CN113637986B - Biphase nickel selenide double-function electrolytic water catalyst, preparation method and application thereof - Google Patents
Biphase nickel selenide double-function electrolytic water catalyst, preparation method and application thereof Download PDFInfo
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 20
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- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 4
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 4
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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
-
- 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 biphase nickel selenide double-function 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 NiSe 2 /Ni 3 Se 4 Hetero-structure of Ni 3 Se 4 Being nanosheets, niSe 2 Ni 3 Se 4 The 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 flexible regulation of OER and HER performances.
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 Oxygen Evolution Reaction (OER) are electrolytic waterThe key electrode process of the technology, but both of these processes have the problem of slow kinetics, and both require advanced catalysts to promote their kinetics. At present, the noble metal electrode material RuO 2 And IrO 2 Has 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, transition metals and compounds such as carbides, sulfides, selenides, phosphides, oxides, hydroxides and the like thereof have attracted general 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 selection of electrolytic water catalysts.
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 (363 kJ mol) -1 ) And metal phosphide (322 kJ mol) -1 ) Has lower hydrogen bond desorption energy (276 kJ 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. Ni 0.95 Se、NiSe 2 、Ni 3 Se 2 And Ni 3 Se 4 Has good bifunctional catalytic activity to HER and OER. Although NiSe 2 And Ni 3 Se 4 Has HER and OER activity, but has not been related to biphasic NiSe so far 2 /Ni 3 Se 4 Preparation 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 grown in a tube furnace 2 Selenizing 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 controlled 3+ /Ni 2+ Relative molar ratio) and electrocatalytic properties. Prepared biphasic catalysisThe two phases in the agent have obvious shape difference, wherein NiSe 2 Present as nanoparticles, and Ni 3 Se 4 Is in the shape of nano-flake. The obtained NiSe 2 /Ni 3 Se 4 the/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 NiSe 2 Phase and Ni 3 Se 4 Dual 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 NiSe 2 /Ni 3 Se 4 /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) 2 preparation of/NF
Three pieces of the sample are 2.5 multiplied by 4cm 2 Respectively 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)NiSe 2 /Ni 3 Se 4 Preparation of/NF
Mixing the Ni (OH) obtained in (a) 2 Placing 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 N 2 Heating 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 NiSe 2 /Ni 3 Se 4 /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 exists 2 Being nanoparticles of Ni 3 Se 4 Is a nano-sheet, and a clear 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 Ni 3 Se 4 Gradually decreases in phase composition.
The invention also aims to provide the catalytic application of the dual-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 decomposition 2 Better electrochemical performance with Pt/C electrode.
Description of the drawings:
FIG. 1 shows Ni (OH) obtained in comparative example 1 2 NF (A), niSe obtained in example 1 2 /Ni 3 Se 4 NF-1 (B), niSe obtained in example 4 2 /Ni 3 Se 4 SEM image of/NF-4 (C) and NiSe obtained in example 1 2 /Ni 3 Se 4 NF-1 (D) and NiSe obtained in example 4 2 /Ni 3 Se 4 Transmission electron micrograph of/NF-4 (F).
FIG. 2 shows NiSe catalysts obtained in examples 1, 2, 3, 4 and 5 2 /Ni 3 Se 4 /NF-1、NiSe 2 /Ni 3 Se 4 /NF-2、NiSe 2 /Ni 3 Se 4 /NF-3、NiSe 2 /Ni 3 Se 4 /NF-4、NiSe 2 /Ni 3 Se 4 XRD pattern (left) of/NF-5, and NiSe as catalyst obtained in example 1, example 2, example 3, example 4 and example 5 2 /Ni 3 Se 4 /NF-1、NiSe 2 /Ni 3 Se 4 /NF-2、NiSe 2 /Ni 3 Se 4 /NF-3、NiSe 2 /Ni 3 Se 4 /NF-4、NiSe 2 /Ni 3 Se 4 Two phase ratio bar graph of/NF-5 (right).
FIG. 3 shows NiSe obtained in example 1 2 /Ni 3 Se 4 NF-1, niSe obtained in example 4 2 /Ni 3 Se 4 /NF-4, comparative example 1 Ni (OH) 2 /NF and commercial RuO 2 OER linear sweep voltammogram of modified nickel foam.
FIG. 4 shows NiSe obtained in example 1 2 /Ni 3 Se 4 NF-1, niSe obtained in example 2 2 /Ni 3 Se 4 NF-2, niSe obtained in example 3 2 /Ni 3 Se 4 NF-3, niSe obtained in example 4 2 /Ni 3 Se 4 NF-4, niSe obtained in example 5 2 /Ni 3 Se 4 OER linear sweep voltammogram of/NF-5.
FIG. 5 shows NiSe obtained in example 1 2 /Ni 3 Se 4 OER constant voltage i-t of/NF-1 and test 2000 cycles of cyclic voltsLinear sweep voltammogram before and after ampere (right).
FIG. 6 shows NiSe obtained in example 1 2 /Ni 3 Se 4 /NF-1, niSe obtained in example 4 2 /Ni 3 Se 4 /NF-4, comparative example 1 Ni (OH) 2 HER linear sweep voltammogram of/NF and commercial Pt/C modified nickel foam.
FIG. 7 shows NiSe obtained in example 1 2 /Ni 3 Se 4 /NF-1, niSe obtained in example 2 2 /Ni 3 Se 4 /NF-2, niSe obtained in example 3 2 /Ni 3 Se 4 NF-3, niSe obtained in example 4 2 /Ni 3 Se 4 NF-4, niSe obtained in example 5 2 /Ni 3 Se 4 HER linear sweep voltammogram of/NF-5. .
FIG. 8 shows NiSe obtained in example 4 2 /Ni 3 Se 4 HER 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 1 2 /Ni 3 Se 4 /NF-1 as an anode, niSe obtained in example 4 2 /Ni 3 Se 4 the/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 1 2 /Ni 3 Se 4 /NF-1 as an anode, niSe obtained in example 4 2 /Ni 3 Se 4 the/NF-4 is a constant voltage i-t test chart when the cathode forms a two-electrode system and the voltage is 1.56V.
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) 2 preparation of/NF
Three pieces of the sample are 2.5 multiplied by 4cm 2 Respectively 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 in a solution containing 35ml of nickel with a concentration of 1mmPerforming hydrothermal treatment on an ol/L dipotassium hydrogen phosphate solution in a polytetrafluoroethylene high-pressure reaction kettle at 180 ℃ for 12h, naturally cooling to room temperature, washing with deionized water, drying at 50 ℃ for 6h, putting the obtained green precursor foamed nickel into the polytetrafluoroethylene high-pressure reaction kettle containing 30mL of a 0.1mol/L potassium hydroxide aqueous solution, 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)NiSe 2 /Ni 3 Se 4 Preparation of/NF-1
Mixing the Ni (OH) obtained in (a) 2 /NF was placed downstream of the tube furnace in the porcelain boat, selenium powder of 0.1g mass was placed upstream of the tube furnace, in N 2 Heating to 300 ℃ 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 NiSe 2 /Ni 3 Se 4 /NF-1；
Example 2:
(a)Ni(OH) 2 preparation of/NF
Prepared according to the method and conditions of step (a) in example 1;
(b)NiSe 2 /Ni 3 Se 4 preparation of/NF-2
Mixing the Ni (OH) obtained in (a) 2 Placing 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 N 2 Heating 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 NiSe 2 /Ni 3 Se 4 /NF-2；
Example 3:
(a)Ni(OH) 2 preparation of/NF
Prepared according to the method and conditions of step (a) in example 1;
(b)NiSe 2 /Ni 3 Se 4 preparation of/NF-3
Mixing the Ni (OH) obtained in (a) 2 /NF was placed in a porcelain boat at the downstream of the tube furnace, and selenium powder of 0.3g mass was placed at the upstream of the tube furnaceN 2 Heating 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 NiSe 2 /Ni 3 Se 4 /NF-3；
Example 4:
(a)Ni(OH) 2 preparation of/NF
Prepared according to the method and conditions of step (a) in example 1;
(b)NiSe 2 /Ni 3 Se 4 preparation of/NF-4
Mixing the Ni (OH) obtained in (a) 2 Placing 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 N 2 Heating to 300 ℃ 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 NiSe 2 /Ni 3 Se 4 /NF-4；
Example 5:
(a)Ni(OH) 2 preparation of/NF
Prepared according to the method and conditions of step (a) in example 1;
(b)NiSe 2 /Ni 3 Se 4 preparation of/NF-5
Mixing the Ni (OH) obtained in (a) 2 Placing 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 N 2 Heating 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 NiSe 2 /Ni 3 Se 4 /NF-5；
Comparative example 1:
(a) NF pretreatment
Cutting the nickel foam to 2.5X 4cm 2 The 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 6h.
(b)Ni(OH) 2 Preparation of/NF
Prepared according to the method and conditions of step (a) in example 1;
FIG. 1 shows Ni (OH) obtained in comparative example 1 2 NF (A), niSe obtained in example 1 2 /Ni 3 Se 4 NF-1 (B), niSe obtained in example 4 2 /Ni 3 Se 4 SEM image of/NF-4 (C) and NiSe obtained in example 1 2 /Ni 3 Se 4 NF-1 (D) and NiSe obtained in example 4 2 /Ni 3 Se 4 Transmission electron micrograph of/NF-4 (F).
As can be seen from FIG. A, ni (OH) 2 Has obvious sheet structure and good crystallinity. As can be seen in FIG. B, the product NiSe after selenization 2 /Ni 3 Se 4 the/NF-1 has denser lamellar structure and obvious Ni 3 Se 4 Structure, while less nano-particle NiSe can be observed on the frame 2 And (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 5 2 /Ni 3 Se 4 /NF-1、NiSe 2 /Ni 3 Se 4 /NF-2、NiSe 2 /Ni 3 Se 4 /NF-3、NiSe 2 /Ni 3 Se 4 /NF-4、NiSe 2 /Ni 3 Se 4 XRD pattern (left) of/NF-5, and NiSe catalyst obtained in example 1, example 2, example 3, example 4 and example 5 2 /Ni 3 Se 4 /NF-1、NiSe 2 /Ni 3 Se 4 /NF-2、NiSe 2 /Ni 3 Se 4 /NF-3、NiSe 2 /Ni 3 Se 4 /NF-4、NiSe 2 /Ni 3 Se 4 Two phase ratio bar graph of/NF-5 (right). Through comparison with a standard card, the main component of the selenized sample is NiSe 2 And Ni 3 Se 4 Corresponding to standard cards JCPDS 88-1711 and 89-7162 respectively. Indicating that the structure is two-phase nickel selenide after selenizationThe heterostructure is beneficial to the 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 powder 2 The proportion of the phase increases, corresponding to Ni 3 Se 4 The 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 1 2 /Ni 3 Se 4 /NF-1, niSe obtained in example 4 2 /Ni 3 Se 4 /NF-4, comparative example 1 Ni (OH) 2 /NF and commercial RuO 2 OER linear sweep voltammogram of modified nickel foam. As can be seen from the figure, the current density reached 100mA/cm 2 Then, niSe 2 /Ni 3 Se 4 the/NF-1 catalyst had the lowest overpotential, indicating that the transition metal selenide NiSe 2 And Ni 3 Se 4 The 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 1 2 /Ni 3 Se 4 NF-1, niSe obtained in example 2 2 /Ni 3 Se 4 NF-2, niSe obtained in example 3 2 /Ni 3 Se 4 /NF-3, niSe obtained in example 4 2 /Ni 3 Se 4 NF-4, niSe obtained in example 5 2 /Ni 3 Se 4 OER linear sweep voltammogram of/NF-5. Due to Ni 3 Se 4 The OER activity of (A) is higher than that of NiSe 2 To investigate NiSe 2 And Ni 3 Se 4 The 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 improved 3 Se 4 When the component is higher, the catalyst has more excellent OER performance,namely NiSe 2 /Ni 3 Se 4 NF-1 has optimum OER performance, niSe 2 /Ni 3 Se 4 NF-2 times with Ni 3 Se 4 The 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 1 2 /Ni 3 Se 4 OER stability test of/NF-1. Biphase nickel selenide electrocatalyst NiSe 2 /Ni 3 Se 4 the/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 1 2 /Ni 3 Se 4 NF-1, niSe obtained in example 4 2 /Ni 3 Se 4 /NF-4, comparative example 1 Ni (OH) 2 HER linear sweep voltammogram of/NF and commercial Pt/C modified nickel foam. As can be seen from the figure, the current density reached 10mA/cm 2 Or even 100mA/cm 2 Then, niSe 2 /Ni 3 Se 4 the/NF-4 catalysts all had the lowest overpotential, indicating that the transition metal selenide NiSe 2 And Ni 3 Se 4 The 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 1 2 /Ni 3 Se 4 NF-1, niSe obtained in example 2 2 /Ni 3 Se 4 NF-2, niSe obtained in example 3 2 /Ni 3 Se 4 NF-3, niSe obtained in example 4 2 /Ni 3 Se 4 NF-4, niSe obtained in example 5 2 /Ni 3 Se 4 HER linear sweep voltammogram of/NF-5. Due to NiSe 2 Has HER activity higher than that of Ni 3 Se 4 To investigate NiSe 2 And Ni 3 Se 4 The 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 ratios 2 When the composition is higherThe catalyst has more excellent HER performance, namely NiSe 2 /Ni 3 Se 4 NF-4 has optimum HER performance, niSe 2 /Ni 3 Se 4 NF-5 times, with NiSe 2 With reduced composition, HER performance is in turn diminished.
FIG. 8 shows NiSe obtained in example 4 2 /Ni 3 Se 4 HER stability test of/NF-4. Biphase nickel selenide electrocatalyst NiSe 2 /Ni 3 Se 4 the/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 1 2 /Ni 3 Se 4 /NF-1 as an anode, niSe obtained in example 4 2 /Ni 3 Se 4 the/NF-4 is a full-hydrolytic linear sweep voltammogram of a two-electrode system consisting of a cathode. As can be seen from the figure, when the current density reached 10mA/cm 2 The required potential of the target catalyst is significantly less than that of the noble metal RuO 2 (+) | | 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 1 2 /Ni 3 Se 4 /NF-1 as an anode, niSe obtained in example 4 2 /Ni 3 Se 4 the/NF-4 is a constant voltage i-t test chart when the cathode forms a two-electrode system and the voltage is 1.56V. As can be seen from the figure, in a 36-hour test, the performance of the dual-phase nickel selenide electrocatalyst is hardly attenuated, the good long-term stability of the electrolyzed water is shown, the application of the dual-phase nickel selenide electrocatalyst in the aspect of new energy in the future is of great significance, and the dual-phase nickel selenide electrocatalyst has potential application value in the field of electrode materials of the electrolyzed water technology.
Claims (2)
1. The biphase nickel selenide bifunctional electrolytic water catalyst is characterized in that the catalyst simultaneously contains NiSe 2 Phase and Ni 3 Se 4 Phase (1); the catalyst is prepared by changing the quality of selenium powder in the catalystThe ratio of the two phases; the biphase bifunctional water electrolysis catalyst grows on the foam nickel in situ and is marked as NiSe 2 /Ni 3 Se 4 /NF；
The preparation method of the biphase nickel selenide bifunctional electrolytic water catalyst is characterized by comprising the following specific steps:
(a) Ni(OH) 2 preparation of/NF
A slice of the standard is 2.5 multiplied by 4cm 2 The nickel foam is respectively treated with 3mol/L hydrochloric acid solution, deionized water and ethanol for 30, 5 and 10min by ultrasonic treatment, and dried at 50 ℃ for 6h; immersing the nickel foam into a polytetrafluoroethylene high-pressure reaction kettle containing dipotassium hydrogen phosphate solution with 35ml concentration of 1mmol/L, carrying out hydrothermal treatment on 12h at 180 ℃, naturally cooling to room temperature, washing with deionized water, drying 6h at 50 ℃, putting the obtained green precursor nickel foam into the polytetrafluoroethylene high-pressure reaction kettle containing potassium hydroxide aqueous solution with 30mL concentration of 0.1mol/L, carrying out hydrothermal reaction at 120 ℃ for 5h, washing with deionized water, and naturally drying at 50 ℃ for one night to obtain light gray catalyst Ni (OH) 2 /NF；
(b) NiSe 2 /Ni 3 Se 4 Preparation of/NF
Mixing Ni (OH) obtained in (a) 2 Placing the NF in a porcelain boat at the downstream of a tube furnace, placing selenium powder with the mass of 0.1 to 0.5g at the upstream of the tube furnace, and placing the NF in a porcelain boat at the N 2 Heating to 250-450 ℃ at a heating rate of 3 ℃/min in the atmosphere of (A), then preserving heat until the selenium powder is completely sublimated, and cooling to room temperature to obtain the catalyst NiSe 2 /Ni 3 Se 4 /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 exists 2 Being nanoparticles of Ni 3 Se 4 Is 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 Ni 3 Se 4 Gradually 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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