CN113637986A - Double-phase nickel selenide double-function electrolytic water catalyst and preparation method and application thereof - Google Patents
Double-phase nickel selenide double-function electrolytic water catalyst and preparation method and application thereof Download PDFInfo
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- QHASIAZYSXZCGO-UHFFFAOYSA-N selanylidenenickel Chemical compound [Se]=[Ni] QHASIAZYSXZCGO-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 167
- 239000006260 foam Substances 0.000 claims abstract description 17
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 14
- 239000002135 nanosheet Substances 0.000 claims abstract description 9
- 239000002105 nanoparticle Substances 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 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
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- 239000011669 selenium Substances 0.000 claims description 122
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229910052573 porcelain Inorganic materials 0.000 claims description 14
- -1 polytetrafluoroethylene Polymers 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000011144 upstream manufacturing Methods 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000005868 electrolysis reaction Methods 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 4
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 238000010335 hydrothermal treatment Methods 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 230000007423 decrease Effects 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 230000005501 phase interface Effects 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000010411 electrocatalyst Substances 0.000 abstract description 17
- 238000000034 method Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 5
- 229910000510 noble metal Inorganic materials 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 230000033228 biological regulation Effects 0.000 abstract description 2
- 150000003346 selenoethers Chemical class 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 2
- 230000005540 biological transmission Effects 0.000 abstract 1
- 239000013078 crystal Substances 0.000 abstract 1
- 239000002086 nanomaterial Substances 0.000 abstract 1
- 238000001075 voltammogram Methods 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 230000007774 longterm Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 5
- 229910052711 selenium Inorganic materials 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 238000011056 performance test Methods 0.000 description 4
- 238000013112 stability test Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000002238 attenuated effect Effects 0.000 description 3
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- 230000008859 change Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
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- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000004615 ingredient Substances 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
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000002060 nanoflake Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000012353 t test Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003624 transition metals Chemical class 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
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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
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Abstract
A biphase nickel selenide bifunctional electrolytic water catalyst, a preparation method and application thereof. The invention prepares the non-noble metal selenide double-phase nano-structure composite electrocatalyst by a hydrothermal and gas-phase selenization method. The electrocatalyst has NiSe2/Ni3Se4Heterostructure of Ni3Se4Being nanosheets, NiSe2Ni3Se4The catalyst is nano-particles, the two-phase heterogeneous composite structure greatly improves the exposure of active sites of the catalyst, increases the specific surface area and improves the hydrogen evolution and oxygen evolution electrocatalytic activity of the catalyst in an alkaline medium; the electrochemical stability of the catalyst material is improved by selecting the foam nickel material; the synergistic effect between the two-phase heterostructure promotes the generation of more crystal faces, enhances the electrical conductivity, is beneficial to the transmission of electrons, and greatly improves the electrocatalytic performance of the material; the controllable regulation and control between two phases of the two-phase catalyst can realize the control ofFlexible adjustment of OER and HER performance.
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 biphase nickel selenide bifunctional electrolytic water catalyst; 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 of them suffer from slow kinetics and require advanced catalysts to promote the kinetics. At present, the noble metal electrode material RuO2And IrO2Has the best OER activity under alkaline conditions, and Pt/C is the best electrocatalyst for HER and ORR. Their scarcity and poor electrochemical stability have limited their widespread use as electrolytic water catalysts in energy storage and conversion systems. It is therefore of great importance to develop new efficient and inexpensive electrocatalysts. In recent years, the transition metals and the compounds such as carbide, sulfide, selenide, phosphide, oxide and hydroxide thereof have attracted the attention of researchers due to the advantages of abundant reserves, low cost, long-term durability, unique d-orbitals and the like, and provide more possibilities for the selection of the water electrolysis catalyst.
Nickel selenide is a novel transition metal sulfide, and has gained great attention in the field of electrocatalysis due to its high conductivity, low band gap, high chemical stability, and low cost. Nickel selenide to metal sulfide (363kJ mol)-1) And metal phosphide (322kJ mol)-1) Has lower hydrogen bond desorption energy (276kJ mol)-1) This makes them good candidates for HER electrocatalysts. On the other hand, nickel selenide also shows good OER catalytic ability due to the presence of local negative charges on the selenium sites. Some nickel selenide phases, e.g. Ni0.95Se、NiSe2、Ni3Se2And Ni3Se4Has good bifunctional catalytic activity on HER and OERAnd (4) sex. Although NiSe2And Ni3Se4Has HER and OER activity, but has not been related to biphasic NiSe so far2/Ni3Se4Preparation of the catalyst and reporting of catalytic performance.
The invention takes foam nickel as a substrate, and Ni (OH) growing on the nickel foam in situ is put in a tube furnace2Selenizing to prepare the biphase nickel selenide electrolytic water catalyst. By adjusting the initial quality of the selenium source, the phase composition and charge state (Ni) of the nickel selenide catalyst are controlled3+/Ni2+Relative molar ratio) and electrocatalytic properties. The two phases in the prepared two-phase catalyst have obvious shape difference, wherein NiSe2Present as nanoparticles, and Ni3Se4Is in the shape of nano-flake. The obtained NiSe2/Ni3Se4the/NF catalyst has rich interfaces, 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 heterogeneous heterostructure electrocatalysts and energy conversion and storage devices of transition metal selenides.
The invention content is as follows:
aiming at the defects of the prior art and the requirements of research and application in the field, one of the purposes of the invention is to provide a dual-function water electrolysis catalyst of two-phase nickel selenide; i.e. containing only NiSe2Phase and Ni3Se4Dual function electrolytic water catalyst of phase; the biphase nickel selenide bifunctional electrolytic water catalyst with phase proportion is not used in the preparation by adjusting the quality of the selenium source in the reaction process; wherein the biphase nickel selenide bifunctional electrolytic water catalyst is marked as NiSe2/Ni3Se4/NF。
The invention also aims to provide a preparation method of the double-phase nickel selenide double-function electrolytic water catalyst, which comprises the following steps:
(a)Ni(OH)2preparation of/NF
Three pieces of the sample are 2.5 multiplied by 4cm2Respectively carrying out ultrasonic treatment on the nickel foam for 30, 5 and 10min by using 3mol/L hydrochloric acid solution, deionized water and ethanol, and drying for 6h at 50 ℃; getImmersing a piece of nickel foam into a polytetrafluoroethylene high-pressure reaction kettle containing 35mL of dipotassium hydrogen phosphate solution with the concentration of 1mmol/L, carrying out hydrothermal treatment for 12h at 180 ℃, naturally cooling to room temperature, washing with deionized water, drying at 50 ℃ for 6h, putting the obtained green precursor nickel foam into a polytetrafluoroethylene high-pressure reaction kettle containing 30mL of potassium hydroxide solution with the concentration of 0.1mol/L, carrying out hydrothermal reaction for 5h at 120 ℃, washing with deionized water, and naturally drying at 50 ℃ overnight to obtain a light gray catalyst Ni (OH)2/NF；
(b)NiSe2/Ni3Se4Preparation of/NF
Mixing the Ni (OH) obtained in (a)2Placing the NF in the porcelain boat at the downstream of the tube furnace, placing the selenium powder with the mass of 0.1-0.5 g at the upstream of the tube furnace, and placing the NF in the porcelain boat at the N2Heating to 250-450 ℃ at a heating rate of 3 ℃/min in the atmosphere, then preserving heat until the selenium powder is completely sublimated, and cooling to room temperature to obtain the catalyst NiSe2/Ni3Se4/NF；
The prepared biphase nickel selenide bifunctional electrolytic water catalyst has the coexistence of the nano-sheet structure and the nano-particle structure, wherein the NiSe exists2Being nanoparticles of Ni3Se4Is a nano-sheet, and an obvious phase interface is arranged between the nano-sheet and the nano-sheet; with the increase of the quality of the selenium powder, the nano flaky Ni3Se4Gradually decreases in phase composition.
The invention also aims to provide the catalytic application of the double-phase nickel selenide double-function electrolytic water catalyst in the electrolytic water cathode HER and anode OER.
The invention prepares the bifunctional electrolytic water catalyst with excellent performance by adjusting the proportion of two phases in the two-phase nickel selenide; the two-phase 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 biphase nickel selenide bifunctional electrolytic water catalyst is a non-noble metal composite material, the used raw materials are easy to purchase, the resources are rich, the cost is low, the experimental method is easy to operate, and the large-scale production is facilitated;
2) the bifunctional electrolytic water catalyst is a two-phase nickel selenide material, has better OER and HER catalytic activities, and has obvious advantages compared with the unilateral OER or HER activity of a non-noble metal catalyst reported in the current research;
3) the biphase nickel selenide bifunctional electrolytic water catalyst has RuO (RuO) which is more commercial than that of the catalyst in the aspect of total water decomposition2Better electrochemical performance with Pt/C electrode.
Description of the drawings:
FIG. 1 shows Ni (OH) obtained in comparative example 12/NF (A), NiSe obtained in example 12/Ni3Se4NF-1(B), NiSe obtained in example 42/Ni3Se4SEM image of/NF-4 (C) and NiSe obtained in example 12/Ni3Se4NF-1(D) and NiSe obtained in example 42/Ni3Se4Transmission electron micrograph of/NF-4 (F).
FIG. 2 shows NiSe catalysts obtained in examples 1, 2, 3, 4 and 52/Ni3Se4/NF-1、NiSe2/Ni3Se4/NF-2、NiSe2/Ni3Se4/NF-3、NiSe2/Ni3Se4/NF-4、NiSe2/Ni3Se4XRD pattern (left) of/NF-5, and NiSe as catalyst obtained in example 1, example 2, example 3, example 4 and example 52/Ni3Se4/NF-1、NiSe2/Ni3Se4/NF-2、NiSe2/Ni3Se4/NF-3、NiSe2/Ni3Se4/NF-4、NiSe2/Ni3Se4Two phase ratio bar graph of/NF-5 (right).
FIG. 3 shows NiSe obtained in example 12/Ni3Se4NF-1, NiSe obtained in example 42/Ni3Se4/NF-4, Ni (OH) obtained in comparative example 12/NF and commercial RuO2OER linear sweep voltammogram for modified nickel foamFigure (a).
FIG. 4 shows NiSe obtained in example 12/Ni3Se4NF-1, NiSe obtained in example 22/Ni3Se4NF-2, NiSe obtained in example 32/Ni3Se4NF-3, NiSe obtained in example 42/Ni3Se4NF-4, NiSe obtained in example 52/Ni3Se4OER linear sweep voltammogram of/NF-5.
FIG. 5 shows NiSe obtained in example 12/Ni3Se4OER constant voltage i-t of/NF-1 (left) and linear sweep voltammogram before and after 2000 cycles of cyclic voltammetry of the test (right).
FIG. 6 shows NiSe obtained in example 12/Ni3Se4NF-1, NiSe obtained in example 42/Ni3Se4/NF-4, Ni (OH) obtained in comparative example 12HER linear sweep voltammogram of/NF and commercial Pt/C modified nickel foam.
FIG. 7 shows NiSe obtained in example 12/Ni3Se4NF-1, NiSe obtained in example 22/Ni3Se4NF-2, NiSe obtained in example 32/Ni3Se4NF-3, NiSe obtained in example 42/Ni3Se4NF-4, NiSe obtained in example 52/Ni3Se4HER linear sweep voltammogram of/NF-5. .
FIG. 8 shows NiSe obtained in example 42/Ni3Se4HER constant voltage i-t of/NF-4 (left) and linear sweep voltammogram before and after 2000 cycles of cyclic voltammogram (right).
FIG. 9 shows NiSe obtained in example 12/Ni3Se4/NF-1 as an anode, NiSe obtained in example 42/Ni3Se4the/NF-4 is a full-hydrolytic linear sweep voltammogram carried out by a two-electrode system consisting of a cathode.
FIG. 10 shows NiSe obtained in example 12/Ni3Se4/NF-1 as an anode, NiSe obtained in example 42/Ni3Se4The constant voltage i-t measurement of a two-electrode system consisting of a cathode and a NF-4 at 1.56VAn attempt is made.
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)Ni(OH)2preparation of/NF
Three pieces of the sample are 2.5 multiplied by 4cm2Respectively carrying out ultrasonic treatment on the nickel foam for 30, 5 and 10min by using 3mol/L hydrochloric acid solution, deionized water and ethanol, and drying for 6h at 50 ℃; soaking a piece of nickel foam into a polytetrafluoroethylene high-pressure reaction kettle containing 35mL of dipotassium hydrogen phosphate solution with the concentration of 1mmol/L, performing hydrothermal treatment for 12h at 180 ℃, naturally cooling to room temperature, washing with deionized water, drying at 50 ℃ for 6h, putting the obtained green precursor nickel foam into a polytetrafluoroethylene high-pressure reaction kettle containing 30mL of potassium hydroxide solution with the concentration of 0.1mol/L, performing hydrothermal reaction for 5h at 120 ℃, washing with deionized water, and naturally drying at 50 ℃ overnight to obtain a light gray catalyst Ni (OH)2/NF；
(b)NiSe2/Ni3Se4Preparation of/NF-1
Mixing the Ni (OH) obtained in (a)2Placing NF in porcelain boat at downstream of tube furnace, placing selenium powder with mass of 0.1g at upstream of tube furnace, and placing the powder in porcelain boat at N2Heating to 300 ℃ at a heating rate of 3 ℃/min, then preserving heat until the selenium powder is completely sublimated, and cooling to room temperature to obtain the catalyst NiSe2/Ni3Se4/NF-1；
Example 2:
(a)Ni(OH)2preparation of/NF
Prepared according to the method and conditions of step (a) in example 1;
(b)NiSe2/Ni3Se4preparation of/NF-2
Mixing the Ni (OH) obtained in (a)2Placing NF in porcelain boat at downstream of tube furnace, placing selenium powder with mass of 0.2g at upstream of tube furnace, and placing the powder in porcelain boat at N2Heating to 300 ℃ at a heating rate of 3 ℃/min in the atmosphere, and then preserving heat until the selenium powder is fullPartially sublimating, and cooling to room temperature to obtain the catalyst NiSe2/Ni3Se4/NF-2；
Example 3:
(a)Ni(OH)2preparation of/NF
Prepared according to the method and conditions of step (a) in example 1;
(b)NiSe2/Ni3Se4preparation of/NF-3
Mixing the Ni (OH) obtained in (a)2Placing NF in porcelain boat at downstream of tube furnace, placing selenium powder with mass of 0.3g at upstream of tube furnace, and placing the powder in porcelain boat at N2Heating to 300 ℃ at a heating rate of 3 ℃/min, then preserving heat until the selenium powder is completely sublimated, and cooling to room temperature to obtain the catalyst NiSe2/Ni3Se4/NF-3；
Example 4:
(a)Ni(OH)2preparation of/NF
Prepared according to the method and conditions of step (a) in example 1;
(b)NiSe2/Ni3Se4preparation of/NF-4
Mixing the Ni (OH) obtained in (a)2Placing NF in porcelain boat at downstream of tube furnace, placing selenium powder with mass of 0.4g at upstream of tube furnace, and placing the powder in porcelain boat at N2Heating to 300 ℃ at a heating rate of 3 ℃/min, then preserving heat until the selenium powder is completely sublimated, and cooling to room temperature to obtain the catalyst NiSe2/Ni3Se4/NF-4；
Example 5:
(a)Ni(OH)2preparation of/NF
Prepared according to the method and conditions of step (a) in example 1;
(b)NiSe2/Ni3Se4preparation of/NF-5
Mixing the Ni (OH) obtained in (a)2Placing NF in porcelain boat at downstream of tube furnace, placing selenium powder with mass of 0.5g at upstream of tube furnace, and placing the powder in porcelain boat at N2Heating to 300 ℃ at a heating rate of 3 ℃/min, then preserving heat until the selenium powder is completely sublimated, and cooling to room temperature to prepare the selenium-enriched powderObtaining the catalyst NiSe2/Ni3Se4/NF-5；
Comparative example 1:
(a) NF pretreatment
Cutting the nickel foam to 2.5X 4cm2The sheets of (a) were sonicated with 3mol/L hydrochloric acid solution, deionized water and ethanol for 30, 5 and 10min, respectively, to remove surface oxides and organic molecules, and then dried at 50 ℃ for 6 h.
(b)Ni(OH)2Preparation of/NF
Prepared according to the method and conditions of step (a) in example 1;
FIG. 1 shows Ni (OH) obtained in comparative example 12/NF (A), NiSe obtained in example 12/Ni3Se4NF-1(B), NiSe obtained in example 42/Ni3Se4SEM image of/NF-4 (C) and NiSe obtained in example 12/Ni3Se4NF-1(D) and NiSe obtained in example 42/Ni3Se4Transmission electron micrograph of/NF-4 (F).
As can be seen from FIG. A, Ni (OH)2Has obvious sheet structure and excellent crystallinity. As can be seen in FIG. B, the product NiSe after selenization2/Ni3Se4the/NF-1 sheet structure is more dense and has obvious Ni3Se4Structure, while less nano-particle NiSe can be observed on the frame2And (4) phase(s). In the graph C, the number of lamellar structures is significantly reduced, while the arrangement of smaller-sized nanoparticles is more significant. Both the graph D and the graph F can clearly show that the sheet structure and the particle structure exist simultaneously, which shows that the catalyst is a two-phase heterostructure after gas phase selenization and has a very obvious interface.
FIG. 2 shows NiSe catalysts obtained in examples 1, 2, 3, 4 and 52/Ni3Se4/NF-1、NiSe2/Ni3Se4/NF-2、NiSe2/Ni3Se4/NF-3、NiSe2/Ni3Se4/NF-4、NiSe2/Ni3Se4XRD pattern of/NF-5 (left), and implementationNiSe catalyst obtained in example 1, example 2, example 3, example 4 and example 52/Ni3Se4/NF-1、NiSe2/Ni3Se4/NF-2、NiSe2/Ni3Se4/NF-3、NiSe2/Ni3Se4/NF-4、NiSe2/Ni3Se4Two phase ratio bar graph of/NF-5 (right). Through comparison with a standard card, the main component of the selenized sample is NiSe2And Ni3Se4Corresponding to standard cards JCPDS 88-1711 and 89-7162 respectively. The selenized structure is a heterogeneous structure of two-phase nickel selenide, and the structure is beneficial to regulation and control of an electronic structure and improves the electrocatalytic performance of the catalyst. Meanwhile, due to the different mass of the selenium powder participating in the reaction, the proportion of two phases in the generated two-phase catalyst is different, and it can be seen from the histogram that NiSe is added with the mass of the selenium powder2The proportion of the phase increases, corresponding to Ni3Se4The ratio of the phases is reduced. The difference in the proportions of the two phases will contribute to the difference in performance of OER and HER over the two-phase catalyst.
The electrocatalysis performance test takes a saturated Ag/AgCl electrode as a reference electrode, a stone grinding rod electrode as a counter electrode, the sweeping speed is 2mV/s, and the electrolyte is 1M KOH.
FIG. 3 shows NiSe obtained in example 12/Ni3Se4NF-1, NiSe obtained in example 42/Ni3Se4/NF-4, Ni (OH) obtained in comparative example 12/NF and commercial RuO2OER linear sweep voltammogram of modified nickel foam. As can be seen from the figure, the current density reached 100mA/cm2Then, NiSe2/Ni3Se4the/NF-1 catalyst had the lowest overpotential, indicating that the transition metal selenide NiSe2And Ni3Se4The presence of the catalyst has a synergistic promotion effect on the OER performance of the catalyst, promotes the migration of electrons, improves the surface property of the catalyst and improves the catalytic performance.
FIG. 4 shows NiSe obtained in example 12/Ni3Se4NF-1, NiSe obtained in example 22/Ni3Se4NF-2, example 3NiSe2/Ni3Se4NF-3, NiSe obtained in example 42/Ni3Se4NF-4, NiSe obtained in example 52/Ni3Se4OER linear sweep voltammogram of/NF-5. Due to Ni3Se4The OER activity of (A) is higher than that of NiSe2To investigate NiSe2And Ni3Se4The results of OER performance tests on the two-phase nickel selenide electrocatalyst with different phase ratios show that when Ni is different from the nickel selenide electrocatalyst with different phase ratios, the results show that the performance of the nickel selenide electrocatalyst with different phase ratios is improved3Se4When the component is higher, the catalyst has more excellent OER performance, namely NiSe2/Ni3Se4NF-1 has optimum OER performance, NiSe2/Ni3Se4NF-2 times with Ni3Se4The ingredients are reduced and the OER performance is successively weakened until no further change occurs with the phase ratio.
FIG. 5 shows NiSe obtained in example 12/Ni3Se4OER stability test of/NF-1. Biphase nickel selenide electrocatalyst NiSe2/Ni3Se4the/NF-1 undergoes an OER stability test for 60h, and the catalytic performance is not obviously attenuated. After 2000 cycles of CV test, there was also little change in the LSV curve, indicating excellent long-term stability of the catalyst.
FIG. 6 shows NiSe obtained in example 12/Ni3Se4NF-1, NiSe obtained in example 42/Ni3Se4/NF-4, Ni (OH) obtained in comparative example 12HER linear sweep voltammogram of/NF and commercial Pt/C modified nickel foam. As can be seen from the figure, the current density reached 10mA/cm2Or even 100mA/cm2Then, NiSe2/Ni3Se4the/NF-4 catalysts all had the lowest overpotential, indicating that the transition metal selenide NiSe2And Ni3Se4The existence of the catalyst plays a role in synergistically promoting the HER performance of the catalyst, promotes the migration of electrons, improves the surface property of the catalyst and improves the catalytic performance.
FIG. 7 shows NiSe obtained in example 12/Ni3Se4NF-1, NiSe obtained in example 22/Ni3Se4NF-2, NiSe obtained in example 32/Ni3Se4NF-3, NiSe obtained in example 42/Ni3Se4NF-4, NiSe obtained in example 52/Ni3Se4HER linear sweep voltammogram of/NF-5. Due to NiSe2Has HER activity higher than that of Ni3Se4To investigate NiSe2And Ni3Se4The results of HER performance tests on the biphasic nickel selenide electrocatalyst with different phase ratios show that the results of the HER performance tests on the biphasic nickel selenide electrocatalyst with different phase ratios show that the NiSe is not influenced by different phase ratios2At higher composition, the catalyst has more excellent HER performance, namely NiSe2/Ni3Se4NF-4 has optimum HER performance, NiSe2/Ni3Se4NF-5 times, with NiSe2With reduced composition, HER performance is in turn diminished.
FIG. 8 shows NiSe obtained in example 42/Ni3Se4HER stability test of/NF-4. Biphase nickel selenide electrocatalyst NiSe2/Ni3Se4the/NF-4 undergoes a stability test for 60h, and the HER catalytic performance is not obviously attenuated. After 2000 cycles of CV test, there was also little change in the LSV curve, indicating that the catalyst had excellent HER long-term stability.
FIG. 9 shows NiSe obtained in example 12/Ni3Se4/NF-1 as an anode, NiSe obtained in example 42/Ni3Se4the/NF-4 is a full-hydrolytic linear sweep voltammogram carried out by a two-electrode system consisting of a cathode. As can be seen from the figure, when the current density reached 10mA/cm2The required potential of the target catalyst is significantly less than that of the noble metal RuO2(+) | | Pt/C (-), shows that the synergistic effect between the heterogeneous structures of the two-phase nickel selenide electrocatalyst generates rich interfaces, promotes the transfer of electrons, and thus improves the electrocatalytic performance.
FIG. 10 shows NiSe obtained in example 12/Ni3Se4/NF-1 as an anode, NiSe obtained in example 42/Ni3Se4the/NF-4 is a constant voltage i-t test chart when the cathode forms a two-electrode system and the voltage is 1.56V. Can be seen from the figureIn a 36-hour test, the performance of the biphase nickel selenide electrocatalyst is hardly attenuated, good long-term stability of electrolyzed water is shown, the application of the biphase nickel selenide electrocatalyst in the aspect of new energy in the future is of great significance, and the biphase nickel selenide electrocatalyst has potential application value in the field of electrode materials of an electrolyzed water technology.
Claims (2)
1. The biphase nickel selenide bifunctional electrolytic water catalyst is characterized in that the catalyst simultaneously contains NiSe2Phase and Ni3Se4Phase (1); the catalyst is prepared by adjusting the proportion of two phases in the catalyst by changing the quality of selenium powder; the biphase bifunctional water electrolysis catalyst grows on the foam nickel in situ and is marked as NiSe2/Ni3Se4/NF；
The preparation method of the biphase nickel selenide bifunctional electrolytic water catalyst is characterized by comprising the following specific steps:
(a)Ni(OH)2preparation of/NF
Three pieces of the sample are 2.5 multiplied by 4cm2Respectively carrying out ultrasonic treatment on the nickel foam for 30, 5 and 10min by using 3mol/L hydrochloric acid solution, deionized water and ethanol, and drying for 6h at 50 ℃; soaking a piece of nickel foam into a polytetrafluoroethylene high-pressure reaction kettle containing 35mL of dipotassium hydrogen phosphate solution with the concentration of 1mmol/L, performing hydrothermal treatment for 12h at 180 ℃, naturally cooling to room temperature, washing with deionized water, drying at 50 ℃ for 6h, putting the obtained green precursor nickel foam into a polytetrafluoroethylene high-pressure reaction kettle containing 30mL of potassium hydroxide solution with the concentration of 0.1mol/L, performing hydrothermal reaction for 5h at 120 ℃, washing with deionized water, and naturally drying at 50 ℃ overnight to obtain a light gray catalyst Ni (OH)2/NF；
(b)NiSe2/Ni3Se4Preparation of/NF
Mixing the Ni (OH) obtained in (a)2Placing the NF in the porcelain boat at the downstream of the tube furnace, placing the selenium powder with the mass of 0.1-0.5 g at the upstream of the tube furnace, and placing the NF in the porcelain boat at the N2Heating to 250-450 ℃ at a heating rate of 3 ℃/min in the atmosphere, then preserving heat until the selenium powder is completely sublimated, and cooling to room temperature to obtain the catalyst NiSe2/Ni3Se4/NF；
The prepared biphase nickel selenide bifunctional electrolytic water catalyst has the coexistence of the nano-sheet structure and the nano-particle structure, wherein the NiSe exists2Being nanoparticles of Ni3Se4Is a nano-sheet, and an obvious phase interface is arranged between the nano-sheet and the nano-sheet; with the increase of the quality of the selenium powder, the nano flaky Ni3Se4Gradually decreases in phase composition.
2. The dual-function bi-phase nickel selenide catalyst for water electrolysis according to claim 1, wherein the catalyst is used for hydrogen evolution reaction at the cathode and oxygen evolution reaction at the anode of water electrolysis.
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