CN110699702B - Hillock-shaped in-situ nickel-vanadium double metal hydroxide catalyst and preparation method and application thereof - Google Patents
Hillock-shaped in-situ nickel-vanadium double metal hydroxide catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 24
- HBVFXTAPOLSOPB-UHFFFAOYSA-N nickel vanadium Chemical compound [V].[Ni] HBVFXTAPOLSOPB-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910000000 metal hydroxide Inorganic materials 0.000 title claims abstract description 16
- 150000004692 metal hydroxides Chemical class 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 116
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 54
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000012046 mixed solvent Substances 0.000 claims abstract description 12
- 238000004729 solvothermal method Methods 0.000 claims abstract description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004202 carbamide Substances 0.000 claims abstract description 10
- 230000007935 neutral effect Effects 0.000 claims abstract description 10
- 229910021550 Vanadium Chloride Inorganic materials 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 9
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 claims abstract description 9
- 238000002791 soaking Methods 0.000 claims abstract description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 235000019441 ethanol Nutrition 0.000 claims description 22
- 239000006260 foam Substances 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 10
- 239000012498 ultrapure water Substances 0.000 claims description 10
- 238000011049 filling Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 12
- 238000004140 cleaning Methods 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000010411 electrocatalyst Substances 0.000 description 21
- 238000004502 linear sweep voltammetry Methods 0.000 description 8
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- AJGNQFYKDIENNF-UHFFFAOYSA-G [OH-].[V+5].[Ni+2].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-] Chemical compound [OH-].[V+5].[Ni+2].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-] AJGNQFYKDIENNF-UHFFFAOYSA-G 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
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- 239000013078 crystal Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- 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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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8472—Vanadium
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- B01J35/33—
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
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- 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
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
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Abstract
The invention discloses a hill-shaped in-situ nickel-vanadium double metal hydroxide catalyst and a preparation method and application thereof, and the method comprises the following steps: pretreating foamed nickel; step two: adding vanadium chloride and urea into a mixed solvent of alcohol and N-methyl pyrrolidone; step three: soaking the foamed nickel in the solution A to perform a solvothermal reaction at 115-125 ℃ for 23-25 h; step four: after the reaction is finished, naturally cooling the reaction kettle to room temperature, alternately cleaning the reaction kettle by water and alcohol, collecting and drying the reaction kettle to obtain a hill-shaped in-situ nickel-vanadium double metal hydroxide catalyst; the method has the characteristics of simple preparation process, low synthesis temperature, no need of large-scale equipment and harsh conditions and the like by adopting a solvothermal method, and the prepared hill-shaped in-situ nickel-vanadium double metal hydroxide catalyst has high activity and high stability and has good full-hydrolytic performance under alkaline and neutral conditions.
Description
Technical Field
The invention belongs to the field of electrocatalytic materials, and particularly relates to a hillock-shaped in-situ nickel-vanadium double metal hydroxide catalyst, and a preparation method and application thereof.
Background
With the increasing environmental pollution and the rapid consumption of fossil fuels, the development of renewable sustainable energy sources is imperative. Electrolysis of water to produce hydrogen (H) due to its carbon-free emission2) And oxygen (O)2) Is considered to be one of the most promising and competitive solutions[1]In the field of electrocatalysis, noble metal-based materials (oxides of Pt, Ru or Ir) are currently the best hydrogen-generating electrocatalysts, and their practical application is severely limited by scarcity and high cost.
Therefore, in recent years, researchers have been dedicated to the development of non-noble metal hydrogen production electrocatalysts with high catalytic activity, which are composed of elements with high abundance of crusta. Long term Ni-based Layered Double Hydroxides (LDH)Which has been regarded as promising anode catalysts, whose properties can be achieved by doping with heteroatoms[2](transition metals V, Fe, Co, Mn, etc.; non-metals N, S, P, Se, etc.) and compounding with conductive substrates[3]Further improvements have been made in methods such as carbon nanotubes, nickel foam, graphene, carbon fiber paper, and the like. Therefore, Ni-based LDHs show great potential as Oxygen Evolution Reaction (OER) anode catalysts and Hydrogen Evolution Reaction (HER) cathode catalysts and ultimately are able to drive bulk water splitting reactions at low operating potentials. Luan[4]Et al report on two-dimensional alpha-Ni (OH)2The influence of the structure of the material on the performance of the electrocatalytic oxygen evolution reaction can be prepared by regulating and controlling different solvent ratios to prepare four alpha-Ni (OH) with different structures (bud, flower, petal and sheet)2A material.
Experiments show that the petal-like alpha-Ni (OH)2The catalyst has the characteristics of high efficiency of hydrogen production and oxygen production, high electrocatalytic activity and stability, which can be attributed to the small size of the catalyst, so that the more the boundary active sites are, the more the active sites are exposed, the surface area is increased, the electrolyte permeation is facilitated, and meanwhile, the catalyst has good toughness and the electrocatalytic activity is obviously improved. In addition, in the previous reports on LDH synthesis, the solvent used was mainly water or a mixed solvent of water and alcohol, and few reports have used a mixed solvent of alcohol and azomethylpyrrolidone as a solvent.
[1]Zou X,Zhang Y.Noble Metal-Free Hydrogen Evolution Catalysts forWater Splitting.Chem.Soc.Rev.2015,44,5148-5180.
[2]Jiang J,Sun F,Zhou S,et al.Atomic-level insight into super-efficient electrocatalytic oxygen evolution on iron and vanadium co-dopednickel(oxy)hydroxide[J].Nature Communications,2018,9(1):2885.
[3]Ren J,Yuan G,Weng C,Chen L and Yuan Z.Uniquely integrated Fe-dopedNi(OH)2nanosheets for highly efficient oxygen and hydrogen evolutionreactions[J].Nanoscale,2018,10,10620-10628.
[4]Luan C,Liu G,Liu Y,Yu L,Wang Y,Xiao Y,Qiao H,Dai Xand ZhangX.Structure Effects of 2D Materials onα-Nickel Hydroxide for Oxygen Evolu@onReac@on[J].ACS Nano 2018,12,3875-3885.
Disclosure of Invention
The invention aims to provide a hill-shaped in-situ nickel-vanadium double hydroxide catalyst which is simple in preparation process, low in cost and easy to control in process, and a preparation method and application thereof.
In order to achieve the above object, the present invention adopts the following technical solutions.
A preparation method of a hill-shaped in-situ nickel-vanadium double metal hydroxide catalyst comprises the following steps:
the method comprises the following steps: pretreating foamed nickel;
step two: adding 62.92-70.78 mg of vanadium chloride and 66-78 mg of urea into a mixed solvent of alcohol and N-methylpyrrolidone, and uniformly stirring to obtain a solution A;
step three: soaking the foamed nickel treated in the step one in the solution A, pouring the foamed nickel into an inner reaction kettle, fixing the inner kettle in an outer kettle, placing the inner kettle in a homogeneous phase reactor, and carrying out solvothermal reaction at the rotating speed of 5-8 r/min and at the temperature of 115-125 ℃ for 23-25 h;
step four: after the reaction is finished, naturally cooling the reaction kettle to room temperature, then taking out the product foamed nickel after the reaction, and collecting the product foamed nickel after the product foamed nickel is alternately cleaned by water and alcohol;
step five: and drying the foamed nickel collected in the fourth step to obtain the hill-shaped in-situ nickel-vanadium double metal hydroxide catalyst.
Further, the step one, namely, the foam nickel pretreatment, comprises the steps of ultrasonically cleaning cut foam nickel of 1cm multiplied by 4.5cm in an acetone solution for 12-15 min, then pouring the foam nickel into prepared hydrochloric acid of 1-3 mol/L for ultrasonic cleaning for 5-8 min, finally alternately washing the foam nickel for 3-4 times by using absolute ethyl alcohol and ultrapure water respectively, and then drying the foam nickel for 10-15 h in vacuum at the temperature of 28-33 ℃.
Furthermore, the volume ratio of the azomethyl pyrrolidone to the alcohol in the mixed solvent in the second step is 1 (9-11).
Further, magnetic stirring is adopted in the stirring process in the second step, and the stirring time is 15-20 min.
Further, the solution A in the third step reacts in a reaction inner kettle, and the filling ratio is 60-64%.
Further, in the fourth step, the washing is carried out by alternately washing with ultrapure water and absolute ethyl alcohol for 3-4 times.
Further, the drying temperature in the fifth step is 70-75 ℃, and the time is 4-6 hours.
An application of hillock-shaped in-situ Ni-V bimetal hydroxide catalyst in hydrogen and oxygen evolution reaction under alkaline and neutral conditions.
Compared with the prior art, the method has the following specific beneficial effects:
1) compared with a synthesis strategy, the invention adopts a one-step solvothermal method, and has the characteristics of simple preparation process, low synthesis temperature, no need of large-scale equipment and harsh conditions and the like.
2) Ethanol is adopted as a solvent, and the solvent is non-toxic and non-corrosive; compared with the common water solvent, the water-soluble organic acid has lower boiling point, lower viscosity and surface tension, and low ionic strength, and has better reaction performance than water; the temperature of the reaction is determined depending on factors such as the activity temperature of the catalyst, the thermal effect of the reaction, the boiling points of the raw materials and products, and the thermal stability of the catalyst, and thus, the optimum reaction temperature may be different when the ratio of the raw materials to the solvent is changed.
3) In the invention, a small amount of nitrogen methyl pyrrolidone is added into a reaction solvent, and the control of the existing state of nickel vanadium hydroxide in the reaction is realized by strictly and synergistically controlling the volume of the nitrogen methyl pyrrolidone and alcohol, the concentration and proportion of a vanadium source and urea, the reaction time, the reaction temperature, the reaction filling ratio and other parameters.
4) Foam Nickel (NF) is not only a hard template agent, but also provides a nickel source. NF is a typical 3D porous foam metal, and the unique three-dimensional structure of the NF increases the loading capacity of the material and provides more reactive sites; the porous structure is beneficial to the transmission of substances and the timely overflow of gas; the use of expensive adhesives can be avoided to reduce contact resistance and improve conductivity. In addition, the integrated bone-meat connected structure is not only beneficial to improving the conductivity of the electrocatalyst, but also can enhance the mechanical stability of the electrode, thereby improving the activity and stability of the catalyst.
5) When the material is applied to a full-electrolysis water catalyst, the material shows good electrochemical activity. The NiV-LDH/NF electrodes of the invention were subjected to full-hydrolysis electrocatalytic tests in alkaline (pH 14) and neutral (pH 7) solutions, respectively. The catalytic test is carried out in an alkaline environment, and when the current density reaches 10mA/cm2The HER and OER overpotentials required were 208mV and 260mV, respectively. The catalyst is tested in a neutral environment, and when the current density reaches 10mA/cm2The required overpotentials for HER and OER were 324mV and 560mV, respectively. The result shows that the NiV-LDH/NF electrode has good full-hydrolytic performance under alkaline and neutral conditions.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of NiV-LDH/NF electrocatalyst prepared in example 1 of the present invention
FIG. 2 is a Scanning Electron Microscope (SEM) micrograph of NiV-LDH/NF electrocatalyst prepared according to example 1 of the present invention
FIG. 3 is a high magnification Scanning Electron Microscope (SEM) photograph of NiV-LDH/NF electrocatalyst prepared in example 1 of the present invention
FIG. 4 is a low power Transmission Electron Microscope (TEM) photograph of NiV-LDH/NF electrocatalyst prepared in example 1 of the present invention
FIG. 5 is a high-power Transmission Electron Microscope (TEM) photograph of NiV-LDH/NF electrocatalyst prepared in example 1 of the present invention
FIG. 6 is a graph of hydrogen production performance (HER) of Linear Sweep Voltammetry (LSV) curves under alkaline conditions for NiV-LDH/NF electrocatalyst prepared in example 1 of the present invention
FIG. 7 is a graph of oxygen evolution performance (OER) of Linear Sweep Voltammetry (LSV) curves under alkaline conditions for NiV-LDH/NF electrocatalyst prepared in example 1 of the present invention
FIG. 8 is a graph of oxygen evolution performance (HER) of Linear Sweep Voltammetry (LSV) curves under neutral conditions for NiV-LDH/NF electrocatalyst prepared in example 1 of the present invention
FIG. 9 is a graph of oxygen evolution performance (OER) of Linear Sweep Voltammetry (LSV) curves under neutral conditions for NiV-LDH/NF electrocatalyst prepared in example 1 of the present invention
Detailed Description
The present invention will be described in further detail with reference to the following examples, which are not intended to limit the invention thereto.
Example 1:
the method comprises the following steps: the cut foam nickel with the size of 1cm multiplied by 4.5cm is firstly cleaned by ultrasonic in acetone for 12min, then cleaned by ultrasonic in 1mol/L hydrochloric acid for 8min, then washed by absolute ethyl alcohol and ultrapure water for 3 times, and finally dried in vacuum at 28 ℃ for 15h for later use.
Step two: adding 62.92mg of vanadium chloride and 66mg of urea into a mixed solvent of nitrogen methyl pyrrolidone and alcohol with the volume ratio of 1:11, and uniformly stirring for 15min to obtain a solution A;
step three: pouring the solution A into a 50mL reaction inner kettle, obliquely putting the foamed nickel treated in the step one into the reaction inner kettle for soaking, further putting the inner kettle into an outer kettle for fixing, putting the inner kettle into a homogeneous phase reactor with the filling ratio of 61%, and carrying out solvothermal reaction for 25 hours at the rotating speed of 5r/min and the temperature of 115 ℃;
step four: after the reaction is finished, naturally cooling the reaction kettle to room temperature, then taking out the product foamed nickel after the reaction, alternately cleaning for 3-4 times by using water and alcohol, and collecting;
step five: and (4) drying the foamed nickel collected in the fourth step at the temperature of 70 ℃ for 6 hours to obtain the hill-shaped in-situ nickel-vanadium double metal hydroxide catalyst (NiV-LDH/NF) electrode.
FIG. 1 is an X-ray diffraction (XRD) pattern of a NiV-LDH/NF electrocatalyst prepared according to example 1 of the present invention, from which it can be seen that there are two phases, one is a peak of substrate Ni (PDF #65-0380) and the other is a pure phase of α -Ni (OH) grown on a foamed nickel substrate2(PDF#38-0715)。
FIG. 2 is a Scanning Electron Microscope (SEM) photograph of NiV-LDH/NF electrocatalyst prepared in example 1 of the present invention, which shows the dense hilly-shaped array morphology formed by the NiV-LDH nanosheets vertically grown on the foamed nickel.
FIG. 3 is a high magnification Scanning Electron Microscope (SEM) photograph of NiV-LDH/NF electrocatalyst prepared in example 1 of the present invention, in which the surface roughness of NiV-LDH can be seen, and the thickness is about 20 nm.
FIG. 4 is a low-power Transmission Electron Microscope (TEM) photograph of the NiV-LDH/NF electrocatalyst prepared in example 1 of the present invention, in which a hilly morphology of NiV-LDH can be observed, consistent with the scanning results.
FIG. 5 is a high-power Transmission Electron Microscope (TEM) photograph of the NiV-LDH/NF electrocatalyst prepared in example 1 of the present invention, with a lattice fringe spacing of about 0.232nm, which corresponds to the (015) crystal plane of the LDH phase, further validating the phase.
FIG. 6 is a graph of hydrogen production performance (HER) of Linear Sweep Voltammetry (LSV) curve of NiV-LDH/NF electrocatalyst prepared in example 1 of the present invention under alkaline condition, NiV-LDH/NF shows good electrocatalytic hydrogen production activity, and current density reaches 10mA/cm2The overpotentials required were 203mV, respectively.
FIG. 7 is an oxygen evolution performance graph (OER) of a Linear Sweep Voltammetry (LSV) curve of an NiV-LDH/NF electrocatalyst prepared in example 1 of the present invention under alkaline conditions, the NiV-LDH/NF shows good electrocatalytic oxygen evolution activity, and the current density reaches 10mA/cm2The overpotentials required were 160mV, respectively.
FIG. 8 is a graph of oxygen evolution performance (HER) of the Linear Sweep Voltammetry (LSV) curve of the NiV-LDH/NF electrocatalyst prepared in example 1 of the present invention under neutral conditions, the NiV-LDH/NF shows good electrocatalytic hydrogen production activity, and the current density reaches 10mA/cm2The overpotentials required were 327mV respectively.
FIG. 9 is an oxygen evolution performance graph (OER) of the Linear Sweep Voltammetry (LSV) curve of the NiV-LDH/NF electrocatalyst prepared in example 1 of the present invention under neutral condition, the NiV-LDH/NF shows good electrocatalytic oxygen evolution activity, and the current density reaches 10mA/cm2The overpotentials required were 500mV each.
Example 2:
the method comprises the following steps: the cut foam nickel with the size of 1cm multiplied by 4.5cm is firstly cleaned by ultrasonic in acetone for 15min, then cleaned by ultrasonic in 3mol/L hydrochloric acid for 5min, then washed by absolute ethyl alcohol and ultrapure water for 4 times alternately, and finally dried in vacuum at 29 ℃ for 14h for later use.
Step two: 70.78mg of vanadium chloride and 78.00mg of urea are simultaneously added into a mixed solvent of nitrogen methyl pyrrolidone and alcohol with the volume ratio of 1:9, and the mixture is uniformly stirred for 16min to obtain a solution A;
step three: pouring the solution A into a 50mL reaction inner kettle, obliquely putting the foamed nickel treated in the step one into the reaction inner kettle for soaking, further putting the inner kettle into an outer kettle for fixing, then putting the inner kettle into a homogeneous phase reactor, wherein the filling ratio is 60%, and carrying out solvothermal reaction for 25h at the rotating speed of 6r/min and the temperature of 118 ℃;
step four: after the reaction is finished, naturally cooling the reaction kettle to room temperature, then taking out the product foamed nickel after the reaction, alternately cleaning for 3-4 times by using water and alcohol, and collecting;
step five: and (4) drying the foamed nickel collected in the fourth step at the temperature of 71 ℃ for 6 hours to obtain the hill-shaped in-situ nickel-vanadium double metal hydroxide catalyst (NiV-LDH/NF) electrode.
Example 3:
the method comprises the following steps: taking cut foam nickel with the size of 1cm multiplied by 4.5cm, firstly carrying out ultrasonic cleaning in acetone for 13min, then carrying out ultrasonic cleaning in 2mol/L hydrochloric acid for 7min, then alternately washing with absolute ethyl alcohol and ultrapure water for 3 times, and finally carrying out vacuum drying at 30 ℃ for 13h for later use.
Step two: adding 62.89mg of vanadium chloride and 68.40mg of urea into a mixed solvent of N-methyl pyrrolidone and alcohol with the volume ratio of 1:10, and uniformly stirring for 17min to obtain a solution A;
step three: pouring the solution A into a 50mL reaction inner kettle, obliquely putting the foamed nickel treated in the step one into the reaction inner kettle for soaking, further putting the inner kettle into an outer kettle for fixing, putting the inner kettle into a homogeneous phase reactor with a filling ratio of 62%, and carrying out solvothermal reaction for 24 hours at a rotating speed of 7r/min and a temperature of 120 ℃;
step four: after the reaction is finished, naturally cooling the reaction kettle to room temperature, then taking out the product foamed nickel after the reaction, alternately cleaning for 3-4 times by using water and alcohol, and collecting;
step five: and (4) drying the foamed nickel collected in the fourth step at the temperature of 72 ℃ for 5 hours to obtain the hill-shaped in-situ nickel-vanadium double metal hydroxide catalyst (NiV-LDH/NF) electrode.
Example 4:
the method comprises the following steps: the cut foam nickel with the size of 1cm multiplied by 4.5cm is firstly cleaned by ultrasonic in acetone for 14min, then cleaned by ultrasonic in 3mol/L hydrochloric acid for 6min, then washed by absolute ethyl alcohol and ultrapure water for 4 times alternately, and finally dried in vacuum at 31 ℃ for 12h for later use.
Step two: 64.86mg of vanadium chloride and 70.80mg of urea are simultaneously added into a mixed solvent of nitrogen methyl pyrrolidone and alcohol with the volume ratio of 1:10.5, and the mixture is uniformly stirred for 18min to obtain a solution A;
step three: pouring the solution A into a 50mL reaction inner kettle, obliquely putting the foamed nickel treated in the step one into the reaction inner kettle for soaking, further putting the inner kettle into an outer kettle for fixing, putting the inner kettle into a homogeneous phase reactor with a filling ratio of 63%, and carrying out a solvothermal reaction at a rotating speed of 8r/min and at a temperature of 123 ℃ for 23 hours;
step four: after the reaction is finished, naturally cooling the reaction kettle to room temperature, then taking out the product foamed nickel after the reaction, alternately cleaning for 3-4 times by using water and alcohol, and collecting;
step five: and (4) drying the foamed nickel collected in the fourth step at 73 ℃ for 5 hours to obtain the hill-shaped in-situ nickel-vanadium double metal hydroxide catalyst (NiV-LDH/NF) electrode.
Example 5:
the method comprises the following steps: the cut foam nickel with the size of 1cm multiplied by 4.5cm is firstly cleaned by ultrasonic in acetone for 14min, then cleaned by ultrasonic in 3mol/L hydrochloric acid for 5min, then washed by absolute ethyl alcohol and ultrapure water for 3 times alternately, and finally dried in vacuum at 32 ℃ for 11h for later use.
Step two: 66.84mg of vanadium chloride and 73.20mg of urea are simultaneously added into a mixed solvent of nitrogen methyl pyrrolidone and alcohol with the volume ratio of 1:9.5, and the mixture is uniformly stirred for 19min to obtain a solution A;
step three: pouring the solution A into a 50mL reaction inner kettle, obliquely putting the foamed nickel treated in the step one into the reaction inner kettle for soaking, further putting the inner kettle into an outer kettle for fixing, putting the inner kettle into a homogeneous phase reactor with a filling ratio of 64%, and carrying out solvothermal reaction for 23 hours at 125 ℃ at a rotating speed of 5 r/min;
step four: after the reaction is finished, naturally cooling the reaction kettle to room temperature, then taking out the product foamed nickel after the reaction, alternately cleaning for 3-4 times by using water and alcohol, and collecting;
step five: and (4) drying the foamed nickel collected in the fourth step at the temperature of 74 ℃ for 4-6 h to obtain the hill-shaped in-situ nickel-vanadium double metal hydroxide catalyst (NiV-LDH/NF) electrode.
Example 6:
the method comprises the following steps: the cut foam nickel with the size of 1cm multiplied by 4.5cm is firstly cleaned by ultrasonic in acetone for 14min, then cleaned by ultrasonic in 1mol/L hydrochloric acid for 7min, then washed by absolute ethyl alcohol and ultrapure water for 4 times alternately, and finally dried in vacuum at 33 ℃ for 10h for later use.
Step two: 68.81mg of vanadium chloride and 75.6mg of urea are simultaneously added into a mixed solvent of nitrogen methyl pyrrolidone and alcohol with the volume ratio of 1:10, and the mixture is uniformly stirred for 20min to obtain a solution A;
step three: pouring the solution A into a 50mL reaction inner kettle, obliquely putting the foamed nickel treated in the step one into the reaction inner kettle for soaking, further putting the inner kettle into an outer kettle for fixing, putting the inner kettle into a homogeneous phase reactor with a filling ratio of 62%, and carrying out solvothermal reaction for 24 hours at a rotating speed of 6r/min and a temperature of 120 ℃;
step four: after the reaction is finished, naturally cooling the reaction kettle to room temperature, then taking out the product foamed nickel after the reaction, alternately cleaning for 3-4 times by using water and alcohol, and collecting;
step five: and (4) drying the foamed nickel collected in the fourth step at the temperature of 75 ℃ for 4 hours to obtain the hill-shaped in-situ nickel-vanadium double metal hydroxide catalyst (NiV-LDH/NF) electrode.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the above embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the embodiments of the invention without departing from the spirit and scope of the invention, which is to be covered by the claims.
Claims (7)
1. A preparation method of a hill-shaped in-situ nickel-vanadium double metal hydroxide catalyst is characterized by comprising the following steps:
the method comprises the following steps: pretreating foamed nickel;
step two: adding 62.92-70.78 mg of vanadium chloride and 66-78 mg of urea into a mixed solvent of ethanol and N-methyl pyrrolidone at the same time, wherein the volume ratio of N-methyl pyrrolidone to ethanol is 1 (9-11), and uniformly stirring to obtain a solution A;
step three: soaking the foamed nickel treated in the step one in the solution A, then pouring the foamed nickel into an inner reaction kettle with a filling ratio of 60-64%, then placing the inner kettle into an outer kettle for fixing, then placing the inner kettle into a homogeneous reactor, and carrying out solvothermal reaction at a rotating speed of 5-8 r/min and at a temperature of 115-125 ℃ for 23-25 h;
step four: after the reaction is finished, naturally cooling the reaction kettle to room temperature, then taking out the product foamed nickel after the reaction, and collecting the product foamed nickel after the product foamed nickel is alternately cleaned by water and alcohol;
step five: and drying the foamed nickel collected in the fourth step to obtain the hill-shaped in-situ nickel-vanadium double metal hydroxide catalyst.
2. The method of preparing a hill-shaped in situ nickel vanadium double hydroxide catalyst as claimed in claim 1, wherein: the step one, foam nickel pretreatment, namely, performing ultrasonic cleaning on cut 1cm multiplied by 4.5cm foam nickel in an acetone solution for 12-15 min, then pouring the foam nickel into prepared 1-3 mol/L hydrochloric acid for ultrasonic cleaning for 5-8 min, finally alternately washing the foam nickel for 3-4 times by using absolute ethyl alcohol and ultrapure water respectively, and then performing vacuum drying for 10-15 h at the temperature of 28-33 ℃.
3. The method of preparing a hill-shaped in situ nickel vanadium double hydroxide catalyst as claimed in claim 1, wherein: and in the second step, magnetic stirring is adopted in the stirring process, and the stirring time is 15-20 min.
4. The method of preparing a hill-shaped in situ nickel vanadium double hydroxide catalyst as claimed in claim 1, wherein: and in the fourth step, washing is carried out for 3-4 times by alternately washing with ultrapure water and absolute ethyl alcohol.
5. The method of preparing a hill-shaped in situ nickel vanadium double hydroxide catalyst as claimed in claim 1, wherein: and the drying temperature in the fifth step is 70-75 ℃, and the drying time is 4-6 h.
6. A hillock-like in-situ nickel vanadium double hydroxide catalyst prepared by the method of any one of claims 1 to 5.
7. Use of the hill-shaped in situ nickel vanadium double hydroxide catalyst of claim 6 in hydrogen and oxygen evolution reactions under basic and neutral conditions.
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