CN115627493A - Platinum-doped catalyst electrode and preparation method and application thereof - Google Patents
Platinum-doped catalyst electrode and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention belongs to the technical field of electrocatalysts, and particularly relates to a platinum-doped catalyst electrode and a preparation method and application thereof. The platinum-doped catalyst electrode provided by the invention takes a nickel net as a substrate, and Ni (OH) is loaded on the substrate 2 The nanowire/sheet compound is used as a carrier, and the doping on the carrier is not higher than 0.06 mg/cm 2 Pt of (2). The invention is realized by doping Pt and Ni (OH) 2 The synergistic effect of the composite nano structure optimizes the HER/OER catalytic activity and catalytic reaction rate of the whole catalyst electrode and reduces reaction energy consumption. The electrode shows over commercial noble metal combination Pt/C @ NM | | RuO in alkaline water electrolyzer 2 The actual electrolytic Water Performance of @ NM.
Description
Technical Field
The invention belongs to the technical field of electrocatalysts, and particularly relates to a platinum-doped catalyst electrode and a preparation method and application thereof.
Background
With the rapid development of society, the shortage of energy is more and more severe, and the exploration and research of new energy are urgent. The research of environment-friendly clean energy sources such as solar energy, wind energy and the like is extremely advanced, but the use of the energy sources is severely restricted by external factors such as seasonality, regionality, volatility and the like. The hydrogen energy has the characteristics of high combustion heat value, wide source, no pollution and the like, and has extremely wide application prospect as secondary energy storage energy.
The water decomposition to generate the green hydrogen is the most ideal way for preparing hydrogen energy, and the whole water decomposition reaction consists of two half reactions of Hydrogen Evolution Reaction (HER) and Oxygen Evolution Reaction (OER). However, the high reaction energy barrier results in lower HER, OER reaction kinetics, requiring more energy to be expended to drive the reaction. Among them, pt proved to be the most ideal catalyst for HER, but its wide application was limited by high cost. At present, most of water decomposition catalysts are researched in laboratories and are based on a Nickel Foam (NF) substrate, a unique three-dimensional structure and a network-shaped open channel can bring good catalytic activity, and the actual application of the water decomposition catalysts in an electrolytic cell is greatly limited by extremely low toughness and large contact resistance after the water decomposition catalysts are assembled. Current commercial catalysts are frequently used (NM) for mechanical strength and cycle stability considerations, but their higher overpotential and lower energy efficiency result in greater energy losses in the hydrogen production process.
And a small amount of Pt is doped, so that the cost can be controlled, and the electrode performance can be greatly improved. However, pt often needs to be bonded to a substrate using a binder (e.g., nafion), which results in loss of active sites of the catalyst and affects the catalytic activity and catalytic reaction rate of the electrode.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects that in the prior art, pt in a Pt-doped catalyst electrode is combined with a substrate through a binder, so that the loss of an active site of a catalyst is easily caused, and the catalytic activity and the catalytic reaction rate of the electrode are influenced, so that the platinum-doped catalyst electrode, the preparation method and the application thereof are provided.
The technical scheme adopted by the invention is as follows:
the invention provides a platinum-doped catalyst electrode which takes a nickel screen as a substrate, wherein Ni (OH) is loaded on the substrate 2 The nanowire/sheet compound is used as a carrier, and the doping on the carrier is not higher than 0.06 mg/cm 2 Pt of (2).
Preferably, the Pt is a nanoparticle;
and/or doping of said PtThe amount is 0.04-0.06 mg/cm 2 。
The invention also provides a preparation method of the platinum-doped catalyst electrode, which comprises the following steps:
1) Mixing NiCl 2 Mixing urea and water to obtain a mixed solution;
2) Immersing a nickel screen into the mixed solution obtained in the step 1), carrying out hydrothermal reaction, cooling, washing and drying to obtain the carrier;
3) Depositing Pt on the surface of the support in step 2) by electrochemical deposition to obtain the platinum-doped catalyst electrode (Pt-Ni (OH) 2 @NM）。
Preferably, niCl in step 1) 2 The molar ratio to urea is 1: (3-5);
and/or, the NiCl 2 The dosage ratio of the water to the water is 1: (20-30) with the unit of mol/L.
Optionally, the components in step 1) may be mixed uniformly, for example, a uniform mixed solution may be obtained by magnetic stirring for 20min, and the mixed solution is a transparent green mixed solution.
Preferably, the reaction temperature of the hydrothermal reaction in the step 2) is 110-130 ℃, and the reaction time is 5-6 h; carrying out hydrothermal reaction in the inner liner of a polytetrafluoroethylene reaction kettle, and then naturally cooling to room temperature; the top surface of the nickel screen is covered by a teflon tape so that the product is deposited on the other side of the nickel screen.
Preferably, the specific operation of electrochemical deposition in step 3) is: the carrier in the step 2) is used as a working electrode, the mercury oxide electrode is used as a reference electrode, the carbon rod is used as a counter electrode, a three-electrode system is assembled and placed in an alkaline Pt-containing system +4 Is subjected to electrochemical deposition in the electrolyte.
Preferably, the alkaline Pt-containing compound in step 3) +4 The electrolyte is 1-1.2M KOH aqueous solution containing H with the concentration of 15-20 mu M 2 PtCl 6 ；
And/or, the electrochemical deposition adopts cyclic voltammetry, the scanning rate is 40-60 mV/s, the voltage range is-0.5-0V, and the cycle period is 40-50 weeks.
Preferably, the solvents for washing in the step 2) are water and ethanol in sequence; cleaning with deionized water and then ethanol;
and/or the washing times are 3-5 times respectively;
and/or the drying temperature is 60-80 ℃, and the drying time is 12-24 h; optionally but not limited to vacuum drying.
Preferably, the nickel screen in the step 2) is cleaned in advance;
and/or washing the nickel screen by acetone, ethanol, deionized water, hydrochloric acid aqueous solution and deionized water in sequence;
and/or the concentration of the hydrochloric acid aqueous solution is 2-3M HCl;
and/or, the cleaning is ultrasonic cleaning, and the cleaning time of each solvent is 10-20 min.
Optionally, the nickel screen is dried after being cleaned, typically but not limitatively, in a vacuum drying oven at 60 ℃ for 12 h.
The invention also provides an application of the platinum-doped catalyst electrode or the platinum-doped catalyst electrode prepared by the method in electrolytic water.
The technical scheme of the invention has the following advantages:
(1) The platinum-doped catalyst electrode provided by the invention takes a nickel screen as a substrate, and Ni (OH) is loaded on the substrate 2 The nanowire/sheet compound is used as a carrier, and the doping on the carrier is not higher than 0.06 mg/cm 2 Pt of (2). The nickel mesh substrate of the present invention contributes to the construction of Ni (OH) 2 Nanowire/sheet composite structures, ni (OH) 2 The characteristics of the nanowire/sheet two-dimensional material greatly improve the integral surface area of the material, and are beneficial to the load and anchoring of Pt, and the special combination mode of Pt and the substrate plays an important role in improving the active site and maintaining the cycle life; the invention is realized by doping Pt and Ni (OH) 2 The synergistic effect of the structure jointly adjusts the charge dynamics, the electrochemical active area and the intrinsic activity of the active sites of the electrode, thereby optimizing the integral HER/OER catalytic activity and catalytic reaction rate of the catalyst and reducing the reaction energy consumption. The electrode prepared by the catalyst has strong water electrolysis performance and cycle life advantages, and is beneficial to implementationThe method is applied in the actual working condition.
(2) The platinum doped catalyst electrode provided by the invention has the advantages that the doped Pt is nano particles, and the doping amount of the Pt is 0.04-0.06 mg/cm 2 The doping condition of Pt is further limited, the utilization rate of noble metal is further improved while the cost is reduced, the electrochemical active area of the catalyst electrode is greatly improved, and the reaction energy consumption is reduced.
(3) The preparation method of the platinum-doped catalyst electrode provided by the invention comprises the following steps: 1) Mixing NiCl 2 Mixing urea and water to obtain a mixed solution; 2) Immersing a nickel screen into the mixed solution obtained in the step 1), carrying out hydrothermal reaction, cooling, washing and drying to obtain the carrier; 3) Depositing Pt on the surface of the carrier in the step 2) through electrochemical deposition to obtain the platinum-doped catalyst electrode. The present invention forms Ni (OH) on a substrate by hydrothermal reaction 2 The nano-wire/nano-sheet structure, the nano-wire is formed by convolution of nano-sheets in the hydrothermal reaction process. While in Ni (OH) 2 The electrochemical deposition of Pt on the nanowire/sheet composite structure is more beneficial to the effective loading and anchoring of Pt, the active site is improved, the cycle life is maintained, and the activity and the catalytic reaction rate of the catalyst electrode are integrally optimized.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a flow chart of the preparation of a platinum-doped catalyst electrode provided in example 1 of the present invention;
FIG. 2 is an XRD spectrum of example 1 (b), comparative example 1 (a), comparative example 2 (b), comparative example 3 (a), comparative example 4 (b), comparative example 5 (a) of the present invention and the corresponding substrate NM (b), NF (a);
FIG. 3 is SEM photographs of example 1 (d), comparative example 2 (b), comparative example 4 (c) of the present invention and the substrate NM (a) used;
FIG. 4 is SEM photographs of comparative example 1 (d), comparative example 3 (b), and comparative example 5 (c) of the present invention and the substrate NF (a) used;
FIG. 5 is SEM and TEM photographs of example 1 of the present invention and comparative example 1, wherein a is Pt-Ni (OH) in example 1 2 SEM photograph of @ NM, and TEM photograph thereof in terms of b and c; d is Pt-Ni (OH) in comparative example 1 2 SEM photograph of @ NF, and e and f are TEM photographs thereof;
FIG. 6 is an SEM photograph of (a) in example 1 of the present invention; (b) TEM picture, inset is SAED diffraction pattern and particle diameter statistical histogram of corresponding region; (c, d) HRTEM photograph; (e) A Fourier/inverse Fourier transform map and a lattice fringe measurement screenshot of the selected region; (f) a TEM spectrum;
FIG. 7 is a HER (a) polarization curve, (b) Tafel slope curve for the catalyst electrodes of examples 1-3 and comparative examples 1-6 of the present invention and the substrates used;
FIG. 8 is an OER (a) polarization curve for the catalyst electrodes of examples 1-3 of the present invention and comparative examples 1-5, 7 and the substrates used, (b) Tafel slope curve;
FIG. 9 is a polarization curve (a) of a fully hydrolyzed three-electrode system of example 1 of the present invention, a polarization curve (b) of a fully hydrolyzed two-electrode system assembled from the combination of example 1, comparative example 6 and comparative example 7;
FIG. 10 shows Pt-Ni (OH) in example 1 of the present invention 2 The cycle life curves of @ NM (a) HER, (b) OER and (c) total hydrolysis bipolar system, inset is the potentiostatic test curve;
FIG. 11 shows Pt-Ni (OH) in example 1 of the present invention 2 @ NM and base NM, comparative example 1 Pt-Ni (OH) 2 @ NF and combination of comparative examples 6 and 7 (Pt/C @ NM | | | RuO) 2 @ NM) electrolytic cell structure schematic diagram assembled to alkaline water electrolytic cell (a), (b) polarization curve, (c) 400 mA/cm 2 And 1000 mA/cm 2 Voltage versus voltage plot of (a), (b) impedance plot; cost, voltage consumption comparison graph (e) for catalyst electrode and substrate of example 1; voltage-time curves (f) for example 1 and comparative example 1.
Detailed Description
The following examples are provided to better understand the present invention, not to limit the best mode, and not to limit the content and protection scope of the present invention, and any product that is the same or similar to the present invention and is obtained by combining the present invention with other features of the prior art and the present invention falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
The platinum-doped catalyst electrode provided in this example was a nickel mesh (NM, hebei ultra-invasive metal mesh industry, 100 mesh nickel mesh, 3 × 3 cm) 2 ) Is a substrate loaded with Ni (OH) 2 The nanowire/sheet compound is used as a carrier, and the carrier is doped with 0.06 mg/cm 2 And (3) nano Pt.
The preparation method of the platinum-doped catalyst electrode provided in this embodiment has a process flow as shown in fig. 1, and includes the following steps:
1) The preparation method of clean NM comprises the following steps:
and (3) sequentially ultrasonically cleaning the cut nickel screen NM by using acetone, ethanol, deionized water, 3M HCl and deionized water, cleaning each reagent for 10 min, and then drying in a vacuum drying oven at 60 ℃ for 12 h to obtain clean NM.
2) Ni (OH) based on NM substrate 2 Nanowire/sheet composite structures (Ni (OH) 2 @ NM) preparation:
using a typical one-step hydrothermal reaction, 4 mmol of NiCl was added 2 And 16 mmol urea was dissolved in 100 mL deionized water and magnetically stirred for 20min to obtain a clear green solution. Next, the mixed solution was poured into the teflon reactor liner and a piece of clean NM was dipped into it (the top surface of NM was covered with teflon tape so that the product was deposited on the other side of the nickel mesh). Then, the reaction kettle is put intoKeeping at 120 deg.C for 6 h, and naturally cooling to room temperature. Finally, NM was taken out and washed with deionized water 3 times, then with ethanol 3 times, and dried in a vacuum oven at 80 ℃ for 12 hours to obtain Ni (OH) 2 @NM。
3) Pt doped Ni (OH) based on NM substrate 2 Catalyst electrode (Pt-Ni (OH) 2 @ NM) preparation:
target sample Pt-Ni (OH) 2 @ NM is prepared by electrodeposition. Ni (OH) 2 @ NM is assembled as a three-electrode system, with Ni (OH) 2 The @ NM is used as a working electrode, the mercury oxide electrode is used as a reference electrode, and the carbon rod is used as a counter electrode. The corresponding electrochemical process is to contain 20 μ M H 2 PtCl 6 In the 1M KOH electrolyte, the scanning speed is 50 mV/s, the relative RHE cycle is 50 weeks at-0.5-0V, and the Pt-Ni (OH) is obtained through the cyclic CV cathodic polarization process 2 @ NM, measured by inductively coupled plasma emission spectrometer (ICP-OES), the doping amount of Pt is 0.06 mg/cm 2 。
Example 2
In the platinum-doped catalyst electrode provided in this example, NM was used as a substrate, and Ni (OH) was supported on the substrate 2 The nanowire/sheet compound is used as a carrier, and the carrier is doped with 0.05mg/cm 2 And (3) nano Pt.
The preparation method of the platinum-doped catalyst electrode provided in this embodiment has a process flow as shown in fig. 1, and includes the following steps:
1) The preparation method of clean NM comprises the following steps:
and (3) sequentially ultrasonically cleaning the cut nickel screen NM by using acetone, ethanol, deionized water, 2M HCl and deionized water, cleaning each reagent for 15 min, and then drying in a vacuum drying oven at 60 ℃ for 12 h to obtain clean NM.
2) Ni (OH) based on NM substrate 2 Nanowire/sheet composite structures (Ni (OH) 2 @ NM) preparation:
using a typical one-step hydrothermal reaction, 4 mmol of NiCl was added 2 And 20 mmol urea was dissolved in 120 mL deionized water and magnetically stirred for 20min to obtain a clear green solution. Then, the mixed solution is poured into the inner lining of a polytetrafluoroethylene reaction kettle, and a clean piece is takenNM is immersed in it (top surface of NM is covered by teflon tape so that the product is deposited on the other side of the nickel mesh). Subsequently, the reaction vessel was kept at 130 ℃ for 5 hours and allowed to cool to room temperature. Finally, NM was taken out and washed with deionized water 5 times, then with ethanol 5 times, and dried in a vacuum drying oven at 60 ℃ for 24 hours to obtain Ni (OH) 2 @NM。
3) Pt doped Ni (OH) based on NM substrate 2 Preparation of catalyst electrode:
target sample Pt-Ni (OH) 2 @ NM is prepared by electrodeposition. Ni (OH) 2 @ NM is assembled as a three-electrode system, with Ni (OH) 2 @ NM as working electrode, mercury oxide electrode as reference electrode, and carbon rod as counter electrode. The corresponding electrochemical process is to contain 17 μ M H 2 PtCl 6 The catalyst electrode is obtained by circulating CV cathode polarization process in 1.2M KOH electrolyte, with the scanning speed of 60 mV/s and the relative RHE of-0.5-0V for 50 weeks. The doping amount of Pt is 0.05mg/cm by ICP-OES test 2 。
Example 3
In the platinum-doped catalyst electrode provided in this example, NM was used as a substrate, and Ni (OH) was supported on the substrate 2 The nanowire/sheet composite is used as a carrier, and the carrier is doped with 0.04 mg/cm 2 And (3) nano Pt.
The preparation method of the platinum-doped catalyst electrode provided in this embodiment has a process flow as shown in fig. 1, and includes the following steps:
1) The preparation method of clean NM comprises the following steps:
and (3) sequentially ultrasonically cleaning the cut nickel screen NM by using acetone, ethanol, deionized water, 3M HCl and deionized water, cleaning each reagent for 13 min, and then drying in a vacuum drying oven at 60 ℃ for 12 h to obtain clean NM.
2) Ni (OH) based on NM substrate 2 Nanowire/sheet composite structures (Ni (OH) 2 @ NM) preparation:
using a typical one-step hydrothermal reaction, 4 mmol of NiCl was added 2 And 12 mmol of urea were dissolved in 80 mL of deionized water and magnetically stirred for 20min to obtain a clear green solution. Then, the mixed solution was poured into poly (tetra-poly)The vinyl fluoride autoclave was lined and a clean piece of NM was dipped into it (the top surface of NM was covered with teflon tape so that the product was deposited on the other side of the nickel mesh). Subsequently, the reaction vessel was kept at 110 ℃ for 6 hours and allowed to cool to room temperature. Finally, the NM was taken out and washed with deionized water 4 times, then with ethanol 4 times, and dried in a vacuum oven at 80 ℃ for 12 hours to obtain Ni (OH) 2 @NM。
3) Pt doped Ni (OH) based on NM substrate 2 Preparation of catalyst electrode:
target sample Pt-Ni (OH) 2 @ NM is prepared by electrodeposition. Ni (OH) 2 @ NM is assembled as a three-electrode system, with Ni (OH) 2 The @ NM is used as a working electrode, the mercury oxide electrode is used as a reference electrode, and the carbon rod is used as a counter electrode. The corresponding electrochemical process is to contain 15 μ M H 2 PtCl 6 The catalyst electrode is obtained in 1.1M KOH electrolyte by a cyclic CV cathode polarization process, the scanning speed is 40 mV/s, the scanning speed is minus 0.5-0V is relative to RHE cycle for 40 weeks, and the Pt doping amount is 0.04 mg/cm through ICP-OES test 2 。
Comparative example 1
The catalyst electrode provided by the comparative example takes foam nickel (NF, saibo electrochemical material net, 1.5 mm thick, 0.2-0.6 mm aperture, 97.2% porosity) as a substrate, and Ni (OH) is loaded on the substrate 2 The nanowire/sheet compound is used as a carrier, and the carrier is doped with 0.11 mg/cm 2 And (3) nano Pt.
This comparative example provides a method for producing a catalyst electrode, comprising the steps of:
the NM in example 1 was replaced by Nickel Foam (NF) and the remaining steps were unchanged to obtain a NF-based catalyst Pt-Ni (OH) 2 @ NF, ICP-OES test shows that the doping amount of Pt is 0.11 mg/cm 2 。
Comparative example 2
The catalyst electrode provided in this comparative example had NM as a substrate on which Ni (OH) was supported 2 A nanowire/sheet composite.
This comparative example provides a method for preparing a catalyst electrode, comprising step 1) and step 2) of example 1, and the obtained carrier is the comparative exampleCatalyst Ni (OH) 2 @NM。
Comparative example 3
The catalyst electrode provided by the comparative example takes NF as a substrate, and Ni (OH) is loaded on the substrate 2 A nanowire/sheet composite.
This comparative example provides a method for preparing a catalyst electrode, comprising steps 1) and 2) of example 2), the obtained support being the catalyst Ni (OH) of this comparative example 2 @NF。
Comparative example 4
The catalyst electrode provided in this comparative example had NM as a substrate, and Pt was supported on the substrate.
This comparative example provides a method of preparing a catalyst electrode, comprising the steps of:
NM is used as a working electrode, a mercury oxide electrode is used as a reference electrode, and a carbon rod is used as a counter electrode. The corresponding electrochemical process is carried out in the presence of 20. Mu.M H 2 PtCl 6 The catalyst Pt @ NM is obtained by a cyclic CV cathodic polarization process, wherein the scanning speed is 50 mV/s, and the relative RHE is cycled for 50 weeks at-0.5-0V. Measured by ICP-OES, the doping amount of Pt is 0.03 mg/cm 2 。
Comparative example 5
The catalyst electrode provided by the comparative example takes NF as a substrate, and Pt is loaded on the substrate.
This comparative example provides a method for producing a catalyst electrode, comprising the steps of:
the NM in comparative example 1 was replaced with Nickel Foam (NF) and the rest of the procedure was unchanged to give the platinum doped catalyst Pt @ NF. Measured by ICP-OES, the doping amount of Pt is 0.07 mg/cm 2 。
Comparative example 6
The catalyst electrode provided in this comparative example had NM as a substrate, and commercial 20% Pt/C (brand: macklin, specification: pt 20%) was supported on the substrate.
This comparative example provides a method of preparing a catalyst electrode, comprising the steps of:
10mg of commercial 20% Pt/C purchased was dispersed in 330 μ L water/ethanol/5% Nafion (inochem, nafion 117) solvent (V/V = 150). The catalyst preparedThe reagent solution was dropped on the NM substrate and air dried naturally to obtain Pt/C @ NM. The doping amount of Pt is 0.5 mg/cm by ICP-OES test 2 。
Comparative example 7
The catalyst electrode provided by the comparative example uses NM as a substrate, and commercial RuO is loaded on the substrate 2 。
This comparative example provides a method of preparing a catalyst electrode, comprising the steps of:
10mg of commercial RuO 2 (brand: macklin, specification: 99.9%) was dispersed in 330 μ L of water/ethanol/5% nafion solvent (V/V = 150. Dropping the prepared catalyst solution on an NM substrate, and naturally airing to obtain RuO 2 @ NM. Through ICP-OES test, the doping amount of Ru is 0.8 mg/cm 2 。
The following tests were carried out on the examples and comparative examples:
1. structural testing
The catalyst electrodes and substrates prepared in examples 1 to 3 and comparative examples 1 to 7 were subjected to ICP-OES element content measurement and structural tests such as XRD, SEM, TEM, SAED diffraction, particle diameter statistics, HRTEM, fourier/inverse fourier transform, TEM spectrum, and the like.
The test results are shown below:
table 1 shows the elemental contents of the samples of examples 1 to 3 of the present invention and comparative examples 1 to 7 measured by ICP-OES. Because of the Ni substrate used, the Ni mass is primarily the substrate mass.
TABLE 1
FIG. 2 shows Pt-Ni (OH) in example 1 of the present invention 2 @ NM (b), comparative example 1 Pt-Ni (OH) 2 @ NF (a), comparative example 2 Ni (OH) 2 @ NM (b), comparative example 3 Ni (OH) 2 XRD spectra of @ NF (a), comparative example 4 Pt @ NM (b), comparative example 5 Pt @ NF (a) and corresponding substrates NM (b), NF (a).
As can be seen from the figure: in Ni (OH) 2 After growth, corresponding characteristic peaks appear, butIs due to the strong shielding effect of Ni in NM and NF, resulting in Ni (OH) 2 And Pt has weak characteristic peak intensity and needs to be characterized by other means.
FIG. 3 shows Pt-Ni (OH) in example 1 of the present invention 2 @ NM (d), comparative example 2 Ni (OH) 2 SEM photographs of @ NM (b), comparative example 4 Pt @ NM (c), and substrate NM (a) used.
As can be seen from the figure: after hydrothermal method, ni (OH) 2 @ NM A large number of Ni (OH) of about 10NM in width as measured by a ruler 2 The nanowire array grows on the NM substrate and is compact and uniform in appearance; whereas directly deposited Pt stacks into particles of about 30 nm in diameter; pt-Ni (OH) 2 Micro-morphology of @ NM and Ni (OH) 2 @ NM is consistent, also being an array of nanowires. In Ni (OH) 2 Pt deposited on the surface of the nanowire cannot be directly observed under a 100 nm scale, and therefore the Pt particles are fine. The finer the Pt particles are, the larger the dispersed area is, the higher the utilization rate of the noble metal is, and the lower the cost is.
FIG. 4 shows comparative example 1 Pt-Ni (OH) according to the present invention 2 @ NF (d), comparative example 3 Ni (OH) 2 SEM photographs of @ NF (b), pt @ NF (c) as compared to comparative example 5, and the substrate NF (a) used.
As can be seen from the figure, the NF substrate sample and the NM substrate sample have similar morphology rules and show a nanowire/nanosheet composite structure, but the composite structure slightly collapses due to the low mechanical strength of the NM substrate.
FIG. 5 shows Pt-Ni (OH) in example 1 of the present invention 2 @ NM (a) SEM and (b, c) TEM photographs; COMPARATIVE EXAMPLE 1 Pt-Ni (OH) 2 @ NF (d) SEM and (e, f) TEM photographs.
It can be seen from the figure that although only dense nanowire arrays can be seen in the two SEM photographs, after the structure of the substrate surface is stripped by the conventional ultrasonic treatment before the TEM test, very much nanosheet fragments can be observed in the low-power TEM photograph. At a higher magnification, it can be seen that the nanowire grows at a position which is the edge of the nanosheet and is formed by convolution of the nanosheet. Wherein, pt-Ni (OH) is measured using a scale 2 @ NF nanowire of about 10nm, and Pt-Ni (OH) 2 In @ NMThe nanowires of (a) are much finer, about 5 nm.
FIG. 6 shows Pt-Ni (OH) in example 1 of the present invention 2 @ NM (a) SEM photograph; (b) TEM picture, inset is SAED diffraction pattern and particle diameter statistical histogram of corresponding region; (c, d) HRTEM photograph; (e) A Fourier/inverse Fourier transform map and a lattice fringe measurement screenshot of the selected region; (f) TEM energy spectrum.
As can be seen from the figure, some Pt nanoparticles with a diameter of about 3.14 nm are firmly anchored to Ni (OH) 2 In a nanowire/sheet composite structure. SAED diffraction Pattern and Ni (OH) 2 The (100), (102) and (110) crystal planes of (A) and the Pt (111) crystal plane of (B) correspond, which is consistent with the XRD results. HRTEM image of dark Pt nanoparticles dispersed homogeneously in light Ni (OH) 2 On the nano-wire, the Pt nano-particles are further magnified and characterized, and clear lattice stripes can be seen. After further Fourier transform and inverse Fourier transform are carried out on the selected region, the stripe spacing of the selected region is easily measured to be 0.227 nm and corresponds to a Pt (111) crystal face, and successful doping of the Pt nano particles is proved. In the energy spectrum, it can be seen that the Ni and O elements are widely and uniformly distributed in the catalyst sample, while the Pt element is present only in the bright white particle region.
2. Electrolytic water catalysis performance test
The electrolytic water catalysis performance evaluation is carried out on the catalyst, and the test method comprises the following steps: cyclic voltammetry testing is carried out by adopting a three-electrode system with a ring-disc electrode, wherein the catalyst electrode prepared in each embodiment and comparative example in the three-electrode system is used as a working electrode, the Hg | HgO electrode is used as a reference electrode, and a carbon rod is used as a counter electrode; the two-electrode water splitting system is assembled by taking the catalyst electrodes of the tested examples as an anode and a cathode respectively, or taking the comparative example 6 as a cathode and taking the comparative example 7 as an anode; the electrolyte is 1M KOH solution, and H is respectively introduced into the electrolyte before HER and OER tests 2 And O 2 20 nim to exclude the effect of product dissolution in the electrolyte on performance.
The LSV test temperature was 25 ℃ at room temperature, the scan rate was 5mV/s, and the current density-time test curve was run at the corresponding potential.
The frequency range of EIS impedance test is 10 kHz-0.01 Hz.
All LSV curves are corrected by iR and converted by a Reversible Hydrogen Electrode (RHE) corresponding to a reference electrode according to a Nernst equation:
E (RHE) = E (Hg|HgO) + 0.0591 × pH + 0.098 (V)
whereinE (Hg|HgO) Is the measured potential relative to Hg | HgO, 0.098V is the standard potential of Hg | HgO at 25 ℃.
The test results are shown below:
table 2 shows the HER density at 10 mA/cm for the samples of examples 1 to 3 of the present invention and comparative examples 1 to 7 2 And 100 mA/cm 2 And OER at 100 mA/cm 2 And 400 mA/cm 2 Over-potential of (c).
TABLE 2
Fig. 7 is a HER (a) polarization curve, (b) Tafel slope curve for the catalyst electrodes of examples 1-3 of the present invention and comparative examples 1-6 and the substrates used.
As can be seen from Table 2 and FIG. 7, when the current density was 10 mA/cm 2 And 100 mA/cm 2 In time, none of examples 1-3 had a higher HER over-potential than comparative examples 1-6, in which example 1 had Pt-Ni (OH) 2 Both @ NM showed the best HER activity with overpotentials of 31 mV and 68 mV, respectively, combined with the polarization curve of (a) in FIG. 7, indicating that example 1 was the most active for HER catalysis, exceeding the commercial noble metal Pt/C @ NM. While the Tafel slopes of examples 1-3 are lower than comparative examples 1-6, example 1 has the smallest Tafel slope (42 mV/dec) exceeding the performance of Pt/C @ NM. The minimum overpotential represents lower energy consumption to produce the same hydrogen, with a lower Tafel slope corresponding to faster HER reaction kinetics. It can be seen that the embodiments of the present invention can improve the catalytic activity and catalytic reaction rate of the electrode. Comparative example 1 the NF has a large resistance and a complex three-dimensional structure, and the NF is easily collapsed in a strong alkali environment and has low mechanical strength, and is assembledThe test system brings more contact resistance and is less favorable for catalytic reactions than the embodiments of the present invention.
FIG. 8 is a comparison of OER (a) polarization curves, (b) Tafel slope curves for catalyst electrodes of inventive examples 1-3 and comparative examples 1-5, 7 and substrates used.
As can be seen from Table 2 and FIG. 8, when the current density was 100 mA/cm 2 And 400 mA/cm 2 In time, pt-Ni (OH) of example 1 2 The @ NM overpotential is 269 mV and 301 mV respectively, and the best OER catalytic activity is also shown, and the voltage consumed by electrolyzing water to generate the same amount of oxygen is the minimum. Example 1 had a minimum Tafel slope (51 mV/dec), not only lower than comparative examples 1-5, but also exceeded the RuO of a commercial standard noble metal catalyst electrode 2 OER catalytic performance of @ NM. Examples 2 and 3 also showed OER catalytic performance superior to comparative examples 1-5, 7. It can be seen that the embodiments of the present invention can improve the catalytic activity and catalytic reaction rate of the electrode.
FIG. 9 is a polarization curve (a) of a fully hydrolyzed three-electrode system of example 1 of the present invention, a polarization curve (b) of a fully hydrolyzed two-electrode system assembled from the combination of example 1, comparative example 6 and comparative example 7;
it can be seen that the desired Δ of example 1V（∆V = V OER - V HER ) 1.53V and 1.57V to drive the water splitting reaction to 50 mA/cm 2 And 100 mA/cm 2 . Next, with Pt-Ni (OH) 2 @ NM as anode and cathode respectively to construct a two-electrode water splitting system (Pt-Ni (OH) 2 @NM || Pt-Ni(OH) 2 @ NM). Dual-stage system Pt/C @ NM | | RuO assembled with comparative examples 6 and 7 2 @ NM comparison, pt-Ni (OH) 2 @NM || Pt-Ni(OH) 2 The @ NM system needs 1.491V and 1.652V to reach 10 mA/cm 2 And 100 mA/cm 2 Is superior to Pt/C @ NM | | RuO 2 @ NM combination: (E 10 = 1.553 V，E 100 = 1.736 V）。
FIG. 10 shows Pt-Ni (OH) in example 1 of the present invention 2 Cycles of (a) HER, (b) OER and (c) Total hydrolysis double electrode System testing of @ NMThe ring life curve, inset is the constant potential test curve.
As can be seen from the figure, pt-Ni (OH) 2 The polarization curve of @ NM after 10000 CV cycles was substantially coincident with the initial phase, whereas the current density remained 99.3% and 98.5% of the initial state after 40 h of HER and OER potentiostatic tests, respectively, and remained 96.6% of the initial state after 100 h of perhydrolysis potentiostatic tests.
FIG. 11 shows Pt-Ni (OH) in example 1 of the present invention 2 @ NM, base NM of example 1, comparative example 1 Pt-Ni (OH) 2 @ NF and combination of comparative examples 6 and 7 (Pt/C @ NM | | | RuO) 2 @ NM) electrolytic cell structure schematic diagram assembled to alkaline water electrolytic cell (a), (b) polarization curve, (c) 400 mA/cm 2 And 1000 mA/cm 2 Voltage versus voltage plot of (a), (b) impedance plot; cost, voltage consumption comparison graph (e) for catalyst electrode and substrate of example 1; example 1 and comparative example 1 400 mA/cm at 80 deg.C 2 Voltage-time curve (f) of (a).
As can be seen from the figure, pt-Ni (OH) 2 The @ NM still shows the minimum potential requirement after being assembled in the alkaline water electrolyzer, and reaches 400 mA/cm 2 And 1000 mA/m 2 Only 1.87V and 2.24V are needed, which is better than Pt/C @ NM | | RuO 2 A @ NM electrode; pt-Ni (OH) 2 @ NF up to 400 mA/cm 2 And 1000 mA/cm 2 Is also lower than Pt/C @ NM | | | RuO 2 The @ NM electrode is low in potential; the embodiment of the invention has the advantages of low voltage consumption and high energy utilization efficiency when electrolyzing water to generate the same amount of hydrogen and oxygen. Compared with commercial standard noble metal combination, the embodiment of the invention can successfully reduce the cost on the premise of ensuring better electrolytic effect. Compared with pure NM, the cost is only 0.013 yuan/cm higher 2 And reaches 1000 mA/cm 2 The required voltage is reduced by 0.84V. As can be seen from the impedance diagram, pt-Ni (OH) 2 @ NM has the smallest contact resistance (only 0.23 Ω). The constant current test curve shows that at 400 mA/cm 2 At a current density of (2), pt-Ni (OH) 2 The voltage increase rate of @ NM in 600 h is only 0.13 mV/h 1 It can be seen that Pt-Ni (OH) 2 The stability of the @ NM catalytic electrode is very good.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications derived therefrom are intended to be within the scope of the invention.
Claims (10)
1. The platinum-doped catalyst electrode is characterized in that a nickel net is used as a substrate, and Ni (OH) is loaded on the substrate 2 The nanowire/sheet compound is used as a carrier, and the doping on the carrier is not higher than 0.06 mg/cm 2 And (3) Pt of (1).
2. The platinum doped catalyst electrode according to claim 1, wherein the Pt is a nanoparticle;
and/or the doping amount of the Pt is 0.04-0.06 mg/cm 2 。
3. A method for preparing a platinum doped catalyst electrode according to claim 1 or 2, comprising the steps of:
1) Mixing NiCl 2 Mixing urea and water to obtain a mixed solution;
2) Immersing a nickel screen into the mixed solution obtained in the step 1), carrying out hydrothermal reaction, cooling, washing and drying to obtain the carrier;
3) Depositing Pt on the surface of the carrier in the step 2) through electrochemical deposition to obtain the platinum-doped catalyst electrode.
4. The method for preparing a platinum-doped catalyst electrode according to claim 3, wherein NiCl is used in the step 1) 2 The molar ratio to urea is 1: (3-5);
and/or, the NiCl 2 The dosage ratio of the water to the water is 1: (20-30) with the unit of mol/L.
5. The method for preparing a platinum-doped catalyst electrode according to claim 3 or 4, wherein the reaction temperature of the hydrothermal reaction in the step 2) is 110 to 130 ℃ and the reaction time is 5 to 6 hours.
6. The method for preparing a platinum-doped catalyst electrode according to claim 3 or 4, wherein the electrochemical deposition in the step 3) is performed by: the carrier in the step 2) is used as a working electrode, the mercuric oxide electrode is used as a reference electrode, the carbon rod is used as a counter electrode, a three-electrode system is assembled and placed in an alkaline Pt-containing system +4 Is subjected to electrochemical deposition in the electrolyte.
7. The method for preparing a platinum-doped catalyst electrode according to claim 6, wherein the basic Pt-containing in step 3) +4 The electrolyte is 1-1.2M KOH aqueous solution containing H with the concentration of 15-20 mu M 2 PtCl 6 ；
And/or, the electrochemical deposition adopts cyclic voltammetry, the scanning rate is 40-60 mV/s, the voltage range is-0.5-0V, and the cycle period is 40-50 weeks.
8. The method for preparing a platinum-doped catalyst electrode according to claim 3, wherein the solvent for washing in step 2) is water, ethanol;
and/or the washing times are 3-5 times respectively;
and/or the drying temperature is 60-80 ℃, and the drying time is 12-24 h.
9. The method for preparing a platinum-doped catalyst electrode according to claim 3, wherein the nickel mesh is previously subjected to a cleaning process in the step 2);
and/or the nickel screen is washed by acetone, ethanol, deionized water, hydrochloric acid water solution and deionized water in sequence;
and/or the concentration of the hydrochloric acid aqueous solution is 2-3M HCl;
and/or, the cleaning is ultrasonic cleaning, and the cleaning time of each solvent is 10-20 min.
10. Use of a platinum doped catalyst electrode according to claim 1 or 2 or a platinum doped catalyst electrode prepared by a process according to any one of claims 3 to 9 in the electrolysis of water.
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Application publication date: 20230120 |