalytic activity, and for NiS2-FeS2NC, when catalyzing OER, 10mA/cm is achieved2Current density of (1.47V vs. RHE, MnS-FeS)2instead,/NC shows worse catalytic performance.
FIG. 5 depicts the CoS obtained in example 12-FeS2OER stability test conducted on/NC modified carbon cloth. Catalyst CoS supported on carbon cloth2-FeS2and/NC, the catalytic performance is not obviously attenuated after a stability test for 25 h. After 1500 cycles of CV testing, the LSV curves almost coincide, indicating that the catalyst has excellent long-term stability.
FIG. 6 depicts the CoS obtained in example 12-FeS2NC, FeS from comparative example 12HER linear sweep voltammograms for the modified carbon cloths of/NC and commercial Pt/C, respectively. It can be seen that the current density reached 10mA/cm2Of CoS2-FeS2the/NC heterostructure has the lowest overpotential, indicating the transition metal sulfide CoS2-FeS2The existence of the catalyst plays a role in synergistically promoting the OER performance of the catalyst, further increases the active sites of the carbon material, improves the surface property of the catalyst, and ensures that CoS2-FeS2The electrochemical activity of the/NC is better than that of single-phase FeS2/NC。
FIG. 7 shows the CoS obtained in example 12-FeS2Comparative example 1 FeS/NC2NC NiS from comparative example 22-FeS2MnS-FeS obtained by/NC and comparative example 32HER linear sweep voltammogram of/NC modified carbon cloth. Further examination of NiS2-FeS2/NC，MnS-FeS2Catalytic activity of two materials,/NC on HER, as shown in FIG. 7, material NiS2-FeS2The NC reaches 10mA/cm2The current density of (A) is 327mV, obviously greater than CoS2-FeS2the/NC reaches the overpotential generated in the same case. MnS-FeS2The NC reaches 10mA/cm2The overpotential generated at the current density of (1) is 437mV compared with sulfide FeS of single-phase metallic Fe2Good performance of/NC.
FIG. 8 shows the CoS obtained in example 12-FeS2The graph shows that when the current density reaches 10mA/cm, the total water splitting linear scanning voltammetry curve of the carbon cloth modified by the NC non-noble metal electrocatalyst2When the target catalystThe required potential of which is significantly less than that of the noble metal RuO2Indicating CoS distributed at the edges of the cube2-FeS2Is beneficial to the direct contact of reactants or reaction intermediates and active sites, thereby improving the electrocatalytic performance.
FIG. 9 depicts the CoS obtained in example 12-FeS2A constant voltage i-t test chart when the/NC non-noble metal electrocatalyst modified carbon cloth is arranged at 1.61V. As can be seen from the figure, in the 16h test, CoS2-FeS2The performance of the/NC is only attenuated by 5.8%, the good long-term stability of the electrolyzed water is shown, the method has important significance in the application of new energy in the future, and has potential application value in the field of electrode materials of the electrolyzed water technology.
Claims (2)
1. The Prussian blue analogue derived metal sulfide/nitrogen-doped carbon electrocatalyst is characterized in that the catalyst takes a cobalt-iron Prussian blue analogue as a template, and CoS is obtained by ammonia etching and gas phase sulfidation2-FeS2A nitrogen-doped carbon catalyst; wherein the cobalt iron Prussian blue analogue is marked as CoFe-PBA, CoS2-FeS2N-doped carbon catalyst is described as CoS2-FeS2/NC；
The preparation method of the metal sulfide/nitrogen-doped carbon electrocatalyst derived based on the blue analogue is characterized by comprising the following specific steps of:
(a) preparation of CoFe-PBA
Weighing 870mg Co (NO)3)2·6H2Dissolving O and 1.32g of sodium citrate in 100mL of deionized water, and marking as a solution A; weighing 658mg of potassium ferricyanide and dissolving the potassium ferricyanide into another 100mL of deionized water, and marking as a solution B; adding the solution B into the solution A under the condition of stirring, stirring for three minutes, standing for 10 hours, centrifuging to collect a sample, washing with ionized water and absolute ethyl alcohol for three times respectively, and drying at 50 ℃ for 12 hours;
(b)CoS2-FeS2preparation of/NC
Dispersing 20mg Co-Fe PBA in 50mL ethanol, adding into 50mL 25% ammonia water solution, stirring for reaction for 10min, centrifuging to collect sample, and removing ionsWashing with water until the solution is nearly neutral, and drying at 60 ℃ for 24h to obtain a cobalt-iron nano-framework marked as CoFe-NFs; weighing 20mg of CoFe-NFs in a magnetic boat, placing the magnetic boat in the lower end of a tube furnace, weighing 200-400 mg of sulfur powder in the magnetic boat, placing the magnetic boat in the upper end of the tube furnace, heating to 200-500 ℃ at the speed of 2 ℃/min, and vulcanizing in a nitrogen atmosphere for 1-5 hours to obtain the catalyst CoS2-FeS2/NC；
The metal sulfide/nitrogen-doped carbon electrocatalyst is of a hollow nano cubic cage structure, elements are uniformly distributed on the edges of a cube, and the average particle size of nano cubic cage units of the catalyst is 100-200 nm; metal sulfide CoS2-FeS2The average grain diameter of the nano-particles is 5-30nm, and the nano-particles are uniformly embedded on the nitrogen-doped carbon nano-chip.
2. The prussian blue analog-derived metal sulfide/nitrogen-doped carbon electrocatalyst according to claim 1, characterized in that the catalyst is used for cathodic hydrogen evolution reaction and anodic oxygen evolution reaction of electrolyzed water.
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