CN115505958A - Foam metal loaded bi-spinel type oxide CuCo 2 O 4 -Co 3 O 4 Preparation and application of derivatives thereof - Google Patents
Foam metal loaded bi-spinel type oxide CuCo 2 O 4 -Co 3 O 4 Preparation and application of derivatives thereof Download PDFInfo
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- 229910020599 Co 3 O 4 Inorganic materials 0.000 title claims abstract description 60
- 229910016507 CuCo Inorganic materials 0.000 title claims abstract description 60
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 21
- 239000002184 metal Substances 0.000 title claims abstract description 21
- 239000011029 spinel Substances 0.000 title claims abstract description 17
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000002070 nanowire Substances 0.000 claims abstract description 21
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000137 annealing Methods 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 3
- 230000003647 oxidation Effects 0.000 claims abstract description 3
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 98
- 229910052759 nickel Inorganic materials 0.000 claims description 49
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- 238000010438 heat treatment Methods 0.000 claims description 22
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 229940011182 cobalt acetate Drugs 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 4
- 229940044175 cobalt sulfate Drugs 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
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- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 244000189548 Chrysanthemum x morifolium Species 0.000 claims 1
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- 229910021641 deionized water Inorganic materials 0.000 description 25
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- 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 2
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- 229910002480 Cu-O Inorganic materials 0.000 description 1
- 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 1
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Images
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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
-
- 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
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
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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
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
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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
The invention provides a foam metal loaded bi-spinel type oxide CuCo 2 O 4 ‑Co 3 O 4 And the preparation and application of the derivative thereof. Firstly, preparing Co (OH) on a foam metal substrate by adopting a one-step hydrothermal method 2 Nanowire to obtain Co (OH) 2 a/MF; then hydrothermal reaction is carried out on Co (OH) 2 CuCo layered double hydroxide grows on the surface of the nanowire to obtain CuCo LDH-Co (OH) 2 /MF; then adopting a low-temperature oxidation method to carry out the reaction on CuCo LDH-Co (OH) in the air 2 performing/MF annealing to finally obtain three-dimensional chrysanthemum-shaped CuCo 2 O 4 ‑Co 3 O 4 and/MF. According to the invention, through the design and regulation of the carrier-active component, a three-dimensional chrysanthemum-shaped structure formed by one-dimensional nanowires is formed, each nanowire is mutually connected and mutually contacted, and the unique structure provides more active sites, so that oxygen is easier to discharge. In addition, the mutual staggering of crystal lattices changes the electronic structure in the material, and the inherent activity of the electrocatalyst is improved; co having spinel structure 3 O 4 Middle, octahedral site Co III Co-O is formed as an active site of OER, and the electrocatalytic performance is enhanced.
Description
Technical Field
The invention relates to the technical field of nano composite materials, in particular to a foam metal loaded bi-spinel oxide CuCo 2 O 4 -Co 3 O 4 And the preparation and application of the derivative thereof.
Background
The excessive use and rapid depletion of fossil energy such as coal, oil, and natural gas have caused global warming and other environmental problems, and thus the development of sustainable and environmentally friendly energy is imperative. The hydrogen energy has high efficiency and zero CO 2 The advantages of emissions are considered to be the most promising renewable energy source, however the low efficiency of hydrogen production from electrolysis of water makes efficient and clean hydrogen production technology still a challenge. In general, the electrocatalyst that works best for the OER reaction in alkaline electrolytes is RuO 2 And IrO 2 The high cost and low abundance on earth of noble metal-based oxides hinders their application and industrialization. Therefore, it is important to develop an electrocatalyst that is efficient, inexpensive, and has high stability.
Researches find that the transition metal and the derivatives thereof have high catalytic activity while being low in price, and are very suitable to be used as substitutes of noble metal catalysts. AB composed of 3d transition metals 2 O 4 The spinel oxide (A, B = transition metal) has good electrochemical activity, oxygen is arranged according to cubic close packing in the crystal structure of the spinel oxide, divalent metal cations are filled in one eighth of tetrahedral voids, and trivalent metal cationsThe cations fill in one-half of the octahedral voids, the remaining unoccupied interstitial spaces tend to open the spinel structure to accommodate the migration of the cations, and the mixed valency of the metal cations also helps provide donor-acceptor sites for oxygen adsorption, thereby facilitating the water electrolysis reaction. That is, the introduction of other atoms into the crystal lattice can greatly affect the electronic structure of the original catalyst, thereby enhancing the inherent activity and conductivity of the catalyst.
Besides, there is a more specific spinel oxide Co 3 O 4 . Co is a large storage, low cost and efficient oxygen evolution in alkaline solutions 3 O 4 Spinel type oxides are considered to be one of the best OER catalysts. It is generally believed that the 3d empty or semi-empty orbitals of Co can interact with pi electrons of oxygen and reduce the adsorption energy of O, HO and HO in the center of the 3d band, while the introduction of other atoms can improve the oxygen evolution performance of the cobalt-based catalyst, promote the breaking of Co-O bonds and the formation of O-O bonds, to increase the electrical conductivity of the material and accelerate proton transport. Since the Cu-based compound has a structure corresponding to O 2 Similar bionic chemical action makes the Cu-based electrocatalyst attract much attention, and the introduction of Cu into the Co-based electrocatalyst can change not only the environment around the 3d orbit and 3d electron of Co, but also increase the adsorption energy of water and change the Gibbs free energy of adsorption intermediates, thereby improving the catalytic activity of the catalyst.
Disclosure of Invention
The invention aims to provide a foamed metal loaded bi-spinel type oxide CuCo 2 O 4 -Co 3 O 4 And derivatives thereof, comprising the steps of: (a) Preparation of Co (OH) on a Metal Foam (MF) substrate 2 Nanowire to obtain (Co (OH) 2 /MF: (b) In order (Co (OH) 2 /MF as starting material, in Co (OH) 2 Preparing CuCo layered double hydroxide on the nano-wire to obtain CuCo LDH-Co (OH) 2 /MF; (c) Mixing CuCo LDH-Co (OH) 2 the/MF is put in an oxygen-containing atmosphere for heat treatment to obtain three-dimensional chrysanthemum-shaped CuCo 2 O 4 -Co 3 O 4 /MF。
Further, step (a) is a one-step hydrothermal process for preparing (Co (OH) 2 The specific process is as follows: mixing cobalt salt and urea (CH) 4 N 2 O)、NH 4 F. Dissolving polyvinylpyrrolidone (PVP) in water, adding foam metal, sealing, heating for hydrothermal reaction, and performing solid-liquid separation, washing and drying.
Further, the cobalt salt in the step (a) is one of cobalt sulfate, cobalt chloride, cobalt nitrate and cobalt acetate, the foam metal is one of foam nickel, foam copper, foam silver and foam cobalt, cobalt salt, urea and NH 4 The molar ratio of F to PVP is 1-6.
Further, step (b) is to prepare CuCo LDH-Co (OH) by a hydrothermal method 2 The specific process is as follows: dissolving copper salt, cobalt salt and urea in water, and adding Co (OH) prepared in the step (a) 2 and/MF, sealing, heating for hydrothermal reaction, and finally performing solid-liquid separation, washing and drying.
Further, the copper salt in the step (b) is one of copper sulfate, copper acetate, copper chloride and copper nitrate, the cobalt salt is one of cobalt sulfate, cobalt chloride, cobalt nitrate and cobalt acetate, the molar ratio of the copper salt to the cobalt salt to urea is 1-3.
Further, the step (c) adopts a low-temperature oxidation method to prepare the three-dimensional chrysanthemum-shaped CuCo 2 O 4 -Co 3 O 4 The specific process is as follows: in an oxygen-containing atmosphere, cuCo LDH-Co (OH) 2 Heating by/MF to perform annealing treatment, and finally cooling to room temperature.
Further, the oxygen-containing atmosphere is one of air atmosphere and pure oxygen atmosphere, the heating and cooling rates in the annealing process are both 3-8 ℃/min, the annealing temperature is 300-800 ℃, and the heat preservation time is 1-7h.
It is another object of the present invention to provide a series of foam metal supported bis-spinel type oxides and derivatives thereof, including Co (OH) 2 /MF、CuCo LDH-Co(OH) 2 /MF、 CuCo 2 O 4 -Co 3 O 4 the/MF; wherein Co (OH) 2 the/MF is in a sea urchin ball shape, the sea urchin ball is surrounded by the nano wires, and the end points of the nano wires are connected with each other; cuCo LDH-Co (OH) 2 the/MF presents a chrysanthemum-like structure; cuCo 2 O 4 -Co 3 O 4 the/MF is a ball-shaped structure of flowers clustered together, and the petals are composed of a plurality of groups of one-dimensional Co (OH) 2 The nano wires are bundled together, the bottom ends of the petals are connected and bundled together, and the outer ends of the petals are connected with the outer ends of the petals of the other flower.
The invention also aims to provide the application of the foam metal supported double-spinel type oxide and the derivative thereof in the aspect of hydrogen production by water electrolysis.
Compared with the prior art, the beneficial effects of the invention are embodied in the following aspects:
(1) The prepared three foam metal-loaded bi-spinel type oxides and derivatives thereof have special three-dimensional (3D) structures, can increase the surface area and active sites of the material to a greater extent and promote the diffusion of reactants and generated gas, wherein CuCo 2 O 4 -Co 3 O 4 The 3D chrysanthemum-shaped morphology of the/MF forms outward active sites and a large specific surface area, so that the electron transfer is greatly accelerated, and the rapid desorption of the generated oxygen is facilitated;
(2) Two spinel-structured oxides (CuCo) were obtained 2 O 4 -Co 3 O 4 /MF) has a more open structure, is easy to migrate metal cations, and simultaneously improves the mobility between electrons by a mixed crystal structure;
(3) The nano array directly grown on the surface of the substrate by the self-supporting electrode enables the catalyst to have larger surface area and more quickly release carriers, so that the interaction and synergistic effect among various species are enhanced; with CuCo 2 O 4 And Co 3 O 4 The double metal oxide will produce synergistic effectFurther regulating the electronic structure and improving the activity of the catalyst;
(4) The obtained CuCo 2 O 4 -Co 3 O 4 the/MF can be directly used as an electrode without a conductive polymer;
(5) The obtained CuCo 2 O 4 -Co 3 O 4 the/MF has excellent OER catalytic performance, and the experimental result shows that the OER catalytic performance is 10 mA-cm -2 The overpotential is as low as 267mV, the Tafel slope is smaller (114.59 mV dec) -1 ) And has a high electrochemical surface area (C) dl ＝26.68mF/cm 2 ) The electrolyte has good electrochemical stability in alkaline electrolyte;
(6) The preparation method provided by the invention is simple to operate, the raw materials are easy to obtain, the price is low, the reaction conditions are easy to achieve, and the preparation method has a great industrial application prospect.
Drawings
FIG. 1 shows Co (OH) obtained in example 1 2 /NF(a)、CuCo LDH-Co(OH) 2 /NF(b)、 CuCo 2 O 4 -Co 3 O 4 A scanning electron micrograph of/NF (c);
FIG. 2 shows CuCo prepared in example 2 2 O 4 -Co 3 O 4 XPS survey spectrum (a), cu 2p (b), co 2p (c) and O1s (d) of/NF;
FIG. 3 shows CuCo prepared in comparative examples 1 to 5 and example 2 2 O 4 -Co 3 O 4 /NF、CuCo LDH-Co(OH) 2 /NF、CuCo 2 O 4 /NF、Co 3 O 4 /NF、CuO-Co 3 O 4 /NF、Co 3 O 4 -Co 3 O 4 /NF、RuO 2 OER polarization plots for/NF and pure NF in 1M aqueous KOH (a) and corresponding Tafel plots (b).
Detailed Description
In order to fully understand the technical solutions and advantages of the present invention, those skilled in the art will further describe the following embodiments with reference to the accompanying drawings.
Example 1
a. Firstly, foamed nickel is firstly(Nickel Foam, NF for short) cut into a geometric area of 1X 3cm 2 The small blocks are put into a clean beaker, a certain amount of absolute ethyl alcohol is poured into the beaker to immerse the foam nickel, and the small blocks are cleaned by ultrasonic for 20min. And after the cleaning is finished, soaking the foamed nickel into 2mol/L hydrochloric acid by the same method, ultrasonically cleaning for 20min, finally washing the foamed nickel for 2-3 times by using deionized water, and drying for later use.
b. 2.811g (10 mmol) of CoSO were weighed in order 4 ·7H 2 O、3.003g(50mmol) CH 4 N 2 O and 0.7408g (20 mmol) NH 4 And F, adding the mixture into 50mL of deionized water, and carrying out ultrasonic dissolution to form a transparent and uniform solution. Adding 40mL of the solution into a polytetrafluoroethylene lining with the capacity of 50mL, then adding pretreated foamed nickel, then putting the polytetrafluoroethylene lining into an autoclave, integrally transferring the autoclave into a muffle furnace, sealing, and carrying out thermal insulation hydrothermal reaction for 5 hours at 120 ℃. Taking out the foamed nickel after the reaction is finished, washing the foamed nickel by deionized water for 3 to 5 times, and then freeze-drying the foamed nickel for 6 to 8 hours to obtain a sample, namely Co (OH) 2 /NF。
Co (OH) produced by this step 2 The SEM photograph of/NF is shown in FIG. 1 (a). As can be seen, each sea urchin sphere is surrounded by nanowires, the ends of which are connected to each other, similar to the target sample.
c. 149.814mg (0.6 mmol) of CuSO were weighed out in turn 4 ·9H 2 O、337.32mg(1.2mmol) CoSO 4 ·7H 2 O、360.36mg(6mmol)CH 4 N 2 And O, adding the mixture into 30mL of deionized water, and carrying out ultrasonic dissolution to form a transparent and uniform solution. The solution was poured into a 50mL Teflon liner and dried Co (OH) was added 2 and/NF, then filling the polytetrafluoroethylene lining into an autoclave, integrally transferring the autoclave into a muffle furnace, sealing, and carrying out thermal hydrothermal reaction for 6 hours at 120 ℃. After the reaction was completed, a solid sample was taken out and washed 3 to 5 times with deionized water to remove surface unreacted materials, followed by freeze-drying for 6 to 8 hours, whereby the resulting sample was named CuCo LDH-Co (OH) 2 /NF。
CuCo LDH-Co (OH) prepared by the step 2 The SEM image of/NF is shown in FIG. 1 (b). As can be seen from the figure, inIn the process of growing CuCo LDH, sea urchins are spherical and disappear, and develop into flower-like structures, and the whole body presents chrysanthemum-like prototypes, which is because Cu 2+ The addition of (b) rearranges the structure.
d. Mixing CuCo LDH-Co (OH) 2 Putting the quartz boat into a tube furnace in air atmosphere, heating to 350 ℃ at a heating rate of 5 ℃/min, preserving heat for 2 hours, and finally cooling to room temperature at the same cooling rate to obtain CuCo 2 O 4 -Co 3 O 4 /NF。
CuCo prepared by the step 2 O 4 -Co 3 O 4 The SEM photograph of/NF is shown in FIG. 1 (c). As can be seen from the figure, the product presents a ball-shaped structure of flowers clustered together under low magnification, and after amplification, the products can be seen to be obviously chrysanthemum-shaped, the bottom ends of the 'petals' are connected and bundled together, and at the outer ends of the 'petals', each chrysanthemum is connected with another chrysanthemum; the petals of the chrysanthemum are actually formed by the nanowires, the surfaces of the nanowires are not smooth, the end points of every few nanowires are bundled together, the bundled nanowires are simultaneously contacted with the nanowires with similar structures, and mass transfer paths are further increased. The hierarchical structure formed by the one-dimensional nanowires and the three-dimensional chrysanthemum greatly increases the surface area of the material and is beneficial to improving the catalytic activity of the material.
Example 2
a. Firstly, cutting the foam nickel into a geometrical area of 1 multiplied by 3cm 2 The small blocks are put into a clean beaker, a certain amount of absolute ethyl alcohol is poured into the beaker to immerse the foam nickel, and the small blocks are cleaned for 20min by ultrasonic. And after the cleaning is finished, soaking the foamed nickel into 2mol/L hydrochloric acid by the same method, ultrasonically cleaning for 20min, finally washing the foamed nickel for 2-3 times by using deionized water, and drying for later use.
b. 2.811g (10 mmol) of CoSO were weighed out in this order 4 ·7H 2 O、3.003g(50mmol)CH 4 N 2 O and 0.7408g (20 mmol) NH 4 And F, adding the weighed raw materials into 50mL of deionized water, and performing ultrasonic dissolution to form a transparent and uniform solution. 40mL of the solution was added to a 50 mL-volume, washed and dried polytetrafluoroethylene linerAnd then putting the pretreated foamed nickel, then putting the polytetrafluoroethylene lining into an autoclave, integrally transferring the autoclave into a muffle furnace, sealing, and carrying out heat preservation and hydrothermal reaction for 5 hours at 120 ℃. Taking out the foamed nickel after the reaction is finished, washing the foamed nickel by deionized water for 3 to 5 times, and then freeze-drying the foamed nickel for 6 to 8 hours to obtain a sample, namely Co (OH) 2 /NF。
c. 299.628mg (1.2 mmol) of CuSO are weighed in turn 4 ·9H 2 O、674.64mg(2.4mmol) CoSO 4 ·7H 2 O and 720.72mg (12 mmol) CH 4 N 2 And O, adding the mixture into 60mL of deionized water, and carrying out ultrasonic dissolution to form a transparent and uniform solution. The solution was poured into a 50mL Teflon liner and dried Co (OH) 2 and/NF, then filling the polytetrafluoroethylene lining into the autoclave, integrally transferring the autoclave into a muffle furnace, sealing the autoclave, and carrying out thermal hydrothermal reaction for 6 hours at 120 ℃. After the reaction was completed, a solid sample was taken out and washed 3 to 5 times with deionized water, followed by freeze-drying for 6 to 8 hours, and the thus-obtained sample was named CuCo LDH-Co (OH) 2 /NF。
d. Mixing CuCo LDH-Co (OH) 2 Putting the quartz boat into a tube furnace in air atmosphere, heating to 350 ℃ at a heating rate of 5 ℃/min, preserving heat for 2h, and finally cooling to room temperature at the same cooling rate to obtain CuCo 2 O 4 -Co 3 O 4 /NF。
CuCo prepared by the step 2 O 4 -Co 3 O 4 The XPS survey spectrum of/NF is shown in FIG. 2 (a), which shows characteristic peaks of C, O, co and Cu. As shown in FIG. 2 (b), cuCo 2 O 4 -Co 3 O 4 Cu 2p in/NF 3/2 Orbitals, peaks at 931.91 and 934.12eV assigned to Cu + And Cu 2+ (ii) a In Cu 2p 1/2 On the orbit, the peaks at 951.43 and 953.99eV are also assigned to Cu + And Cu 2+ . In addition, two satellite peaks (labeled sat.) were observed, at 941.18 and 960.02eV, respectively, which is Cu 2+ Thereby illustrating the CuCo 2 O 4 -Co 3 O 4 Simultaneous presence of Cu in NF + And Cu 2+ 。
As shown in FIG. 2 (c), in CuCo 2 O 4 -Co 3 O 4 Co 2p spectrum of/NF also found two types of Co valence (Co valence) 2+ And Co 3+ ) The fitted peaks at 778.97 and 793.96eV correspond to Co 3+ The fitted peaks at 780.26eV and 795.43eV correspond to Co 2+ 。Cu + 、Cu 2+ And Co 2+ 、Co 3+ The appearance of multiple valence states indicates that a synergistic effect exists between Cu and Co. And in FIG. 2 (d), O at 533.41eV 1 Peaks due to absorbed water; o at 531.97eV 2 Peaks, mainly due to crystal defects, chemisorbed oxygen or coordinated lattice oxygen; o is 3 The peak is at 530.28eV, with typical metal-oxygen bond characteristics, corresponding to Cu-O, co-O. Therefore, the distribution of the electron density is beneficial to enhancing the electron transfer between interfaces, thereby improving the CuCo 2 O 4 -Co 3 O 4 The catalytic activity of/NF.
Comparative example 1
Co 3 O 4 The preparation method of/NF comprises the following steps:
a. firstly, cutting the foam nickel into a geometrical area of 1 multiplied by 3cm 2 The small blocks are put into a clean beaker, a certain amount of absolute ethyl alcohol is poured into the beaker to immerse the foam nickel, and the small blocks are cleaned for 20min by ultrasonic. And after the cleaning is finished, soaking the foamed nickel into 2mol/L hydrochloric acid by the same method, ultrasonically cleaning for 20min, finally washing the foamed nickel for 2-3 times by using deionized water, and drying for later use.
b. 2.811g (10 mmol) of CoSO were weighed in order 4 ·7H 2 O、3.003g(50mmol)CH 4 N 2 O and 0.7408g (20 mmol) NH 4 And F, adding the weighed raw materials into 50mL of deionized water, and carrying out ultrasonic dissolution to form a transparent and uniform solution. Adding 40mL of the solution into a polytetrafluoroethylene lining which has the capacity of 50mL and is washed and dried, then adding pretreated foamed nickel, then putting the polytetrafluoroethylene lining into an autoclave, integrally transferring the autoclave into a muffle furnace, sealing, and carrying out thermal insulation hydrothermal reaction for 5 hours at 120 ℃. Taking out the foamed nickel after the reaction is finished, washing the foamed nickel by deionized water for 3 to 5 times, and then freeze-drying the foamed nickel for 6 to 8 hours to obtain a sampleIs Co (OH) 2 /NF。
c. The obtained Co (OH) 2 Placing NF in a tube furnace in air atmosphere, heating to 350 deg.C at a heating rate of 5 deg.C/min, holding at the temperature for 2h, and cooling to room temperature at the same cooling rate to obtain Co 3 O 4 /NF。
Comparative example 2
CuCo 2 O 4 The preparation method of/NF comprises the following steps:
a. firstly, cutting the foamed nickel into a geometric area of 1 multiplied by 3cm 2 The small blocks are put into a clean beaker, a certain amount of absolute ethyl alcohol is poured into the beaker to immerse the foam nickel, and the small blocks are cleaned by ultrasonic for 20min. And after the cleaning is finished, soaking the foamed nickel into 2mol/L hydrochloric acid by the same method, ultrasonically cleaning for 20min, finally washing the foamed nickel for 2-3 times by using deionized water, and drying for later use.
b. 149.814mg (0.6 mmol) of CuSO were weighed in turn 4 ·9H 2 O、337.32mg(1.2mmol) CoSO 4 ·7H 2 O、360.36mg(6mmol)CH 4 N 2 And O, adding the mixture into 30mL of deionized water, and carrying out ultrasonic dissolution to form a transparent and uniform solution. Pouring the solution into a polytetrafluoroethylene lining with the capacity of 50mL, adding dried foam nickel, then putting the polytetrafluoroethylene lining into an autoclave, integrally transferring the autoclave into a muffle furnace, sealing, and carrying out heat preservation and hydrothermal reaction at 120 ℃ for 6 hours. After the reaction was completed, a solid sample was taken out and washed 3 to 5 times with deionized water to remove surface unreacted materials, followed by freeze-drying for 6 to 8 hours, whereby the resulting sample was named CuCo LDH/NF.
c. Placing the obtained CuCo LDH/NF in a tube furnace in air atmosphere, heating to 350 ℃ at a heating rate of 5 ℃/min, preserving heat for 2h at the temperature, and finally cooling to room temperature at the same cooling rate to obtain CuCo LDH/NF 2 O 4 /NF。
Comparative example 3
CuO-Co 3 O 4 The preparation method of/NF comprises the following steps:
a. firstly, cutting the foam nickel into a geometrical area of 1 multiplied by 3cm 2 The small blocks are put into a clean beaker, and a certain amount of absolute ethyl alcohol is poured into the beaker to immerse the foamAnd (4) carrying out ultrasonic cleaning on nickel for 20min. And after the cleaning is finished, soaking the foamed nickel into 2mol/L hydrochloric acid by the same method, ultrasonically cleaning for 20min, finally washing the foamed nickel for 2-3 times by using deionized water, and drying for later use.
b. 149.814mg (0.6 mmol) of CuSO were weighed out in turn 4 ·9H 2 O、337.32mg(1.2mmol) CoSO 4 ·7H 2 O、360.36mg(6mmol)CH 4 N 2 And O, adding the mixture into 30mL of deionized water, and carrying out ultrasonic dissolution to form a transparent and uniform solution. Pouring the solution into a polytetrafluoroethylene lining with the capacity of 50mL, adding dried foam nickel, then putting the polytetrafluoroethylene lining into an autoclave, integrally transferring the autoclave into a muffle furnace, sealing, and carrying out heat preservation and hydrothermal reaction at 120 ℃ for 6 hours. After the reaction was completed, a solid sample was taken out and washed 3 to 5 times with deionized water to remove surface unreacted materials, followed by freeze-drying for 6 to 8 hours, whereby the resulting sample was named Cu LDH-Co (OH) 2 /NF。
c. Cu LDH-Co (OH) 2 Putting the quartz boat into a tube furnace in air atmosphere, heating to 350 ℃ at a heating rate of 5 ℃/min, preserving heat for 2h, and finally cooling to room temperature at the same cooling rate to obtain CuO-Co 3 O 4 /NF。
Comparative example 4
Co 3 O 4 -Co 3 O 4 The preparation method of the/NF comprises the following steps:
a. firstly, cutting the foamed nickel into a geometric area of 1 multiplied by 3cm 2 The small blocks are put into a clean beaker, a certain amount of absolute ethyl alcohol is poured into the beaker to immerse the foam nickel, and the small blocks are cleaned for 20min by ultrasonic. And after the cleaning is finished, soaking the foamed nickel into 2mol/L hydrochloric acid by the same method, ultrasonically cleaning for 20min, finally washing the foamed nickel for 2-3 times by using deionized water, and drying for later use.
b. 2.811g (10 mmol) of CoSO were weighed out in this order 4 ·7H 2 O、3.003g(50mmol)CH 4 N 2 O and 0.7408g (20 mmol) NH 4 And F, adding the weighed raw materials into 50mL of deionized water, and carrying out ultrasonic dissolution to form a transparent and uniform solution. 40mL of this solution was added to a 50 mL-volume and washed and dried polytetrafluoroethylene liner,and then putting the pretreated foamed nickel, then putting the polytetrafluoroethylene lining into a high-pressure kettle, integrally transferring the high-pressure kettle into a muffle furnace, sealing, and carrying out heat preservation hydrothermal reaction for 5 hours at 120 ℃. Taking out the foamed nickel after the reaction is finished, washing the foamed nickel by deionized water for 3 to 5 times, and then freeze-drying the foamed nickel for 6 to 8 hours to obtain a sample, namely Co (OH) 2 /NF。
c. 337.32mg (1.2 mmol) of CoSO were sequentially weighed 4 ·7H 2 O、360.36mg(6mmol) CH 4 N 2 And O, adding the mixture into 30mL of deionized water, and carrying out ultrasonic dissolution to form a transparent and uniform solution. The solution was poured into a 50mL Teflon liner and dried Co (OH) was added 2 and/NF, then filling the polytetrafluoroethylene lining into the autoclave, integrally transferring the autoclave into a muffle furnace, sealing the autoclave, and carrying out thermal hydrothermal reaction for 6 hours at 120 ℃. After the reaction is finished, taking out a solid sample and washing 3-5 times by deionized water so as to remove unreacted substances on the surface, and then freeze-drying for 6-8h.
d. Putting the sample prepared in the step (c) into a quartz boat, putting the quartz boat into a tube furnace in the air atmosphere, heating to 350 ℃ at the heating rate of 5 ℃/min, preserving heat for 2 hours, and finally cooling to room temperature at the same cooling rate to obtain Co 3 O 4 -Co 3 O 4 /NF。
Comparative example 5
RuO 2 The preparation method of the/NF comprises the following steps:
a. firstly, cutting the foam nickel into a geometrical area of 1 multiplied by 3cm 2 The small blocks are put into a clean beaker, a certain amount of absolute ethyl alcohol is poured into the beaker to immerse the foam nickel, and the small blocks are cleaned for 20min by ultrasonic. And after the cleaning is finished, soaking the foamed nickel into 2mol/L hydrochloric acid by the same method, ultrasonically cleaning for 20min, finally washing the foamed nickel for 2-3 times by using deionized water, and drying for later use.
b. Firstly, 4.0mg of RuO is weighed by an electronic balance 2 The powder (99.90%) and 40 μ L of Nafion solution (5 wt%), were ultrasonically dispersed in 960 μ L of an ethanol aqueous solution (ultrapure water: absolute ethanol = 3.
In order to make the comparison,the products of example 2 and comparative examples 1-5 were tested in comparison, the samples being tested being activated by Cyclic Voltammetry (CV) followed by 2mV s -1 The scan rate of (a) was tested in the range of 0-0.70V (vs. sce), and 85% iR compensation was performed to eliminate the loss caused by the line, the results are shown in fig. 3. Except for CuCo 2 O 4 -Co 3 O 4 /NF、 CuCo LDH-Co(OH) 2 In addition to/NF, cuCo is also shown in FIG. 3 (a) 2 O 4 /NF、 Co 3 O 4 /NF、CuO-Co 3 O 4 /NF、Co 3 O 4 -Co 3 O 4 /NF、RuO 2 Measurement results of/NF and pure NF. Wherein, cuCo 2 O 4 -Co 3 O 4 the/NF showed excellent activity, and only an overpotential of 267mV was required to reach 10mA cm -2 The current density of (1). The performance is far superior to CuCo 2 O 4 /NF (η 10 ＝318mV)、Co 3 O 4 /NF(η 10 ＝299mV)、CuO-Co 3 O 4 /NF(η 10 ＝323mV)、 Co 3 O 4 -Co 3 O 4 /CF(η 10 ＝288mV)、CuCo LDH-Co(OH) 2 /NF(η 10 ＝284mV)、RuO 2 /NF(η 10 =339 mV) and NF (. Eta.) (η) 10 =345 mV). In addition, cuCo 2 O 4 -Co 3 O 4 the/NF only needs 407mV over-potential to reach 100mA cm -2 The large current density further shows that the OER has excellent OER activity.
The Tafel slope of each electrode was obtained from the LSV curve, further explaining the kinetic behavior of the material in the OER process, and the results are shown in fig. 3 (b). With CuCo 2 O 4 /NF(155.02 mV·dec -1 )，Co 3 O 4 /NF(135.69mV·dec -1 )，CuO-Co 3 O 4 /NF(132.26 mV·dec -1 )，Co 3 O 4 -Co 3 O 4 /CF(142.53mV·dec -1 )，CuCo LDH-Co(OH) 2 /NF (140.87mV·dec -1 )，RuO 2 /NF(109.7mV·dec -1 )，NF(140.91mV·dec -1 ) In contrast, cuCo 2 O 4 -Co 3 O 4 The Tafel slope for/NF was significantly lower, only 114.59 mV dec -1 This demonstrates that the catalytic material has a faster catalytic reaction rate.
Claims (9)
1. Foam metal loaded bi-spinel type oxide CuCo 2 O 4 -Co 3 O 4 And a preparation method of the derivative thereof, which is characterized by comprising the following steps: (a) Preparation of Co (OH) on a foamed Metal substrate 2 Nanowire to obtain (Co (OH) 2 /MF: (b) In order (Co (OH) 2 /MF as raw material, in Co (OH) 2 Preparing CuCo layered double hydroxide on the nano-wire to obtain CuCo LDH-Co (OH) 2 /MF; (c) Mixing CuCo LDH-Co (OH) 2 the/MF is put in an oxygen-containing atmosphere for heat treatment to obtain three-dimensional chrysanthemum-shaped CuCo 2 O 4 -Co 3 O 4 /MF。
2. The method of claim 1, wherein: step (a) adopts a one-step hydrothermal method to prepare (Co (OH) 2 The specific process is as follows: mixing cobalt salt, urea and NH 4 F. Dissolving PVP in water, adding foam metal, sealing, heating for hydrothermal reaction, and finally performing solid-liquid separation, washing and drying.
3. The method of claim 2, wherein: the cobalt salt in the step (a) is selected from one of cobalt sulfate, cobalt chloride, cobalt nitrate and cobalt acetate, the foam metal is selected from one of foam nickel, foam copper, foam silver and foam cobalt, cobalt salt, urea and NH 4 The molar ratio of F to PVP is 1-6.
4. The method of claim 1, wherein: step (b) preparing CuCo LDH-Co (OH) by hydrothermal method 2 The specific process is as follows: dissolving copper salt, cobalt salt and urea in water, and adding into the step (a)) Prepared Co (OH) 2 and/MF, sealing, heating for hydrothermal reaction, and finally performing solid-liquid separation, washing and drying.
5. The method of claim 4, wherein: the copper salt in the step (b) is selected from one of copper sulfate, copper acetate, copper chloride and copper nitrate, the cobalt salt is selected from one of cobalt sulfate, cobalt chloride, cobalt nitrate and cobalt acetate, the molar ratio of the copper salt to the cobalt salt to urea is 1-3.
6. The method of claim 1, wherein: step (c) adopts a low-temperature oxidation method to prepare three-dimensional chrysanthemum-shaped CuCo 2 O 4 -Co 3 O 4 The specific process is as follows: in an oxygen-containing atmosphere, cuCo LDH-Co (OH) 2 Heating by/MF to perform annealing treatment, and finally cooling to room temperature.
7. The method of claim 6, wherein: the oxygen-containing atmosphere is specifically one of air atmosphere and pure oxygen atmosphere, the heating and cooling rates in the annealing process are both 3-8 ℃/min, the annealing temperature is 300-800 ℃, and the heat preservation time is 1-7h.
8. A foam metal loaded bi-spinel type oxide and derivative catalyst thereof is characterized in that: the catalyst comprises Co (OH) 2 /MF、CuCo LDH-Co(OH) 2 /MF、CuCo 2 O 4 -Co 3 O 4 /MF; wherein Co (OH) 2 the/MF is in a sea urchin sphere shape, the sea urchin sphere is surrounded by the nano wires, and the end points of the nano wires are connected with each other; cuCo LDH-Co (OH) 2 the/MF is in a chrysanthemum structure; cuCo 2 O 4 -Co 3 O 4 the/MF is a ball-shaped structure of flowers clustered together, and the petals are composed of a plurality of groups of one-dimensional Co (OH) 2 The nano wires are bunched, the bottom ends of the petals are connected and bunched together, and the outer ends of the petals are connected with the outer ends of the petals of the other flower.
9. The use of the foam metal supported bis-spinel type oxide and its derivative catalyst of claim 8 in the production of hydrogen by electrolysis of water.
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