CN110575836B - Pt-loaded Fe-doped alpha-phase nickel hydroxide nanosheet array material, and preparation method and application thereof - Google Patents
Pt-loaded Fe-doped alpha-phase nickel hydroxide nanosheet array material, and preparation method and application thereof Download PDFInfo
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- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 8
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- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical group O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 2
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- 239000002184 metal Substances 0.000 abstract description 2
- 239000000969 carrier Substances 0.000 abstract 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- B01J35/33—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a Pt-loaded Fe-doped alpha-phase nickel hydroxide nanosheet array material, a preparation method and application thereof2Nanosheet array material on nanosheets, Fe3+Partially substituted alpha-Ni (OH)2Ni in lattice2+Providing stronger metal support bonding site anchored ultra-small Pt nanoparticles, Pt nanoparticles and Fe-doped alpha-Ni (OH)2Strong contact between nanosheet carriers (Fe)3+O (H) -Pt bond) contributes to excellent catalytic activity and stability, and the Pt supported Fe doped alpha-Ni (OH) provided by the invention2The nano-sheet array material is used as a hydrogen evolution reaction electrocatalyst and has the advantages of high catalytic activity, excellent stability and simple preparation process.
Description
Technical Field
The invention belongs to the field of nano material preparation methods and electrocatalysis application, and particularly relates to a Pt-loaded Fe-doped alpha-Ni (OH)2A nano-sheet array material, a preparation method and application.
Background
Hydrogen is recognized as a clean energy source due to its high energy density and environmental friendliness. Electrocatalytic alkaline water electrolysis hydrogen production is considered to be an effective strategy due to the advantages of easy availability of reactants, safe preparation, stable output and the like. Pt has strong adsorption and recombination capacity to H atoms of an active intermediate, and is the Hydrogen Evolution Reaction (HER) electrocatalyst with the strongest activity at present. However, due to the slow water dissociation step of the platinum surface in alkaline electrolyte, the catalytic activity of Pt in alkaline electrolyte is about two orders of magnitude less than in acidic media. One effective strategy to increase the HER activity of Pt in alkaline media is to combine Pt with earth-rich materials that have more oxophilic surfaces capable of dissociating H-OH bonds in water.
Transition metal (hydr) oxides are capable of effectively dissociating H-OH bonds, although they convert adsorbed hydrogen atoms into H2The velocity of the molecules is slower. Pt-modified Ni (OH)2The electrode can synergistically catalyze the HER in an alkaline medium, wherein a metal hydroxide interface provides an active site for the dissociation of water and a Pt surface promotes hydrogen atom recombination, thereby accelerating the HER process. The material with abundant earth reserves is combined with Pt, so that a direction is provided for developing a commercial hydrogen production catalyst with high efficiency, stability and low Pt loading capacity.
In the prior art, Pt-loaded Ni (OH) applied to HER2And NiFe LDH catalysts are typically synthesized by a two-step reaction route, i.e., Pt nanoparticles are deposited on pre-prepared Ni (OH)2Or on a NiFe LDH support. This synthetic route does not guarantee that all Pt nanocrystals are grown directly on the support, and therefore, it is difficult to separate the target composite from the self-nucleated Pt nanoparticles grown in solution. In addition, some catalysts need to be prepared into modified electrodes with binders for electrocatalytic reaction after synthesis, which can prevent the full exertion of the inherent catalytic performance. In addition, the consumption of Pt in most of the Pt-supported catalysts is still high at present, which hinders the commercial application. It is a feasible route to construct high performance HER catalysts with excellent activity and durability in alkaline media by further reducing the Pt loading, increasing the Pt utilization, and providing sufficient active sites to dissociate the H-OH bonds in water.
In the prior art, the preparation method of the Pt supported nano-structured catalyst is complex and has low HER catalytic activity. Therefore, it is of great significance to synthesize a Pt-supported HER catalyst having high activity and durability by a simple method.
Disclosure of Invention
The invention aims to provide a Pt-loaded Fe-doped alpha-Ni (OH)2A nano-plate array structure and its preparing process features that the low-temp chemical liquid phase method is used to directly synthesize Pt carried Fe doped alpha-Ni (OH) on the substrate of electrically conductive foam nickel in one step2The nano-sheet array structure has simple synthesis process and low cost.
Another objective of the invention is to provide a Pt-loaded Fe-doped alpha-Ni (OH)2Application of a nanosheet array structure as a Hydrogen Evolution Reaction (HER) electrocatalyst.
The invention provides a Pt-loaded Fe-doped alpha-Ni (OH)2The preparation method of the nanosheet array structure comprises the following steps:
sequentially dissolving nickel salt, ferric salt, urea, a sodium citrate aqueous solution and a chloroplatinic acid aqueous solution in absolute methanol, transferring the solution to a reaction kettle, obliquely placing foamed nickel in the solution, carrying out a solvothermal reaction, cooling to room temperature after the reaction is finished, washing and drying a product to obtain the Pt-loaded Fe-doped alpha-Ni (OH)2A nanosheet array.
Further, the nickel salt is nickel nitrate hexahydrate; the iron salt is ferric nitrate nonahydrate.
The ratio of the nickel salt, the iron salt, the urea, the sodium citrate and the chloroplatinic acid is 0.75-1.25: 0.1-0.3: 1:0.1: 0.006-0.018, preferably 1:0.2:1:0.1: 0.012.
The concentration of urea in anhydrous methanol was 0.03M.
The concentration of the aqueous sodium citrate solution was 0.05M.
The concentration of the chloroplatinic acid aqueous solution is 0.03M.
The solvent thermal reaction condition is that the reaction is carried out for 6-10h at 130-150 ℃, and the reaction is preferably carried out for 8h at 140 ℃.
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 oxide film on the surface, and cleaning with deionized water and anhydrous ethanol for 3-5 times; when in use, the foam nickel is cut into the size of 2 multiplied by 3 cm.
The washing is 3-5 times by using deionized water and absolute ethyl alcohol respectively.
The drying is carried out in a vacuum drying oven at 60 ℃ for 6-12 h.
The invention also provides a Pt loaded Fe doped alpha-Ni (OH) prepared by the preparation method2Nano-sheet arrayColumn structure, Pt nanoparticles all grown directly on Fe doped alpha-Ni (OH)2And (3) a nano-sheet array material. When the Pt loading is 2.3 percent, the Pt loading Fe is doped with alpha-Ni (OH)2The shape of the nano-sheet array structure is an array structure formed by crossing nano-sheets with the transverse dimension of 500-700 nm; fe doped alpha-Ni (OH)2Pt nano particles with the size of 2-3.7 nm are uniformly distributed on the nano-chip.
The invention also provides a Pt loaded Fe doped alpha-Ni (OH)2Application of a nanosheet array structure as a Hydrogen Evolution Reaction (HER) electrocatalyst.
The Pt-loaded Fe-doped alpha-Ni (OH)2When the nano-sheet array material is applied as a hydrogen evolution reaction electrocatalyst, the specific method comprises the following steps: the Pt supported Fe doped alpha-Ni (OH) prepared on the foam nickel2The nanosheet array was cut into 0.5X 0.5cm size and used as a working electrode, and a CHI760E electrochemical workstation was used to perform the test using 1M KOH solution as the electrolyte. Carbon rods 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. By scanning at different rates (60, 80, 100, 120, 140, 160, 180 and 200 mV. multidot.s) in the absence of significant Faraday regions-1) Measurement of double layer capacitance (C) by Cyclic Voltammetry (CV)dl) Evaluating an electrochemically active area (ECSA); electrochemical Impedance (EIS) was tested at 100mV overpotential in the frequency range of 100kHz to 0.1 Hz. Fe doped alpha-Ni (OH) supported on nickel foam with commercial Pt/C, respectively2The nanosheet array material was used as a working electrode and HER performance was measured for comparison.
In the present invention, Fe3+Ion doping into alpha-Ni (OH)2Lattice, can pass Fe3+The-o (h) -Pt bond provides a strong bonding site to immobilize the Pt nanoparticles, thus forming a good interface to ensure better exposure of the Pt active sites. Fe doped alpha-Ni (OH)2The orderliness of interface water molecules can be reduced, and the electric charge is transferred through an electric double layer. The hydrophilic layered hydroxyl on the surface of the material can adsorb water molecules through hydrogen bonds. Subsequently, adsorbed water molecules are removed fromElectrons obtained on the electrode are dissociated into adsorbed hydrogen atoms and OH through a Volmer step-Ions. Fe doped alpha-Ni (OH)2The Ni and Fe atoms of the intermediate oxygen-philic alloy can stabilize OH-Ions, adsorbed hydrogen atoms are recombined on the surface of Pt atoms through Tafel step to form hydrogen, and OH-Ion Final doping from Fe alpha-Ni (OH)2And (4) surface desorption. Thus, Fe doped α -Ni (OH)2Synergistic effect of nanoplates and Pt nanoparticles, in which Fe is doped with alpha-Ni (OH)2The nanosheet interface catalyzes a Volmer process of water dissociation, and the surface of the Pt nanoparticle optimizes the adsorption energy of H atoms, so that the H atoms are compounded into hydrogen through a Tafel process.
Compared with the prior art, the method utilizes a one-step solvothermal method to generate NH by hydrolyzing urea3And CO2，NH3Dissolving in water to generate OH-And NH4 +，Ni2+Ions with OH-Ion Generation of Ni (OH)2While being Fe3+Incorporation of Ni (OH)2A crystal lattice. Methanol is selected as solvent and reducer, and H is put into2PtCl6Reducing the Pt nanoparticles into Pt nanoparticles, and regulating the nucleation and growth rate of the Pt nanoparticles by utilizing the chelating function of citrate ions. In the presence of Ni (OH)2Introduction of Fe into crystal lattice3+Partial substitution of Ni by ions2+Ions can provide stronger metal carrier bonding sites to fix Pt nano particles, and Pt-loaded Fe-doped alpha-Ni (OH) is synthesized on foamed nickel2A nanosheet array. The Pt loaded Fe doped alpha-Ni (OH) provided by the invention2The nanosheet array catalyst shows excellent catalytic activity and stability to HER in alkaline electrolyte, is simple in preparation process and environment-friendly, and has a great value in the practical application of hydrogen-producing electro-catalytic electrode materials.
Drawings
FIG. 1 shows Pt-loaded Fe-doped α -Ni (OH) prepared in example 12An X-ray powder diffraction (XRD) pattern of the nanoplatelets;
FIG. 2 shows Pt-loaded Fe-doped α -Ni (OH) prepared in example 12An energy dispersive X-ray spectroscopy (EDX) profile of the nanoplatelets;
FIG. 3 shows Pt minus prepared in example 1Fe-carrying doped alpha-Ni (OH)2A Scanning Electron Microscope (SEM) image of the nanoplatelet array;
FIG. 4 shows Pt supported Fe doped α -Ni (OH) prepared in example 12A Transmission Electron Microscope (TEM) image of the nanoplatelets;
FIG. 5 shows Pt supported Fe doped α -Ni (OH) prepared in example 12Scanning transmission electron microscope pictures (STEM) and corresponding elemental profiles of the nanoplates;
FIG. 6 shows Pt-loaded Fe-doped α -Ni (OH) prepared in example 12High Resolution Transmission Electron Microscopy (HRTEM) images of the nanoplates;
FIG. 7 shows Pt loaded Fe doped α -Ni (OH) with Pt loadings of 1.2% and 3.3% prepared in example 22An energy dispersive X-ray spectroscopy (EDX) profile of the nanoplatelets;
FIG. 8 is a graph of Pt loaded Fe doped α -Ni (OH) with 1.2% Pt loading prepared in example 22A Scanning Electron Microscope (SEM) image of the nanoplatelets;
FIG. 9 shows the Pt loaded Fe doped α -Ni (OH) with 3.3% Pt loading prepared in example 22A Scanning Electron Microscope (SEM) image of the nanoplatelets;
FIG. 10 is a graph of Pt loaded Fe doped α -Ni (OH) with 1.2% Pt loading prepared in example 22A Transmission Electron Microscope (TEM) image of the nanoplatelets;
FIG. 11 is a graph of Pt loaded Fe doped α -Ni (OH) with 3.3% Pt loading prepared in example 22A Transmission Electron Microscope (TEM) image of the nanoplatelets;
FIG. 12 is a plot of Pt loaded Fe doped α -Ni (OH) for different Pt loadings (1.2%, 2.3% and 3.3%) prepared in examples 1 and 22LSV curve diagram of Hydrogen Evolution Reaction (HER) of the nano-sheet array material.
FIG. 13 shows Pt-loaded Fe-doped α -Ni (OH) in example 32Nanosheet array material, Fe-doped alpha-Ni (OH)2LSV curve diagram of Hydrogen Evolution Reaction (HER) of nano sheet array material and Pt/C;
FIG. 14 shows Pt-loaded Fe-doped α -Ni (OH) of example 32A current density time curve diagram of a Hydrogen Evolution Reaction (HER) of the nano sheet array material and Pt/C;
FIG. 15 shows Pt-loaded Fe-doped α -Ni (OH) in example 32Nanosheet array material, Fe-doped alpha-Ni (OH)2A capacitance-current diagram of the nano-sheet array material at different scanning speeds;
FIG. 16 shows Pt supported Fe doped α -Ni (OH) of example 32Nanosheet array material, Fe-doped alpha-Ni (OH)2Impedance plot of the nanosheet array material;
FIG. 17 shows example 3Pt supported Fe doped α -Ni (OH)2Nanosheet array material, mass activity diagram of Pt/C.
Detailed Description
The invention is described in detail below with reference to the following examples and the accompanying drawings.
Example 1
Pt-loaded Fe-doped alpha-Ni (OH)2The preparation method of the nanosheet array material comprises the following steps:
soaking foamed nickel with the size of 2 multiplied by 3cm in 6M hydrochloric acid solution for 15min, and respectively cleaning the foamed nickel for 3 times by using deionized water and absolute ethyl alcohol;
accurately measure 35mL of anhydrous methanol and add to a 50mL clean small beaker, then weigh 1mmol of Ni (NO) separately3)2·6H2O，0.2mmol Fe(NO3)3·9H2O, 1mmol of urea, into a small beaker, then 2mL of 0.05M sodium citrate solution and finally 0.4mL of 0.03M H2PtCl6Stirring and dissolving the solution for 30min to obtain a uniform solution;
transferring the solution into a 50mL stainless steel reaction kettle with a polytetrafluoroethylene lining, obliquely putting clean foamed nickel into the solution, sealing and reacting in a drying oven at 140 ℃ for 8h, naturally cooling to room temperature after the reaction is finished, respectively cleaning the foamed nickel covering the sample with deionized water and absolute ethyl alcohol for 3 times, then putting the foamed nickel in a vacuum drying oven at 60 ℃ for 10h, and obtaining the Pt-loaded Fe-doped alpha-Ni (OH)2A nanosheet array material.
The phase of the product obtained in example 1 was characterized by X-ray powder diffractometer (XRD), and as a result, all diffraction peaks were compared with those of alpha-Ni (OH) in JCPDS: No.38-0715 card, as shown in FIG. 12The diffraction peaks of (a) correspond to each other.
Analysis of the product using energy dispersive X-ray spectroscopy (EDX), as shown in FIG. 2, indicates that Pt is supported on Fe doped α -Ni (OH)2On the nano-sheet, the atomic percentage of Ni, Fe and Pt elements is 95:5:1.1, and the Pt loading amount is calculated to be 2.3 percent.
The sample prepared in example 1 is subjected to morphology analysis by using a Scanning Electron Microscope (SEM), and as shown in FIG. 3, the sample is in an array structure formed by crossing nano sheets, and the transverse dimension of the nano sheets is 500-700 nm.
The appearance of the sample is further observed by using a Transmission Electron Microscope (TEM), and the result is shown in FIG. 4, which shows that the sample is composed of nanosheets loaded with Pt nanoparticles, wherein the size of the Pt nanoparticles is 2-3.7 nm.
The scanning transmission electron microscope picture (STEM) of fig. 5 further illustrates that the sample is a Pt nanoparticle supported nanosheet structure, and the corresponding elemental profile illustrates a uniform distribution of Ni, Fe, O and Pt elements, wherein Fe and Pt are lower in density than Ni and O.
Fig. 6 is a high-resolution transmission electron microscope (HRTEM) picture. The Pt nano particles show clear lattice stripes, the spacing between crystal faces is 0.23nm, and the Pt nano particles are matched with Pt (111) crystal faces; the spacing between the planes of the lattice fringes exhibited on the nanoplatelets was 0.27nm, corresponding to a-Ni (OH)2The (101) crystal plane of (a).
Example 2
Pt-loaded Fe-doped alpha-Ni (OH)2The preparation method of the nanosheet array material comprises the following steps:
accurately measuring 35mL of anhydrous methanol, adding into a clean small beaker, and respectively weighing 1mmol of Ni (NO)3)2·6H2O, 0.2mmol of Fe (NO)3)3·9H2O, 1mmol of urea was dissolved in absolute methanol, then 2mL of 0.05M sodium citrate solution was added, and finally 0.2mL or 0.6mL of 0.03M H was added2PtCl6Stirring and dissolving the solution for 30min to obtain a uniform solution.
The solution was transferred to a 50mL stainless steel reactor lined with Teflon and cleanedPutting the clean foam nickel into the solution obliquely, sealing and reacting in a baking oven at 140 ℃ for 8h, naturally cooling to room temperature after the reaction is finished, respectively cleaning the foam nickel covering the sample by deionized water and absolute ethyl alcohol for 3 times, and then drying the foam nickel in a vacuum drying oven at 60 ℃ for 10h to obtain Pt-loaded Fe-doped alpha-Ni (OH) with 1.2 percent and 3.3 percent of Pt loading capacity2A nanosheet array material; when H is present2PtCl6When the addition amount of the solution is 0.2mL, the obtained Pt-loaded Fe-doped alpha-Ni (OH)2The Pt loading amount of the nanosheet array material is 1.2%; when H is present2PtCl6When the addition amount of the solution is 0.6mL, the obtained Pt-loaded Fe-doped alpha-Ni (OH)2The loading of Pt of the nanosheet array material was 3.3%.
The product was analyzed using energy dispersive X-ray spectroscopy (EDX) as shown in fig. 7, where the atomic percentages of the elements Ni, Fe and Pt were 95:5:0.6 and 95:5:1.6, respectively. The Pt loadings were calculated to be 1.2% and 3.3%.
Morphology analysis of the sample prepared in example 2 was performed using a Scanning Electron Microscope (SEM), FIGS. 8 and 9 are Pt loaded Fe doped α -Ni (OH) with 1.2% and 3.3% Pt loading, respectively2The SEM image of (A) shows that the sample is an array structure formed by crossing nano sheets, wherein when the Pt loading is 1.2%, the transverse dimension of the nano sheets is 1.3-1.7 mu m (figure 8). When the Pt loading amount is 3.3%, the transverse dimension of the nano sheet is 460-860 nm (figure 9).
Morphology analysis of the sample prepared in example 2 was performed using Transmission Electron Microscopy (TEM), FIGS. 10 and 11 are Pt loaded Fe doped α -Ni (OH) with Pt loadings of 1.2% and 3.3%, respectively2The TEM image shows that the samples are all composed of nanosheets loaded with Pt nanoparticles. Wherein, when the Pt loading amount is 1.2%, the size of the Pt nano particles on the nano sheet is 1.6-2.7 nm (figure 10). When the Pt loading is 3.3%, the size of Pt nanoparticles is 2.0-4.3 nm, and part of the nanoparticles are agglomerated (FIG. 11).
Example 3
Pt-loaded Fe-doped alpha-Ni (OH)2Application of the nanosheet array material as a Hydrogen Evolution Reaction (HER) catalyst.
Specific application methodThe method comprises the following steps: the Pt supported Fe obtained in each example with an area of 0.5X 0.5cm was doped with alpha-Ni (OH)2The nanosheet array material was used as a working electrode, a carbon rod was used as a counter electrode, an Ag/AgCl electrode was used as a reference electrode, and the test was performed in a 1.0M KOH electrolyte solution using the CHI760E electrochemical workstation. Linear Sweep Voltammetry (LSV) at 5.0mV · s-1At a scan rate of 90% ohmic compensation, and doping with Pt/C, Fe of alpha-Ni (OH)2Nanosheet array material (Fe doped alpha-Ni (OH)2A comparative test was conducted by omitting a chloroplatinic acid solution in the raw material with respect to the preparation method in example 1) as a working electrode.
FIG. 12 is a Pt loaded Fe doped α -Ni (OH) with different Pt loadings of 1.2%, 2.3% and 3.3%2Hydrogen Evolution Reaction (HER) polarization curve of the nanoplate array material. It is shown that Pt loading significantly affects the HER activity of the catalyst, with the sample with Pt loading of 2.3% being optimal.
As shown in FIG. 13, Pt-loaded Fe-doped α -Ni (OH)2The nano-sheet array material is 10mA cm-2The overpotential of only 18mV under the current density is much less than that of Fe-doped alpha-Ni (OH)2The overpotential (147mV) of the nanosheet array material catalyst is also lower than that (35mV) required by commercial Pt/C. Further, 100mA · cm was driven-2And 500mA · cm-2The high current density only requires overpotentials of 66mV and 159mV, respectively.
FIG. 14 is a graph of current density versus time showing Pt loaded Fe doped α -Ni (OH)2Nanosheet array material (Pt)2.3％-Fe0.05Ni0.95(OH)2) The stability is excellent under low and high current densities, and the current density is kept above 92.3% after 16h of test. Whereas commercial Pt/C catalysts supported on nickel foam by a binder tended to fall off at 20mA cm-2The overpotential at the current density was 54mV, and the current density remained only 52.8% of the original after 16h of testing.
Evaluation of the electrochemically active area of the material with double layer capacitance, Pt loaded Fe doped α -Ni (OH) as shown in FIG. 152Nanosheet array materialThe electric double layer capacitance was 24.7 mF. cm-2Greater than Fe doped alpha-Ni (OH)2Electric double layer capacitor (3.9 mF. cm)-2) Indicating that Pt loading increases the electrochemically active area of the material.
FIG. 16 is an Electrochemical Impedance (EIS) graph showing Pt supported Fe doped α -Ni (OH)2The semicircular diameter of the nanosheet array material is small, which shows that the nanosheet array material has small resistance, and Pt loading is beneficial to promoting electron transfer.
FIG. 17 is a mass activity diagram showing Pt loaded Fe doped α -Ni (OH)2The nanosheet array material has higher activity than commercial Pt/C, wherein the mass activity is 15.22mA · mug at an overpotential of 70mVPt -1Is 28.7 times of that of commercial Pt/C (the commercial Pt/C is only 0.53mA · mugPt -1)。
Reference example above A Pt-loaded Fe doped alpha-Ni (OH)2The detailed description of the nanoplatelet array materials, the methods of preparation and the applications are illustrative and not restrictive, and several examples can be cited within the limits defined, and thus variations and modifications without departing from the general inventive concept are intended to be within the scope of the present invention.
Claims (8)
1. Pt-loaded Fe-doped alpha-Ni (OH)2The preparation method of the nanosheet array material is characterized by comprising the following steps:
dissolving nickel salt, ferric salt, urea, a sodium citrate aqueous solution and a chloroplatinic acid aqueous solution in absolute methanol, transferring the solution to a reaction kettle, obliquely placing foamed nickel in the solution, carrying out a solvothermal reaction, cooling to room temperature after the reaction is finished, washing and drying a product to obtain the Pt-loaded Fe-doped alpha-Ni (OH)2A nanosheet array material;
the solvent thermal reaction condition is that the reaction is carried out for 6-10h at the temperature of 130-150 ℃.
2. The method according to claim 1, wherein the nickel salt is nickel nitrate hexahydrate; the iron salt is ferric nitrate nonahydrate.
3. The method according to claim 1, wherein the ratio of the amounts of the nickel salt, iron salt, urea, sodium citrate and chloroplatinic acid is 0.75-1.25: 0.1-0.3: 1:0.1: 0.006-0.018.
4. The process according to any one of claims 1 to 3, wherein the urea is present in a concentration of 0.03M in dry methanol.
5. The method according to claim 1 or 2, wherein the concentration of the aqueous solution of sodium citrate is 0.05M.
6. The production method according to claim 1 or 2, wherein the concentration of the chloroplatinic acid aqueous solution is 0.03M.
7. Pt-loaded Fe-doped alpha-Ni (OH) prepared by the preparation method of any one of claims 1 to 62A nanosheet array material.
8. The Pt supported Fe doped a-Ni (OH) of claim 72Application of the nanosheet array material as a Hydrogen Evolution Reaction (HER) electrocatalyst.
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| CN111871426B (en) * | 2020-06-11 | 2023-08-29 | 安徽师范大学 | Pd nanoparticle-supported nickel-iron double hydroxide nanosheet array structure material, preparation method and application thereof |
| CN112501645B (en) * | 2020-12-10 | 2021-08-31 | 苏州大学 | Nickel hydroxide/nickel screen composite hydrogen and oxygen evolution electrode, preparation method and application thereof |
| CN112691682A (en) * | 2020-12-23 | 2021-04-23 | 泉州师范学院 | Pt nanowire, Pt NWs/Ni (OH)2Composite material and application |
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