CN111883367A - Cu-doped cobalt hydroxide nanosheet array structure material and preparation method and application thereof - Google Patents
Cu-doped cobalt hydroxide nanosheet array structure material and preparation method and application thereof Download PDFInfo
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- 239000002135 nanosheet Substances 0.000 title claims abstract description 90
- 239000000463 material Substances 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 title abstract description 8
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 title abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000004202 carbamide Substances 0.000 claims abstract description 39
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 27
- 239000001257 hydrogen Substances 0.000 claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 19
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 10
- 239000010411 electrocatalyst Substances 0.000 claims abstract description 9
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 9
- 150000001868 cobalt Chemical class 0.000 claims abstract description 7
- 150000001879 copper Chemical class 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000004729 solvothermal method Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 239000012046 mixed solvent Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 6
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical group O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 2
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical group O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 239000010949 copper Substances 0.000 abstract description 71
- 230000000694 effects Effects 0.000 abstract description 8
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 17
- 238000005868 electrolysis reaction Methods 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 14
- 230000010287 polarization Effects 0.000 description 14
- 238000010586 diagram Methods 0.000 description 11
- 238000004502 linear sweep voltammetry Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000006260 foam Substances 0.000 description 10
- 239000008151 electrolyte solution Substances 0.000 description 9
- 229940021013 electrolyte solution Drugs 0.000 description 9
- 239000002064 nanoplatelet Substances 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 229960004011 methenamine Drugs 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
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- 238000007605 air drying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- XWNPLAZTJRRXIW-UHFFFAOYSA-N nickel;urea Chemical compound [Ni].NC(N)=O XWNPLAZTJRRXIW-UHFFFAOYSA-N 0.000 description 1
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- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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Abstract
The invention discloses a Cu-doped cobalt hydroxide nanosheet array structure material and a preparation method and application thereof; dissolving copper salt, cobalt salt and hexamethylenetetramine in a mixed solvent of water and methanol, transferring the solution to a reaction kettle, obliquely placing foamed nickel in the solution, carrying out solvothermal reaction, cooling to room temperature after the reaction is finished, washing and drying a product to obtain Cu-doped Co (OH)2A nanosheet array structure material; cu doped Co (OH) of the present disclosure2Nanosheet array structure, effective Co (OH) adjustment by Cu doping2The electronic structure of the organic electroluminescent material reduces resistance, increases active sites, improves hydrophilicity and accelerates electron transfer rate; the Cu doped Co (OH)2Nano-sheet array structure material used as urea oxidation reaction, hydrogen evolution reaction and total ureaThe electrocatalyst for the electrolytic reaction has the advantages of high activity, good durability, simple preparation process and low cost, and has great value for researching the practical application of the hydrogen-generating electrocatalyst material.
Description
Technical Field
The invention belongs to the field of nano material preparation methods and electrocatalysis application, and particularly relates to a Cu-doped cobalt hydroxide nanosheet array structure material and a preparation method and application thereof.
Background
At present, hydrogen is considered to be the most attractive energy source to replace traditional fossil fuels due to its high energy density and environmental protection. Hydrogen production by water electrolysis has been considered a sustainable and promising approach, but due to the slow kinetics of anodic Oxygen Evolution (OER) a considerable potential is usually required to produce hydrogen continuously. And in the process of full water electrolysis, H2And O2At the same time, explosive H may be formed2/O2And (3) mixing. Therefore, there is a great need to develop a feasible process for efficiently, safely and massively producing hydrogen using an easier-to-perform oxidation reaction instead of OER.
The theoretical potential of the Urea Oxidation Reaction (UOR) (0.37V vs. rhe) is much smaller than that of the OER (1.23V vs. rhe), and therefore UOR has the potential to replace the slow reacting OER. Moreover, the full-urea electrolysis provides a wide prospect for repairing the waste water rich in urea while saving energy and producing hydrogen. However, due to the inherent slowness 6e of the anode UOR—The transfer process, such that full urea electrolysis still faces the challenges of low activity and high overpotential. Therefore, efforts are being made to develop efficient and earth-resource-rich UOR catalyst materials.
Much research is currently being devoted to the development of various nickel-based materials for use as UOR catalysts, with the nickel-based materials being believed to oxidize the Ni produced in the electrochemical process3+Is the active site of UOR. And some nickel-based materials also have good HER catalytic performance and can be successfully applied to the electrocatalytic hydrogen production of the total urea. Considering Co2+Oxidation to Co3+Is lower than Ni2+Oxidation to Ni3+Should have greater UOR electrocatalytic potential. Cobalt-based materials, however, are rarely used in UOR and all-urea electrolysis processes, and their catalytic activity is to be further improved.
Disclosure of Invention
In order to solve the technical problems, the invention provides a Cu-doped cobalt hydroxide nanosheet array structure material and a preparation method and application thereof. By one step on a foamed nickel substrateLiquid phase method for synthesizing Cu-doped Co (OH)2A nanosheet array structure material is used as a high-efficiency UOR, HER and all-urea electrolytic catalyst. In Co (OH)2In the nanosheet array, a large number of surface atoms are exposed by the two-dimensional nanosheets, so that the number of active sites can be remarkably increased, and the relatively open structure can ensure the rapid diffusion of reactants and products and the rapid transfer of proton-coupled electrons, so that the catalytic active sites are easy to approach. And the introduced foreign metal cation Cu2+Can effectively regulate Co (OH)2The electronic structure of the active metal center Co increases the conductivity of the catalyst, accelerates the electron transfer rate, improves the hydrophilicity, increases the number of active sites, and realizes the outstanding catalytic activity and stability of the full urea electrolysis.
The invention provides a Cu-doped Co (OH)2The preparation method of the nano-sheet array structure material comprises the following steps: dissolving copper salt, cobalt salt and hexamethylenetetramine in a mixed solvent of water and methanol, transferring the solution to a reaction kettle, obliquely placing foamed nickel in the solution, carrying out solvothermal reaction, cooling to room temperature after the reaction is finished, washing and drying a product to obtain Cu-doped Co (OH)2A nanosheet array structure material.
Further, the copper salt is copper nitrate trihydrate; the cobalt salt is cobalt nitrate hexahydrate.
The ratio of the copper salt, the cobalt salt and the hexamethylene tetramine is 0.1-0.3: 2:5, preferably 0.2:2: 5.
The concentration of the hexamethylenetetramine in the mixed solvent of water and methanol is 0.143M.
The volume ratio of water to methanol was 4: 3.
The solvothermal reaction condition is that the reaction is carried out for 6 hours at 120 ℃.
The foam Nickel (NF) needs to be cleaned before use, and the specific cleaning steps are as follows: soaking in 6M hydrochloric acid for 15min to remove the outer oxide film, washing with deionized water and anhydrous ethanol for 3 times, and air drying. When in use, the foam nickel is cut into the size of 2 multiplied by 3 cm.
The washing is 3 times by using deionized water and absolute ethyl alcohol respectively.
The drying is carried out in an oven at 60 ℃ for 8 h.
The invention also provides Cu-doped Co (OH) prepared by the preparation method2Nanosheet array structure material, the Cu doped Co (OH)2The morphology of the nano-sheet array structure material is composed of nano-sheets with the average size of 300-400 nm.
The invention also provides the Cu-doped Co (OH)2The nano-sheet array structure material is applied as an electrocatalyst for urea oxidation reaction or hydrogen evolution reaction or full urea electrolysis reaction.
The Cu doped Co (OH)2When the nano-sheet array structure material is applied as a Urea Oxidation Reaction (UOR) electrocatalyst, the specific method comprises the following steps: cu doped Co (OH) prepared on foamed nickel2The nanosheet array structure material is cut into 0.5 multiplied by 0.5cm to be used as a working electrode, 1M KOH and 0.33M urea solution are used as electrolyte, and the CHI760E electrochemical workstation is used for testing. Platinum wire and Ag/AgCl electrodes were used as counter and reference electrodes, respectively. Linear Sweep Voltammetry (LSV) at 5.0mV · s-1The polarization curve is obtained at a scanning rate of 90% with ohmic compensation; stability was obtained by measuring the current density time curve at constant voltage. Electrochemically active area (ECSA) was determined by scanning at different rates (6, 8, 10, 12, 14, 16, 18 and 20mV · s) without significant faraday region-1) Measuring the electric double layer capacitance (C) of a capacitordl) Carrying out evaluation; electrochemical Impedance (EIS) was tested in the frequency range of 100kHz to 0.1 Hz. Co (OH) prepared on and on nickel foam with commercial Pt/C, respectively2The nanosheets were used as working electrodes and their UOR performance was measured separately for comparison.
The Cu doped Co (OH)2When the nanosheet array structure material is applied as a Hydrogen Evolution Reaction (HER) electrocatalyst, the specific method comprises the following steps: cu doped Co (OH) prepared on foamed nickel2The nanosheet array structure material is cut into 0.5 multiplied by 0.5cm to be used as a working electrode, 1M KOH and 0.33M urea solution are used as electrolyte, and the CHI760E electrochemical workstation is used for testing. Using carbon rod and Ag/AgCl electrode as counter electrode anda reference electrode. Linear Sweep Voltammetry (LSV) at 5.0mV · s-1The polarization curve is obtained at a scanning rate of 90% with ohmic compensation; stability was obtained by measuring the current density time curve at constant voltage. Electrochemically active area (ECSA) was determined by scanning at different rates (6, 8, 10, 12, 14, 16, 18 and 20mV · s) without significant faraday region-1) Measuring the electric double layer capacitance (C) of a capacitordl) Carrying out evaluation; electrochemical Impedance (EIS) was tested in the frequency range of 100kHz to 0.1 Hz. Co (OH) prepared on and on nickel foam with commercial Pt/C, respectively2The nanoplates served as working electrodes and their HER performance was measured separately as a comparison.
The Cu doped Co (OH)2When the nano-sheet array structure material is used as an all-urea electrolytic reaction electrocatalyst, the specific method comprises the following steps: cu doped Co (OH) prepared on foamed nickel2The nano-sheet array structure material is cut into 2 pieces with the size of 0.5 multiplied by 0.5cm and respectively used as a cathode and an anode to be assembled in a double-electrode electrolytic cell, and the electrolysis performance of the total urea is tested through an LSV polarization curve compensated by 90% iR and a current density time curve under constant voltage. By way of comparison, commercial Pt/C supported on nickel foam and Co (OH) prepared on nickel foam were investigated2And the nanosheets are respectively used as LSV polarization curves of cathode and anode full urea electrolysis.
In the invention, Cu doping can adjust the electronic structure of the catalyst and promote high oxidation state Co3+Increase the electrochemical active area and reduce the resistance. Defects generated by Cu doping induction can effectively expose more open active site adsorption reaction intermediates, and the interface charge transfer rate is accelerated. And Cu doping improves the hydrophilicity of the catalyst, enhances the penetration of electrolyte, further accelerates the charge transfer rate between the electrolyte and the catalyst, and improves the catalytic activity. The material shows excellent activity and durability to urea oxidation reaction, hydrogen evolution reaction and full urea electrolysis reaction in alkaline electrolyte, and has great value to research on the practical application of urea-assisted hydrogen production electro-catalytic electrode material.
Compared with the prior art, the invention adopts the simple structureSingle step solvothermal process for the production of NH by decomposition of hexamethylenetetramine3，NH3Dissolving in water to generate OH-And NH4 +，Co2+Ions with OH-Ion generation Co (OH)2While being Cu2+Incorporated into the crystal lattice. Selecting mixed solution of water and methanol as solvent, controlling Co2+The hydrolysis speed of (2) to obtain a thin nanosheet array structure of uniform size. Cu doped Co (OH)2The nano-sheet array structure material shows excellent catalytic activity and stability for urea oxidation reaction, hydrogen evolution reaction and full urea electrolysis reaction, and the preparation process is environment-friendly, simple and low in cost.
Drawings
FIG. 1 shows Cu doped Co (OH) prepared in example 12An X-ray powder diffraction (XRD) pattern of the nanosheet array structure material;
FIG. 2 shows Cu doped Co (OH) prepared in example 12An energy dispersive X-ray spectroscopy (EDX) map of the nanosheet array structure material;
FIG. 3 shows Cu doped Co (OH) prepared in example 12A Scanning Electron Microscope (SEM) image of the nanoplatelet array structure material;
FIG. 4 shows Cu doped Co (OH) prepared in example 12A Transmission Electron Microscope (TEM) image of the nanosheet array structure material;
FIG. 5 shows Cu doped Co (OH) prepared in example 12A High Resolution Transmission Electron Microscope (HRTEM) image of the nanosheet array structure material;
FIG. 6 shows Cu doped Co (OH) prepared in example 12A Scanning Transmission Electron Microscope (STEM) map and corresponding elemental distribution map of the nanosheet array structure material;
FIG. 7 shows Cu doped Co (OH) in example 12A contact angle measurement result graph of the nano-sheet array structure material;
FIG. 8 shows Cu-doped Co (OH) with Cu doping amounts of 3.6% and 9.7% prepared in example 22An X-ray powder diffraction (XRD) pattern of the nanosheet array structure material;
FIG. 9 shows Cu-doped Co (OH) with Cu doping amounts of 3.6% and 9.7% prepared in example 22An energy dispersive X-ray spectroscopy (EDX) map of the nanosheet array structure material;
FIG. 10 shows Cu-doped Co (OH) with a Cu doping amount of 3.6% prepared in example 22A Scanning Electron Microscope (SEM) image of the nanoplatelet array structure material;
FIG. 11 shows Cu-doped Co (OH) with Cu doping amount of 9.7% prepared in example 22A Scanning Electron Microscope (SEM) image of the nanoplatelet array structure material;
FIG. 12 shows Cu-doped Co (OH) with different Cu contents (3.6%, 6.2% and 9.7%) prepared in example 1 and example 22LSV curve diagram of Urea Oxidation Reaction (UOR) of the nano-sheet array structure material;
FIG. 13 shows Cu doped Co (OH) in example 32Nanosheet array structure material, Co (OH)2LSV plots (inset is polarization curve at high current density) for the oxidation reaction (UOR) of nanoplate, Pt/C and foamed nickel urea;
FIG. 14 shows Cu doped Co (OH) in example 32A current density time curve diagram of a nano-sheet array structure material Urea Oxidation Reaction (UOR);
FIG. 15 shows Cu doped Co (OH) in example 32Nanosheet array structure material and Co (OH)2A capacitance-current diagram of the nanosheets under Urea Oxidation Reaction (UOR) conditions at different sweep rates;
FIG. 16 shows Cu doped Co (OH) in example 32Nanosheet array structure material and Co (OH)2Impedance diagram of the nanosheet under Urea Oxidation Reaction (UOR) conditions;
FIG. 17 is a plot of Cu doped Co (OH) with different Cu contents (3.6%, 6.2% and 9.7%) prepared in examples 1 and 22An LSV curve chart of Hydrogen Evolution Reaction (HER) of the nanosheet array structure material;
FIG. 18 shows Cu doped Co (OH) in example 42Nanosheet array structure material, Co (OH)2LSV plots (inset is polarization curve at high current density) for nanosheets, Pt/C and foamed nickel Hydrogen Evolution Reaction (HER);
FIG. 19 shows Cu doped Co (OH) in example 42A current density time curve diagram of Hydrogen Evolution Reaction (HER) of the nanosheet array structure material;
FIG. 20 shows Cu doped Co (OH) in example 42Nanosheet array structure material and Co (OH)2A capacitance-current diagram of the nanosheets under different sweep rates under the condition of Hydrogen Evolution Reaction (HER);
FIG. 21 shows Cu doped Co (OH) in example 42Nanosheet array structure material and Co (OH)2An impedance plot of the nanoplatelets under Hydrogen Evolution Reaction (HER) conditions;
FIG. 22 shows Cu doped Co (OH) in example 52Nanosheet array structure material, Co (OH)2Polarization curve diagrams of the nanosheet and Pt/C in a two-electrode system for all-urea electrolysis (the inset is the polarization curve under high current density);
FIG. 23 shows Cu doped Co (OH) in example 52And (3) a current density time curve diagram of the all-urea electrolysis of the nanosheet array structure material in a two-electrode system.
Detailed Description
The invention is described in detail below with reference to the following examples and the accompanying drawings.
Example 1
Cu-doped Co (OH)2The preparation method of the nano-sheet array structure material comprises the following steps:
soaking foamed nickel with the size of 2 multiplied by 3cm in 6M hydrochloric acid solution, after 15min, respectively cleaning the foamed nickel for 3 times by using deionized water and absolute ethyl alcohol, and naturally airing to obtain the foamed nickel with a clean surface. Accurately weighing 20mL of deionized water and 15mL of methanol, adding into a clean beaker, and respectively weighing 0.2mmol of Cu (NO)3)2·3H2O，2mmol Co(NO3)2·6H2O and 5mmol of hexamethylenetetramine are added into a beaker to obtain a uniform solution. Transferring the solution to a 50mL stainless steel reaction kettle with a polytetrafluoroethylene lining, obliquely inserting the pretreated foamed nickel into the solution, sealing and reacting in an oven at 120 ℃ for 6h, naturally cooling to room temperature after the reaction is finished, washing the foamed nickel covering the sample with deionized water and absolute ethyl alcohol for 3 times respectively, and then drying the foamed nickel in the oven at 60 ℃ for 8h to obtain the Cu-doped Co (OH)2A nanosheet array structure material.
The product obtained in example 1 was subjected to phase characterization by X-ray powder diffractometer, and the results are shown in FIG. 1, all diffraction peaks match with Co (OH) in JCPDS No.51-1731 card2And (5) performing anastomosis.
The product was analyzed using energy dispersive X-ray spectroscopy (EDX), and as shown in fig. 2, the atomic percentages of Cu and Co elements were 0.096:1, indicating that the Cu element was successfully doped into the sample, from which the Cu doping amount was calculated to be 6.2%.
The sample prepared in example 1 was subjected to morphology analysis using a Scanning Electron Microscope (SEM), as shown in fig. 3, indicating that the sample consists of an array of nanosheets having an average size of 300-400 nm.
The morphology of the sample was further observed using Transmission Electron Microscopy (TEM) and the results are shown in fig. 4, further indicating that the sample consists of nanoflakes.
High Resolution Transmission Electron Microscope (HRTEM) images of the nanoplatelets are shown in fig. 5, showing their crystalline nature, but also having some defects, indicating that the nanoplatelets have a rich defect structure. Wherein the interplanar spacing of 0.275nm corresponds to Co (OH)2The (110) crystal plane of (a).
FIG. 6 is a scanning transmission electron microscope elemental distribution diagram illustrating Cu doped Co (OH)2Co, O and Cu elements in the nanosheet array structure material are uniformly distributed.
Cu-doped Co (OH) by contact Angle method2Surface wettability of the nanosheet structure. FIG. 7 shows the dropping of water droplets onto Cu doped Co (OH)2Water drop profile plot of the sample surface immediately after. Cu doped Co (OH)2The contact angle of the sample was 16 deg., indicating the hydrophilicity of the product.
Example 2
Cu doped Co (OH)2The preparation method of the nano-sheet array structure material comprises the following steps:
accurately weighing 20mL of deionized water and 15mL of methanol, adding into a clean beaker, and respectively weighing 0.1mmol or 0.3mmol of Cu (NO)3)2·3H2O，2mmol Co(NO3)2·6H2O and 5mmol of hexamethylenetetramine are added into a beaker and stirred uniformly. The dried foam nickel is driedObliquely inserting the solution into a stainless steel reaction kettle with a lining of 50mL of polytetrafluoroethylene, transferring the solution into the reaction kettle after the solution is fully dissolved, and reacting for 6 hours in an oven at 120 ℃ after sealing. And naturally cooling to room temperature after the reaction is finished, washing the foamed nickel covering the sample by using deionized water and absolute ethyl alcohol for 3 times respectively, and then drying the foamed nickel covering the sample in an oven at 60 ℃ for 8 hours. Cu (NO)3)2·3H2When the amount of O added was 0.1mmol, Cu-doped Co (OH) having a Cu doping amount of 3.6% was obtained2A nanosheet array structure material; cu (NO)3)2·3H2When the amount of O added was 0.3mmol, Cu-doped Co (OH) having a Cu doping amount of 9.7% was obtained2A nanosheet array structure material.
The product obtained in example 2 was subjected to phase characterization by X-ray powder diffractometer, and the results are shown in FIG. 8, in which all diffraction peaks match with Co (OH) in JCPDS No.51-1731 card2And (5) performing anastomosis.
The synthesized nanosheets were analyzed using energy dispersive X-ray spectroscopy (EDX), and as shown in fig. 9, the atomic percentages of Cu and Co elements were 0.054:1 and 0.16:1, respectively, from which Cu doping amounts were calculated to be 3.6% and 9.7%.
The morphology of the sample prepared in example 2 was analyzed using a Scanning Electron Microscope (SEM), and FIGS. 10 and 11 are Cu-doped Co (OH) with Cu doping amounts of 3.6% and 9.7%, respectively2The SEM image shows that the samples are all array structures composed of nanosheets.
Example 3
Cu-doped Co (OH)2The application of the nano-sheet array structure material as a Urea Oxidation Reaction (UOR) catalyst.
The specific application method comprises the following steps: cu of 0.5X 0.5cm area was doped with Co (OH)2The nanosheet array structure material was used as a working electrode, and a Pt wire and an Ag/AgCl electrode were used as a counter electrode and a reference electrode, respectively, for testing in 1.0M KOH and 0.33M urea electrolyte solutions using a CHI760E electrochemical workstation. Co (OH) prepared with commercial Pt/C loading on and on nickel foam, respectively2Nanosheets as working electrodes and their UOR performance measured separately for comparison, Co (OH)2Is prepared byExample 1 in which Cu (NO) in the raw material was omitted3)2·3H2O is prepared. Linear Sweep Voltammetry (LSV) at 5.0mV · s-1And the polarization curve was obtained at 90% ohmic compensation.
FIG. 12 is a Cu doped Co (OH) with different Cu contents of 3.6%, 6.2% and 9.7%2Urea Oxidation Reaction (UOR) polarization curve of the nanoplatelets. Indicating that the doping amount of Cu significantly affects the UOR activity, the sample with the doping amount of Cu of 6.2% is better than the samples of 3.6% and 9.7%.
FIG. 13 shows Cu doped Co (OH)2Nanosheet array structure material, Co (OH)2Urea Oxidation Reaction (UOR) polarization curves of nanosheets, Pt/C and foamed nickel, as can be seen from the figure, Cu doped Co (OH)2The nano-sheet array structure material can realize 10mA cm only by 1.31V low potential-2Current density of (2) is higher than that of Co (OH)2And commercial Pt/C65 mV and 58mV less. Furthermore, Cu-doped Co (OH)2The nano-sheet array structure material can reach 500 mA-cm under the lower potential of 1.418V and 1.486V-2And 1000mA · cm-2High current density.
Figure 14 is an evaluation of UOR electrocatalytic stability using current density time curves at different potentials. It can be seen from the figure that the UOR current density drops by 10% in the first 7 hours at a potential of 1.317V, probably due to the gradual decrease of the urea content in the electrolyte with the increase of the electrolysis time. Whereas, after the original electrolyte solution was replaced with fresh electrolyte solution at 7h, the anode current density was significantly restored to 98% of the original (0h) current density. Similarly, the current density was still able to recover 94% of the original current density after a second replacement of fresh electrolyte solution at 14 h. In addition the catalyst has similar long term durability at 1.362 and 1.418V potentials. Description of Cu6.2％-Co(OH)2The electrodes have excellent UOR stability.
The electrochemical active area of the material under UOR conditions was evaluated using electric double layer capacitance, as shown in fig. 15. Cu doped Co (OH)2The electric double layer capacitance was 20.4 mF. cm-2Greater than Co (OH)210.9mF cm-2Indicates increased Cu dopingThe electrochemically active area of the sample is enlarged.
FIG. 16 is an Electrochemical Impedance (EIS) diagram showing Cu doped Co (OH)2The semicircle diameter of the nano-sheet array structure material is small, which shows that the nano-sheet array structure material has small resistance and faster catalytic kinetics.
Example 4
Cu-doped Co (OH)2Application of the nanosheet array structure material as a Hydrogen Evolution Reaction (HER) catalyst.
The specific application method comprises the following steps: cu of 0.5X 0.5cm area was doped with Co (OH)2The nanosheet array structure material was used as a working electrode, a carbon rod and an Ag/AgCl electrode were used as a counter electrode and a reference electrode, respectively, and the test was performed in 1.0M KOH and 0.33M urea electrolyte solutions using the CHI760E electrochemical workstation. Co (OH) prepared on and on nickel foam with commercial Pt/C, respectively2The nanoplatelets serve as working electrodes and their HER performance was measured as a comparison. Co (OH)2The preparation of (1) is based on the example 1 and omits Cu (NO) in the raw material3)2·3H2O is prepared. Linear Sweep Voltammetry (LSV) at 5.0mV · s-1And the polarization curve was obtained at 90% ohmic compensation.
FIG. 17 is a Cu doped Co (OH) with different Cu contents of 3.6%, 6.2% and 9.7%2Hydrogen Evolution Reaction (HER) polarization curve of the nanoplatelets. The Cu doping amount is shown to also significantly influence the HER activity of the catalyst, and the sample with the Cu doping amount of 6.2% achieves the best.
FIG. 18 is a Cu doped Co (OH)2Nanosheet array structure material, Co (OH)2Hydrogen Evolution Reaction (HER) polarization curves for nanoplates, Pt/C and nickel foam. As can be seen from the figure, Cu-doped Co (OH)2The material with the nano-sheet array structure can reach 10mA cm under the overpotential of 76mV-2Current density much less than that of Co (OH)2131mV of catalyst. Although Pt/C electrodes show outstanding HER activity at low current densities, at high current densities the material is very prone to flaking off and activity is affected. Furthermore, Cu-doped Co (OH)2The nano-sheet array structure material can respectively reach 500mA cm under the overpotential of 234mV and 261mV-2And 1000mA · cm-2High current density.
HER electrocatalytic stability was evaluated using a current density time curve at constant overpotential 76, 194, 234mV, as shown in figure 19. After 21 hours of continuous electrolytic reaction, the current density was maintained at 92.3% or more of the initial current density, and good HER electrocatalytic stability was exhibited.
The electrochemical active area of the material under HER conditions was evaluated using double layer capacitance, as shown in figure 20. Cu doped Co (OH)2The electric double layer capacitance was 7.2 mF. cm-2Greater than Co (OH)23.6 mF. cm-2Indicating that the Cu doping increases the electrochemically active area of the sample.
FIG. 21 is an Electrochemical Impedance (EIS) diagram showing Cu doped Co (OH)2The semicircle diameter of the nano-sheet array structure material is small, which shows that the nano-sheet array structure material has small resistance and faster catalytic kinetics.
Example 5
Cu-doped Co (OH)2The nano-sheet array structure material is applied as a catalyst for the electrolysis reaction of all urea.
The specific application method comprises the following steps: 2 Cu-doped Co (OH) areas of 0.5X 0.5cm2The nanosheet array structure material is assembled in a double-electrode electrolytic cell as an anode and a cathode respectively, and the electrolysis performance of the total urea is tested in 1.0M KOH and 0.33M urea electrolyte solutions. And with Co (OH)2The nanosheets and Pt/C were used as an anode and cathode in combination as a comparative pair.
Fig. 22 is a 90% iR compensated electrode LSV polarization curve. As can be seen from the figure, Cu-doped Co (OH)2The nano-sheet array structure material can reach 10mA cm under the voltage of 1.389V-2The current density is only 1.781V is needed to drive 500mA cm-2High current density. Obviously higher than the electric pair activity of commercial Pt/C composition, and the commercial Pt/C can not reach 500mA cm because the material is easy to fall off-2High current density.
FIG. 23 is a graph of current density versus time at constant voltage. As can be seen from the figure, Cu-doped Co (OH)2The nanosheet array structure material is continuously electrolyzed for 7h at constant voltage of 1.457VThe stream density decreased by 16%. And after the original electrolyte solution is replaced by the fresh electrolyte solution at the 7h, the current density can be remarkably recovered to 92.5 percent of the original (0h) current density. Similarly, the current density was still recovered to 90.5% of the original current density after a second replacement of fresh electrolyte solution at 14 h. In addition the catalyst has similar long term durability at potentials of 1.65 and 1781V. Description of Cu6.2％-Co(OH)2The electrode has excellent long-term stability.
The above detailed description of the Cu-doped cobalt hydroxide nanosheet array structure material, the preparation method and the application thereof with reference to the embodiments are illustrative and not restrictive, and several embodiments can be enumerated according to the limited scope, so that changes and modifications without departing from the general concept of the present invention shall fall within the protection scope of the present invention.
Claims (10)
1. Cu-doped Co (OH)2The preparation method of the nano-sheet array structure material is characterized by comprising the following steps:
dissolving copper salt, cobalt salt and hexamethylenetetramine in a mixed solvent of water and methanol, transferring the solution to a reaction kettle, obliquely placing foamed nickel in the solution, carrying out solvothermal reaction, cooling to room temperature after the reaction is finished, washing and drying a product to obtain Cu-doped Co (OH)2A nanosheet array structure material.
2. The method according to claim 1, wherein the copper salt is copper nitrate trihydrate; the cobalt salt is cobalt nitrate hexahydrate.
3. The method according to claim 1 or 2, wherein the ratio of the amounts of the copper salt, the cobalt salt and the hexamethylenetetramine is 0.1-0.3: 2: 5.
4. The production method according to claim 1 or 2, wherein the concentration of hexamethylenetetramine in the mixed solvent of water and methanol is 0.143M.
5. The production method according to claim 1 or 2, wherein the volume ratio of water to methanol is 4: 3.
6. The method according to claim 1 or 2, wherein the solvothermal reaction is carried out at 120 ℃ for 6 hours.
7. A Cu-doped Co (OH) prepared by the preparation method of any one of claims 1 to 62A nanosheet array structure material.
8. The Cu-doped Co (OH) of claim 72Application of the nanosheet array structure material as a Urea Oxidation Reaction (UOR) electrocatalyst.
9. The Cu-doped Co (OH) of claim 72Application of the nanosheet array structure material as a Hydrogen Evolution Reaction (HER) electrocatalyst.
10. The Cu-doped Co (OH) of claim 72The nanosheet array structure material is applied as an electrocatalyst for a full urea decomposition reaction.
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| CN114807963A (en) * | 2022-04-15 | 2022-07-29 | 浙江大学衢州研究院 | Copper-doped cobalt sulfide porous nanosheet/nickel foam electrode and preparation method and application thereof |
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