CN114289021B - Nickel-iron-based catalyst and preparation and application thereof - Google Patents
Nickel-iron-based catalyst and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to preparation and application of an electrocatalytic material for electrocatalytic oxygen evolution reaction (water oxidation reaction). The catalytic material is mainly nickel-iron based catalytic material (NiFe m (OOH) 1+m ) The material is obtained by further activating a synthesized Prussian blue analog precursor after ion exchange under alkaline conditions. The material structure is ferronickel oxyhydroxide, and is applied to electrolytic water reaction anode electrocatalytic oxygen evolution reaction. The invention greatly reduces the overpotential of the anodic oxygen evolution reaction in the electrolyzed water (reaching 10mAcm ‑2 The overpotential at current density is only 263mV and the Tafil slope is also only 35mV dec ‑1 ) Obviously improves the performance of the catalyst and is obviously superior to the commercial noble metal RuO 2 The catalyst is more superior to NiFe-based hydroxide catalyst produced by conventional means. Can effectively reduce the cost of hydrogen production by water electrolysis and completely meet the requirements of commercial production.
Description
Technical Field
The invention belongs to the field of electrochemistry, and particularly relates to a preparation method and application of a ferronickel-based catalyst for an electro-catalytic oxygen evolution reaction (water oxidation reaction) of an electrolytic water anode.
Background
The shortage of non-renewable fossil energy sources and the increasingly prominent environmental issues have forced the search for alternative new energy sources. Hydrogen has been attracting attention as a new energy source with high efficiency and no pollution, and in the field of new energy sources such as fuel cells. But the production of high purity hydrogen is subject to high costs and thus difficult to be commercially applied on a large scale. The hydrogen production by water electrolysis can utilize waste electricity which is generated by solar energy, wind energy and the like and cannot be combined with a power grid as energy, and directly generates high-purity hydrogen and oxygen to meet the requirements of new energy markets.
The anode oxygen evolution reaction of the electrolytic water hydrogen production is a four-electron step, has higher overpotential compared with the cathode hydrogen evolution reaction, and is a main reason for overlarge integral bias voltage of the electrolytic water, thus being a main factor for restricting commercialization of the electrolytic water. There is therefore a need to develop efficient electrocatalytic oxygen evolution reaction catalysts. However, most of the current commercialized electrocatalytic oxygen evolution catalysts are Ru-based noble metal catalysts, which have low reserves in nature and are too expensive, so that the development of the catalysts is restricted. In order to solve the above problems, it is necessary to develop a novel non-noble metal catalyst having high activity and high stability. Research shows that the NiFe-based non-noble metal catalyst has higher oxygen precipitation reaction activity, so that the NiFe-based catalyst with high activity and excellent stability is designed and synthesized, and an effective solution can be provided for the problems. The NiFe-based non-noble metal catalyst not only can effectively reduce the overpotential of the oxygen evolution reaction and greatly reduce the energy consumption of the electrolytic water reaction, but also has abundant reserves in the natural world of raw materials, thereby providing wide prospect for large-scale commercial application.
Through optimization, the NiFe-based catalyst NiFe prepared by taking Prussian blue as a precursor m (OOH) 1+m Not only has high electrocatalytic oxygen evolution reaction activity, but also reaches 10mA cm when oxygen evolution reaction test is carried out on the glassy carbon electrode -2 Has higher catalytic performance with the overpotential of only 263mV and is obviously superior to the commercial noble metal RuO 2 The catalyst is also far superior to NiFe directly generated by conventional metal salt in alkaline solution m (OH) 2+3m A catalyst. Furthermore, the catalyst was used at 100mA cm -2 The electrocatalytic oxygen evolution activity is hardly reduced when the catalyst is operated for 100 hours in the water electrolysis experiment under the high current density, the overall performance is superior to that of the existing catalyst, and the catalyst has huge commercial application potential.
Disclosure of Invention
The invention aims to solve the technical problems of providing a preparation and application of a novel electrolytic water anode electrocatalytic oxygen evolution reaction catalyst, which takes Prussian blue analogues as precursors to exchange ions with alkali liquor at normal temperature, and generates NiFe after further electrochemical activation m (OOH) 1+m The catalyst has excellent electrocatalytic oxygen evolution reaction performance, and can effectively reduce the overpotential of the electrocatalytic oxygen evolution reaction.
The invention relates to an electrocatalytic oxygen evolution catalytic material which is nickel-iron-based hydroxyl hydroxide.
The ferronickel-based oxyhydroxide is generated after ion exchange at room temperature, the synthesis method is simple and suitable for mass production, wherein the synthesis precursor is generated by directly coprecipitating metal salt and potassium ferricyanide, and the ferronickel-based oxyhydroxide is prepared by the methodThe molar ratio of the ferric salt to the nickel salt is m=0.01-0.5, and the amount of ferricyanide and the total amount of metal salt accord with NiFe m [Fe(CN) 6 ] (m+2/3) Molecular formula stoichiometric ratio. The conductive material (accounting for 2% -20% of the total mass of the reactants) can be added during the synthesis of the precursor, or the conductive material (accounting for unactivated NiFe) can be added during the preparation of the catalyst alkali liquor m (OH) 2+3m 5% -50% of sample)
The preparation method of the electrocatalytic oxygen evolution catalytic material comprises the following steps: preparing a precursor from metal salt and potassium ferricyanide by a coprecipitation method according to a certain proportion, adding a strong alkali solution into the dispersed precursor to carry out ion exchange, centrifugally drying to obtain a catalytic material, and electrochemically activating to obtain a high-activity NiFe-based catalytic material NiFe m (OOH) 1+m 。
The metal salt is nickel salt and ferric salt; the conductive Carbon material is acetylene black, carbon fiber, carbon nanotube, X72 Carbon powder, ketjen black EC300J, ketjenblackEC JD, carbon ECP600 JD; the alkali liquor is one or two of KOH and NaOH, and the molar concentration is 1-3M; the experimental conditions were all room temperature.
The preparation and activation of the catalyst precursor are all carried out at room temperature.
The invention relates to an application of an electrolytic water anode electrocatalytic oxygen evolution catalyst, which is applied to a water decomposition anode O 2 Gas, wherein O 2 The electrode is loaded with NiFe-based catalytic material, and the weight of the electrode-loaded electrolytic water catalytic material is 0.1-10 mg cm -1 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the electrode is carbon paper, glass carbon, foam nickel or carbon fiber.
O of the electrolytic water anode electro-catalysis oxygen evolution reaction catalytic material 2 The preparation method of the gas generating electrode comprises the following steps: dispersing the catalytic material into a mixed solution of isopropanol and water, adding 1-10wt% of perfluorinated sulfonic acid resin Nafion solution, stirring to obtain a mixed solution, and then coating the obtained mixed solution on a working electrode and drying.
Isopropanol in the mixed solution of isopropanol and water: water is 1:5-5:1; the ratio of the metal/carbon material to the mixed solution of the isopropyl alcohol and the water is 0.5 mg-20 mg:1mL; the ratio of the 1-10wt% of the perfluorosulfonic acid resin Nafion solution to the mixed solution of isopropanol and water is 1:100-1:10; the drying condition is that the vacuum is 25-60 ℃.
The invention synthesizes non-activated NiFe through precursor ion exchange m (OH) 2+3m The kind and proportion of the precursor are changed in the synthesis process, and the concentration of alkali liquor is changed, so that NiFe can be regulated and controlled m (OH) 2+3m The amorphous degree and the proportion of metal elements, and the like, thereby adjusting the catalytic activity point position, and synthesizing NiFe m (OH) 2+3m After simple activation, high-activity NiFe-based NiFe can be generated m (OOH) 1+m A catalyst. Meanwhile, the catalytic material has the advantages of rich raw materials, simple synthesis method and excellent catalytic activity and stability effect, so that the catalytic material is suitable for large-scale commercial application.
Activated NiFe produced by this patent m (OOH) 1+m The catalyst has high electrolytic water oxygen evolution reaction activity. It is compared with the conventional synthesis means: niFe obtained directly by reacting metal salt with alkaline solution m (OH) 2+3m Has better catalytic activity and oxygen evolution reaction performance which is not possessed by the conventional NiFe catalyst (figures 10 and 24). Activated NiFe prepared by the patent m -O x H y The activity of the catalyst is also significantly high in RuO 2 Catalysts (FIG. 10, FIG. 11, FIG. 24 and FIG. 25), and which are at 100mA cm -2 The activity was hardly reduced by performing a stability test at a high current density of 100 hours (fig. 14 and 28), and the demand for commercial production was fully satisfied.
The nickel-iron based catalytic material NiFe m (OH) 2+3m After the working electrode is coated, electrochemical activation can be directly carried out to obtain the high-performance nickel-iron-based catalytic material NiFe m -O x H y It can be applied in the catalytic reaction of the electrocatalytic oxygen evolution reaction (water oxidation reaction) and can obviously reduce the overpotential of the electrolytic water oxygen evolution reaction (when reaching 10mA cm -2 The overpotential at current density is only 263mV,and the Tafil slope is only 35mV dec -1 ) The activity and the stability of the composition are obviously superior to those of the commercial RuO 2 Catalyst (which was measured at 10mA cm -2 The overpotential at current density is only 288mV, and the Tafil slope is as high as 55mV dec -1 )。
The material structure is ferronickel oxyhydroxide, and is applied to an anode electrocatalytic oxygen evolution electrode for water electrolysis reaction. The invention greatly reduces the overpotential of the oxygen evolution reaction (when reaching 10mA cm -2 The overpotential at current density is only 263mV and the Tafil slope is also only 35mV dec -1 ) Obviously improves the performance of the catalyst and is obviously superior to the commercial noble metal RuO 2 The catalyst can effectively reduce the cost of preparing high-purity hydrogen by electrolyzing water, and the catalyst can be used for preparing high-purity hydrogen at 100mA cm -2 Still has higher stability under the high current density, the activity is hardly reduced in the stability test for 100h, and the requirement of commercial production is completely met.
Drawings
FIG. 1 is a precursor NiFe of example 1 0.2 Scanning Electron Microscope (SEM) of Fe PBA samples, scale 100nm.
FIG. 2 is NiFe of example 1 0.2 (OH) 2.6 Scanning Electron Microscope (SEM) pictures of the samples, scale 100nm.
FIG. 3 is NiFe of example 1 0.2 (OH) 2.6 The elemental distribution (SEM-EDS) of the sample was plotted on a scale of 4 μm.
FIG. 4 is a precursor NiFe of example 1 0.2 Fe PBA sample and Standard Ni 3 [Fe(CN) 6 ] 2 ·10H 2 X-ray diffraction (XRD) pattern of the O card.
FIG. 5 is NiFe in example 1 0.2 (OH) 2.6 Sample and Standard alpha-Ni (OH) 2 X-ray diffraction (XRD) pattern of the card.
FIG. 6 is a precursor NiFe of example 1 0.2 Mossburg spectra of Fe PBA samples.
FIG. 7 is NiFe of example 1 0.2 (OH) 2.6 Musburg spectra of the samples.
FIG. 8 is NiFe of example 1 0.2 (OH) 2.6 Sample and Standard alpha-Ni (OH) 2 Raman spectra of the samples.
FIG. 9 NiFe in example 1 0.2 (OH) 2.6 Sample and NiFe (OOH) formed after activation 1.2 The sample is tested in the electrocatalytic oxygen evolution reaction to obtain a cyclic voltammogram, the initial potential of a scanning range in the test is 0.02V, the scanning termination potential is 0.5V, and the scanning speed is 10mV s -1 。
FIG. 10 is a NiFe obtained after activation in example 1 0.2 (OOH) 1.2 Sample, commercialized RuO 2 Samples, conventional metal salts (Nickel and iron salts) in strong alkali solution (2 mol L -1 KOH solution) of NiFe formed directly in the aqueous solution 0.2 (OH) 2.6 Electrocatalytic oxygen evolution reaction performance of the samples is compared.
FIG. 11 is a NiFe obtained after activation in example 1 0.2 (OOH) 1.2 Sample, commercialized RuO 2 The sample is subjected to electrocatalytic oxygen evolution reaction to obtain a line scanning voltammogram.
FIG. 12 is a schematic diagram of a composition of NiFe in example 1 0.2 (OOH) 1.2 Sample, commercialized RuO 2 The resulting line scan voltammogram (fig. 11) of the sample resulted in a tafel slope curve.
FIG. 13 is a NiFe-based catalyst NiFe of example 1 0.2 (OOH) 1.2 And commercialized RuO 2 Reaching 10mA cm in the electrolytic water oxygen evolution reaction -2 Over-potential at current density of (c).
FIG. 14 is NiFe of example 1 0.2 (OOH) 1.2 Stability test of sample in electrocatalytic oxygen evolution reaction, catalyst loading in test was 0.16mg cm -2 The current density is 100mA cm -2 The stability test time was 100h.
FIG. 15 is a precursor NiFe of example 2 0.25 Scanning Electron Microscope (SEM) of Fe PBA samples, scale 100nm.
FIG. 16 is NiFe in example 2 0.25 (OH) 2.75 Scanning Electron Microscope (SEM) pictures of the samples, scale 100nm.
FIG. 17 is NiFe in example 2 0.25 (OH) 2.75 Element of samplePlain distribution (SEM-EDS) plot, scale 7 μm.
FIG. 18 is a precursor NiFe of example 2 0.25 Fe PBA sample and Standard Ni 3 [Fe(CN) 6 ] 2 ·10H 2 X-ray diffraction (XRD) pattern of the O card.
FIG. 19 is NiFe in example 2 0.25 (OH) 2.75 Sample and Standard alpha-Ni (OH) 2 X-ray diffraction (XRD) pattern of the card.
FIG. 20 is a precursor NiFe of example 2 0.25 Mossburg spectra of Fe PBA samples.
FIG. 21 is a sample NiFe of example 2 0.25 (OH) 2.75 Musburg spectra of the samples.
FIG. 22 is a NiFe of example 2 0.25 (OH) 2.75 Sample and Standard alpha-Ni (OH) 2 Raman spectra of the samples.
FIG. 23 is NiFe in example 2 0.25 (OH) 2.75 Sample and NiFe (OOH) produced after activation 1.25 The cyclic voltammogram was obtained from tests before and after activation in the electrocatalytic oxygen evolution reaction.
FIG. 24 is a NiFe with high activity after activation in example 2 0.25 (OOH) 1.25 Sample, commercialized RuO 2 Samples, conventional metal salts (Nickel salt, iron salt) in strong alkali solution (2 mol L -1 KOH solution) of NiFe formed directly in the aqueous solution 0.25 (OH) 2.75 Electrocatalytic oxygen evolution reaction performance of the samples is compared.
FIG. 25 is a NiFe with high activity after activation in example 2 0.25 (OOH) 1.25 Sample, commercialized RuO 2 The sample was tested for line-scan voltammograms in an electrocatalytic oxygen evolution reaction.
FIG. 26 is a chart of example 2 of a process for producing a composition from NiFe 0.25 (OOH) 1.25 Sample, commercialized RuO 2 The resulting line scan voltammogram (fig. 25) of the sample gave a tafel slope curve.
FIG. 27 is a NiFe-based catalyst NiFe of example 2 0.25 (OOH) 1.25 And commercialized RuO 2 Reaching 10mA cm in electrocatalytic oxygen evolution reaction -2 Is (1) the current of the (a)Overpotential at density.
FIG. 28 is a diagram representing NiFe in example 2 0.2 -O x H y Stability test of sample in electrocatalytic oxygen evolution reaction, catalyst loading in test was 0.16mg cm -2 The current density is 100mA cm -2 The stability test time was 100h.
FIG. 29 is a NiFe of example 1 0.2 (OOH) 1.2 NiFe in example 2 0.25 (OOH) 1.25 NiFe in example 3 0.11 (OOH) 1.11 NiFe in example 4 0.29 (OOH) 1.29 Commercial RuO 2 Comparison of the activity of the active samples in the electrocatalytic oxygen evolution reaction.
FIG. 30 is NiFe in example 1 0.2 (OOH) 1.2 NiFe in example 2 0.25 (OOH) 1.25 NiFe in example 3 0.11 (OOH) 1.11 NiFe in example 4 0.29 (OOH) 1.29 Commercial RuO 2 Tafil slope plot of active samples obtained in electrocatalytic oxygen evolution reactions.
FIG. 31 is NiFe in example 1 0.2 (OOH) 1.2 NiFe in example 2 0.25 (OOH) 1.25 NiFe in example 3 0.11 (OOH) 1.11 NiFe in example 4 0.29 (OOH) 1.29 Commercial RuO 2 The active sample was at 10mA cm in the electrocatalytic oxygen evolution reaction -2 Over-potential values measured at current density.
Detailed Description
Example 1 high Performance NiFe-based electrocatalyst oxygen evolution catalyst NiFe 0.2 (OOH) 1.2 Preparation of (d) and electrocatalytic oxygen evolution test
1) Precursor NiFe 0.2 Preparation of Fe PBA
First 987.8mg K 3 [Fe(CN) 3 ]Dissolved in a beaker (10 mol L) containing 300mL of ultra-pure water in a volume of 500mL -1 ) Ultrasonic treatment to dissolve the materials fully; then according to Ni 3+ (molar amount of nickel ions in the metallic nickel salt): fe (Fe) 3+ (molar amount of iron ions in the iron metal salt): [ Fe (CN) 6 ] 3+ (molar amount of ferricyanide in ferricyanide) = 1:m (m+2/3), and the value m=0.2, niCl is prepared 2 ·6H 2 O and FeCl 3 ·6H 2 O mixed solution, i.e. 822.8mg NiCl 2 ·6H 2 O and 300mg of 197.1mg FeCl 3 ·6H 2 O was dissolved in a 1L beaker containing 300mL of ultrapure water, while adding the reagents (K 3 [Fe(CN) 3 ]、NiCl 2 ·6H 2 O and FeCl 3 ·6H 2 O) 8% of the total mass (in NiCl) 2 ·6H 2 O and FeCl 3 ·6H 2 161mg (carbon nanotubes with an outer diameter of 10-20 μm and a length of 5-15 μm) of conductive material (15.7% of the total mass of O metal salt) and vigorously stirring to form a solution in which the conductive material and NiFe metal salt are uniformly mixed; then the configured K 3 [Fe(CN) 3 ]Solution (10 mol L) -1 ) 300mL of the mixed metal salt is added dropwise and stirred; stirring for 30min after the dripping is completed, and aging for 20h; finally centrifuging, and drying the solid product at the constant temperature of 60 ℃ for 12 hours to obtain the precursor NiFe 0.2 -Fe PBA。
2)NiFe 0.2 (OH) 2.6 Preparation of samples
To prepare NiFe 0.2 Taking 200mg of Fe PBA precursor as a raw material, dispersing 200mg of Fe PBA precursor in a beaker with a volume of 500mL and containing 100mL of ultrapure water, stirring with intense magnetic force, and adding 200mL of 2mol L after the Fe PBA precursor is uniformly dispersed -1 Centrifuging after stirring for 15min, centrifuging with ultrapure water for 3 times, centrifuging with ethanol for 1 time, and drying the obtained precipitate at 60deg.C for 12 hr to obtain NiFe 0.2 (OH) 2.6 And (3) a sample.
3) High performance NiFe 0.2 (OOH) 1.2 Electrode preparation of catalyst
Taking synthesized NiFe 0.2 (OH) 2.6 Sample 4mg was added to 1mL of the dispersion (490. Mu.L of ultrapure water H) 2 0 (18.2M omega), 490. Mu.L isopropanol, 20. Mu.L nafion solution) ultrasonic (. Gtoreq.6 h) dispersion; the catalyst slurry was then uniformly coated on a commercial glassy carbon electrode having a diameter of 5mm as a working electrode (loading of 0.2mg cm -2 ) Simultaneously, the saturated calomel electrode and a carbon rod with the diameter of 6mm are respectively used as a reference electrode and a counter electrode to form three layersElectrode system using 1mol L -1 KOH is used as electrolyte and is connected into an electrochemical workstation for activation. The specific setting parameters and steps of the activation of the electrochemical workstation are as follows: activating by cyclic voltammetry, wherein the scanning voltage range is 0.02-0.5V; the sweeping speed is 10mV s -1 The method comprises the steps of carrying out a first treatment on the surface of the The number of scanning turns is 200, and the scanning is forward scanning. The cyclic voltammogram of the sample before and after activation (FIG. 9) shows the NiFe formed after activation 0.2 (OOH) 1.2 The activity is remarkably increased.
4) Commercial RuO for reference 2 Electrode preparation of electrocatalytic oxygen evolution catalyst
Commercial RuO for direct purchase 2 Sample 4mg was added to 1mL of the dispersion (490. Mu.L of ultrapure water H) 2 0 (18.2M omega), 490. Mu.L isopropanol, 20. Mu.L nafion solution) ultrasonic (. Gtoreq.6 h) dispersion; the catalyst slurry was then uniformly coated on a commercial glassy carbon electrode having a diameter of 5mm as a working electrode (loading of 0.2mg cm -2 )。
5) NiFe generated by conventional methods for reference 0.2 (OH) 2.6 Electrode preparation of (a)
82.3mg of NiCl was taken separately 2 ·6H 2 O and 300mg of 19.7mg FeCl 3 ·6H 2 O was dissolved in 500/m L beaker containing 100mL of ultra pure water, and NiCl was additionally taken out 2 ·6H 2 O and FeCl 3 ·6H 2 O occupies NiCl 2 ·6H 2 O and FeCl 3 ·6H 2 16.1mg (carbon nano tube with outer diameter of 10-20 μm and length of 5-15 μm) of conductive material with total mass of O metal salt of 15.7% (same proportion as in step 3) and stirring vigorously, adding 200mL 2mol L after dispersing uniformly -1 Centrifugal washing with ultra-pure water for 3 times and ethanol for 1 time after stirring for 15min, and obtaining precipitate which is the conventional NiFe 0.2 (OH) 2.6 The sample was then dried in a thermostatted oven at 60℃for 12h.
Drying to obtain NiFe doped with conductive material 0.2 (OH) 2.6 Sample 4mg was added to 1mL of the dispersion (490. Mu.L of ultrapure water H) 2 0 (18.2M omega), 490. Mu.L isopropanol, 20. Mu.L nafion solution) ultrasonic (. Gtoreq.6 h) dispersion; the catalyst slurry is then uniformly coatedSmeared onto a commercial glassy carbon electrode of 5mm diameter as a working electrode (load of 0.2mg cm) -2 )。
6) High activity NiFe prepared in step 3) of example 1 0.2 (OOH) 1.2 RuO commercialized in step 4) 2 NiFe produced by conventional method in step 5) 0.2 (OH) 2.6 Activity comparison.
The working electrode prepared in the steps 3), 4) and 5) is respectively taken, a three-electrode system is formed by respectively taking a saturated calomel electrode and a carbon rod with the diameter of 6mm as a reference electrode and a counter electrode, and 1mol L is used -1 KOH is used as electrolyte and is connected to an electrochemical workstation to carry out electrochemical test. The reactivity is evaluated by adopting a line scanning voltammetric curve, wherein the scanning mode is positive scanning, and the scanning speed is 5mV s -1 The scan start potential was 0.02V and the scan end potential was 0.5V. The results are shown in FIG. 10.
7) Step 3) NiFe in example 1 0.2 (OOH) 1.2 RuO in step 4) 2 Catalyst performance and tafel slope comparison.
The working electrode prepared in the steps 3) and 4) in the example 1 is respectively taken, a three-electrode system is formed by taking a saturated calomel electrode and a carbon rod with the diameter of 6mm as a reference electrode and a counter electrode respectively, and the linear voltammogram (figure 11) is obtained through slow scanning, and the scanning speed is 1mV s -1 The scan start voltage was 0.02V and the end voltage was 0.05V. Then deriving the logarithm thereof to obtain the Tafil slope curve (figure 12), and simultaneously obtaining the two curves at 10mA cm from figure 11 -2 Overpotential at current density (fig. 13). (the results were converted into standard hydrogen electrode (vs. RHE)).
8)NiFe 0.2 (OOH) 1.2 Stability test of the samples.
Taking synthesized NiFe 0.2 (OH) 2.6 Sample 4mg was added to 1mL of the dispersion (490. Mu.L of ultrapure water H) 2 0 (18.2M omega), 490. Mu.L isopropanol, 20. Mu.L nafion solution) ultrasonic (. Gtoreq.6 h) dispersion; the catalyst slurry was then uniformly applied to a foam nickel having a length of 2cm and a width of 1cm as a working electrode (load of 0.16mg cm -2 ) Simultaneously saturated calomel electrode and diameterA6 mm carbon rod is respectively used as a reference electrode and a counter electrode to form a three-electrode system, and 1mol L of the three-electrode system is used -1 And (3) the KOH serving as electrolyte is connected into an electrochemical workstation for activation, and the activation process is the same as that of the step (3). Meanwhile, the three-electrode system is used as an electrocatalytic oxygen evolution stability evaluation device, a constant current mode is adopted, and the current density is set to be 100mA cm -2 The stability test for 100h was performed, and the results showed that the activity was hardly reduced at all in the stability test for up to 100h, and the excellent stability was fully satisfactory for commercialization.
Example 2 high Performance NiFe-based electrocatalyst oxygen evolution catalyst NiFe 0.25 (OOH) 1.25 Preparation of (d) and electrocatalytic oxygen evolution test
1) Precursor NiFe 0.25 Preparation of Fe PBAs
First 987.8mg K 3 [Fe(CN) 3 ]Dissolved in a beaker (10 mol L) containing 300mL of ultra-pure water in a volume of 500mL -1 ) Ultrasonic treatment to dissolve the materials fully; then according to Ni 3+ (molar amount of nickel ions in the metallic nickel salt): fe (Fe) 3+ (molar amount of iron ions in the iron metal salt): [ Fe (CN) 6 ] 3+ (molar amount of ferricyanide in ferricyanide) = 1:m (m+2/3), and the value m=0.2, niCl is prepared 2 ·6H 2 O and FeCl 3 ·6H 2 O mixed solution, i.e. 777.9mg NiCl 2 ·6H 2 O and 300mg of 221.2mg FeCl 3 ·6H 2 O was dissolved in a 1L beaker containing 300mL of ultrapure water, while adding the reagents (K 3 [Fe(CN) 3 ]、NiCl 2 ·6H 2 O and FeCl 3 ·6H 2 O) 8% of the total mass (in NiCl) 2 ·6H 2 O and FeCl 3 ·6H 2 159.0mg (carbon nano tube with the outer diameter of 10-20 mu m and the length of 5-15 mu m) of conductive material of 15.9% of the total mass of O metal salt is stirred vigorously to form a solution of uniformly mixed conductive material and NiFe metal salt; then the configured K 3 [Fe(CN) 3 ]Solution (10 mol L) -1 ) 300mL of the mixed metal salt is added dropwise and stirred; stirring for 30min after the dripping is completed, and aging for 20h; finally centrifuging, and drying the solid product at the constant temperature of 60 ℃ for 12 hours to obtainTo precursor NiFe 0.25 -Fe PBAs。
2)NiFe 0.25 (OH) 2.75 Preparation of samples
To prepare NiFe 0.25 Taking 200mg of Fe PBA precursor as a raw material, dispersing 200mg of Fe PBA precursor in a beaker with a volume of 500mL and containing 100mL of ultrapure water, stirring with intense magnetic force, and adding 200mL of 2mol L after the Fe PBA precursor is uniformly dispersed -1 Centrifuging after stirring for 15min, centrifuging with ultrapure water for 3 times, centrifuging with ethanol for 1 time, and drying the obtained precipitate at 60deg.C for 12 hr to obtain NiFe 0.25 (OH) 2.75 And (3) a sample.
3) High performance NiFe 0.25 (OOH) 1.25 Electrode preparation of catalyst
Taking synthesized NiFe 0.25 (OH) 2.75 Sample 4mg was added to 1mL of the dispersion (490. Mu.L of ultrapure water H) 2 0 (18.2M omega), 490. Mu.L isopropanol, 20. Mu.L nafion solution) ultrasonic (. Gtoreq.6 h) dispersion; the catalyst slurry was then uniformly coated on a commercial glassy carbon electrode having a diameter of 5mm as a working electrode (loading of 0.2mg cm -2 ) Simultaneously, a saturated calomel electrode and a carbon rod with the diameter of 6mm are respectively used as a reference electrode and a counter electrode to form a three-electrode system, and 1mol L of the three-electrode system is used -1 KOH is used as electrolyte and is connected into an electrochemical workstation for activation. The specific setting parameters and steps of the activation of the electrochemical workstation are as follows: activating by cyclic voltammetry, wherein the scanning voltage range is 0.02-0.5V; the sweeping speed is 10mV s -1 The method comprises the steps of carrying out a first treatment on the surface of the The number of scanning turns is 200, and the scanning is forward scanning. The cyclic voltammograms of the samples before and after activation are shown in FIG. 9, and it can be seen that NiFe is formed after activation 0.25 (OOH) 1.25 The activity is remarkably increased.
4) Commercial RuO for reference 2 Electrode preparation of electrocatalytic oxygen evolution catalyst
Commercial RuO for direct purchase 2 Sample 4mg was added to 1mL of the dispersion (490. Mu.L of ultrapure water H) 2 0 (18.2M omega), 490. Mu.L isopropanol, 20. Mu.L nafion solution) ultrasonic (. Gtoreq.6 h) dispersion; the catalyst slurry was then uniformly coated on a commercial glassy carbon electrode having a diameter of 5mm as a working electrode (loading of 0.2mg cm -2 )。
5) For use inNiFe produced by conventional methods of reference 0.25 (OH) 2.75 Electrode preparation of (a)
77.8mg of NiCl were taken separately 2 ·6H 2 O and 300mg of 22.1mg FeCl 3 ·6H 2 O was dissolved in 500/m L beaker containing 100mL of ultra pure water, and NiCl was additionally taken out 2 ·6H 2 O and FeCl 3 ·6H 2 O (accounting for NiCl) 2 ·6H 2 O and FeCl 3 ·6H 2 15.9mg (same proportion as in step 3) of conductive material 15.9mg (carbon nano tube with outer diameter of 10-20 μm and length of 5-15 μm) of O metal salt and vigorously stirring, and adding 200mL of 2mol L after uniformly dispersing -1 Centrifugal washing with ultra-pure water for 3 times and ethanol for 1 time after stirring for 15min, and obtaining precipitate which is the conventional NiFe 0.25 (OH) 2.75 The sample was then dried in a thermostatted oven at 60 ℃.
Drying to obtain NiFe doped with conductive material 0.25 (OH) 2.75 Sample 4mg was added to 1mL of the dispersion (490. Mu.L of ultrapure water H) 2 0 (18.2M omega), 490. Mu.L isopropanol, 20. Mu.L nafion solution) ultrasonic (. Gtoreq.6 h) dispersion; the catalyst slurry was then uniformly coated on a commercial glassy carbon electrode having a diameter of 5mm as a working electrode (loading of 0.2mg cm -2 )。
6) High activity NiFe prepared in step 3) of example 2 0.25 (OOH) 1.25 RuO commercialized in step 4) 2 NiFe produced by conventional method in step 5) 0.25 (OH) 2.75 Activity comparison.
The working electrode prepared in the steps 3), 4) and 5) is respectively taken, a three-electrode system is formed by respectively taking a saturated calomel electrode and a carbon rod with the diameter of 6mm as a reference electrode and a counter electrode, and 1mol L is used -1 KOH is used as electrolyte and is connected to an electrochemical workstation to carry out electrochemical test. The reactivity is evaluated by adopting a line scanning voltammetric curve, wherein the scanning mode is positive scanning, and the scanning speed is 5mV s -1 The scan start potential was 0.02V and the scan end potential was 0.5V. The results are shown in FIG. 24.
7) Step 3) NiFe in example 2 0.25 (OOH) 1.25 Step by stepRuO in step 4) 2 Catalyst performance and tafel slope comparison.
The working electrode prepared in step 3) and step 4) of example 2 was used as a three-electrode system comprising a saturated calomel electrode and a 6mm diameter carbon rod as a reference electrode and a counter electrode, and a linear voltammogram (25) was obtained by slow scanning at a scanning rate of 1mV s -1 The scan start voltage was 0.02V and the end voltage was 0.05V. Then deriving the logarithm thereof to obtain the Tafil slope curve (FIG. 26), and obtaining the two curves at 10mA cm from FIG. 11 -2 Overpotential at current density (fig. 27). (the results were converted into standard hydrogen electrode (vs. RHE)).
8)NiFe 0.25 (OOH) 1.25 Stability test of the samples.
Taking synthesized NiFe 0.25 (OH) 2.75 The sample was added to 1mL of the dispersion (490. Mu.L of ultrapure water H) 2 0 (18.2M omega), 490. Mu.L isopropanol, 20. Mu.L nafion solution) ultrasonic (. Gtoreq.6 h) dispersion; the catalyst slurry was then uniformly applied to a foam nickel having a length of 2cm, a width of 1cm and a thickness of 0.3mm as a working electrode (load of 0.16mg cm) -2 ) Simultaneously, a saturated calomel electrode and a carbon rod with the diameter of 6mm are respectively used as a reference electrode and a counter electrode to form a three-electrode system, and 1mol L of the three-electrode system is used -1 And (3) the KOH serving as electrolyte is connected into an electrochemical workstation for activation, and the activation process is the same as that of the step (3). Meanwhile, the three-electrode system is used as an electrocatalytic oxygen evolution stability evaluation device, a constant current mode is adopted, and the current density is set to be 100mA cm -2 The stability test was performed for 100h (fig. 28), and the results showed that the activity was hardly reduced at all in the stability test for up to 100h, and the excellent stability was fully satisfactory for commercialization.
Example 3 high Performance NiFe-based electrocatalyst oxygen evolution catalyst NiFe 0.11 (OOH) 1.11 Preparation of (d) and electrocatalytic oxygen evolution test
Example 3 removal of precursor NiFe 0.11 Reactant Ni in the synthesis of Fe PBA 3+ (molar amount of nickel ions in the metallic nickel salt): fe (Fe) 3+ (molar amount of iron ions in the iron metal salt): [ Fe (CN) 6 ] 3+ (molar amount of ferricyanide in ferricyanide) = 1:m (m+2/3) the procedure is the same as in example 1 except that the ratio of (m+2/3) is different from that of example 1 (K) 3 [Fe(CN) 3 ]The dosage is unchanged). In this embodiment, the value m=0.11.
Example 4 high Performance NiFe-based electrocatalyst oxygen evolution catalyst NiFe 0.29 (OOH) 1.29 Preparation of (d) and electrocatalytic oxygen evolution test
Example 4 removal of precursor NiFe 0.29 Reactant Ni in the synthesis of Fe PBA 3+ (molar amount of nickel ions in the metallic nickel salt): fe (Fe) 3+ (molar amount of iron ions in the iron metal salt): [ Fe (CN) 6 ] 3+ (molar amount of ferricyanide in ferricyanide) = 1:m (m+2/3) the procedure is the same as in example 1 except that the ratio of (m+2/3) is different from that of example 1 (K) 3 [Fe(CN) 3 ]The dosage is unchanged). In this example, the value m=0.29 is calculated for example 1, example 2, example 3 and example 4 and for the commercial noble metal RuO 2 Such as shown in fig. 29. The loading of the catalyst on the glassy carbon electrode in the three-electrode system assembly is 0.2mg cm during the test -2 The counter electrode adopts a carbon rod with the diameter of 6mm, and the reference electrode adopts a saturated calomel electrode. Scanning mode: line Scanning Voltammetry (LSV), negative sweep; scanning rate: 1mV s -1 The method comprises the steps of carrying out a first treatment on the surface of the The scanning initial voltage is 0.02V; the scan termination voltage was 0.5V. The result is converted into a standard hydrogen electrode (vs. RHE). Tafil slope plot from line sweep voltammogram at 10mA cm -2 The overpotential values obtained at the current densities are shown in fig. 30 and fig. 31, respectively.
Claims (18)
1. A preparation method of a nickel-iron-based catalyst is characterized by comprising the following steps:
1) Under the condition of room temperature, adding a solution containing metallic nickel salt and metallic ferric salt into ferricyanide solution to directly synthesize Prussian blue analogue serving as a catalytic material precursor NiFe m [Fe(CN)6] m(+2/3) Is denoted as NiFe m -Fe PBAs；
2) Dispersing the precursor of catalytic material in solvent uniformly, and adding alkaline solution to make it undergo the process of ion exchangeUnactivated nickel-iron based catalytic material NiFe m (OH) m2+3 ；
3) NiFe as nickel-iron base catalyst material m (OH) m2+3 Activated by electrochemical pretreatment to obtain NiFe m (OOH) m1+ An electrocatalytic oxygen evolution catalyst; the molar ratio of the iron salt to the nickel salt is m=0.01-0.5;
the metal ferric salt in the step 1) is one or more than two of ferric trichloride hexahydrate, ferric trichloride anhydrous, ferric sulfate and ferric nitrate; the metal nickel salt is one or more than two of anhydrous nickel nitrate, hexahydrate nickel chloride and nickel sulfate;
the ferricyanide in the catalytic material precursor is one or more than two of potassium ferricyanide and sodium ferricyanide;
in step 1), the concentration of ferricyanide in the ferricyanide solution is 0.0001-20 mol L -1 ；
The molar concentration of ferricyanide is used as the standard, and metal nickel salt and ferric salt are added in the reaction according to Ni by the concentration of ferricyanide 3 + ：Fe 3+ ：[Fe(CN) 6 ] 3+ = 1 : m : (m+2/3)；
Dropwise adding the solutions of the metal nickel salt and the metal ferric salt into the potassium ferricyanide solution, stirring, continuing stirring for 10-120 min after the addition is completed, aging for 5-30 h at room temperature, carrying out solid-liquid separation, and drying solids to obtain a catalytic material precursor NiFe m -Fe PBAs。
2. The method for preparing the precursor of the nickel-iron based catalyst material according to claim 1, wherein: in step 1)m= 0.10–0.33。
3. The method for preparing the precursor of the nickel-iron based catalyst material according to claim 1, wherein: in step 1)m=0.15–0.25。
4. The method for preparing the precursor of the nickel-iron based catalyst material according to claim 1, wherein:
in step 1), the concentration of ferricyanide in the ferricyanide solution is 5-15 mol L -1 The method comprises the steps of carrying out a first treatment on the surface of the Stirring is continued for 20-60 min after completion, and aging is carried out at room temperature for 8-20 h.
5. The method for preparing the precursor of the nickel-iron based catalyst material according to claim 1, wherein:
in step 1), the concentration of ferricyanide in the ferricyanide solution is 9-12 mol L -1 The method comprises the steps of carrying out a first treatment on the surface of the Continuing stirring for 25-45 min after completion; aging to 10-15 h at room temperature.
6. A process according to claim 1 or 3, characterized in that:
in the step 2), the precursor of the catalytic material is uniformly dispersed in a solvent, wherein the solvent can be one or more than two of ethanol, methanol, isopropanol and water;
adding alkali solution for ion exchange after uniformly dispersing the precursor of the catalytic material in the solvent, wherein the alkali solution can be one or two solutions of potassium hydroxide or sodium hydroxide, and the concentration of the alkali solution is 0.1-4.5 mol L -1 。
7. The method of manufacturing according to claim 6, wherein:
the concentration of the alkaline solution is 1.5-3.0 mol L -1 。
8. The method of manufacturing according to claim 6, wherein:
the concentration of the alkaline solution is 1.6-2.3 mol L -1 。
9. The method of manufacturing according to claim 1, wherein:
in step 2), the precursor 150-200 mg NiFe is first prepared m Dispersing Fe PBAs precursor in 50-100mL solvent, adding 100-200mL alkaline solution, stirring for 5-30 min to allow full ion exchange for topology conversion, and separating with ultrapure water after stirringWashing heart for 2-5 times, centrifuging with ethanol for 1-3 times, and drying at constant temperature of 40-130deg.C for 8-24 h to obtain unactivated NiFe m (OH) m(2+3) And (3) a sample.
10. The preparation method according to claim 1, characterized in that:
in step 3), the electrochemical pretreatment activation may be performed using cyclic voltammetry or potentiostatic method;
specific cyclic voltammetry: the saturated calomel electrode is used as a reference, and the scanning initial voltage is 0V-0.05V; the scanning termination voltage is 0.45V-0.55V; the scanning rate is 1-200 mV s -1 All can be used; the scanning turns are 50-300 turns; the scanning direction is one of positive scanning or negative scanning;
activating by potentiostatic method: and (3) taking the saturated calomel electrode as a reference, applying a potential of 0.4-0.6-V, and performing 10-60 min.
11. The method of manufacturing according to claim 10, characterized in that:
the scanning rate is 1-50 mV s -1 。
12. The method of manufacturing according to claim 10, characterized in that:
the scanning rate is 15-30 mV s -1 。
13. The method of manufacturing according to claim 1, characterized in that:
in the step 3) of the method,
non-activated NiFe doped with conductive material m (O x H) m(2+3) Dispersing the sample in the dispersion, uniformly coating or dripping on the working electrode, drying, and NiFe m (O x H) m(2+3) The loading amount is 0.1-1 mg cm -2 The method comprises the steps of carrying out a first treatment on the surface of the The three-electrode system is assembled to perform electrochemical activation;
the dispersion liquid is a mixed solution of isopropanol and water added with a perfluorinated sulfonic acid resin binder; the volume ratio of the isopropanol to the water is 0.1:1-3.0:1; the amount of the perfluorinated sulfonic acid resin binder in the dispersion liquid accounts for 0.1-20% of the total volume of isopropanol and water;
the unactivated catalyst is dispersed in the dispersing liquid with ultrasonic wave to form slurry with concentration of 1-6 mg/mL -1 ；
The working electrode is a foam nickel, carbon paper or glassy carbon electrode;
the commercial working electrode loaded with the unactivated NiFe-based catalyst and a commercial counter electrode form a three-electrode system, wherein the commercial counter electrode is a carbon rod or a platinum wire electrode, and the commercial reference electrode is a saturated calomel electrode, a silver chloride electrode or a mercury oxide electrode, and 0.1-4 mol L of the commercial counter electrode is used -1 KOH or NaOH solution is used as electrolyte, and is connected to an electrochemical workstation to perform electrochemical activation, and high-activity ferronickel-based catalytic material NiFe for electrocatalytic oxygen evolution reaction is directly generated on an electrode m (OOH) m1+ 。
14. The method of manufacturing according to claim 13, wherein: the dispersion liquid is a mixed solution of isopropanol and water added with a perfluorinated sulfonic acid resin binder; the volume ratio of the isopropanol to the water is 0.2:1-2:1; the amount of the perfluorinated sulfonic acid resin binder in the dispersion is 0.5% -10% of the total volume of isopropanol and water.
15. The method of manufacturing according to claim 13, wherein: the dispersion liquid is a mixed solution of isopropanol and water added with a perfluorinated sulfonic acid resin binder; the volume ratio of the isopropanol to the water is 0.5:1-1.5:1; the amount of the perfluorinated sulfonic acid resin binder in the dispersion liquid accounts for 2% -10% of the total volume of isopropanol and water.
16. The method of any one of claims 1-5, wherein:
to obtain NiFe m (OOH) m(1+) The active electrocatalytic oxygen evolution catalyst is doped with a conductive material;
the addition of the doped conductive material can be performed in any one step or any two steps or three steps of the reaction process and the three steps;
i.e. can be added before the reaction in the synthesis process of the precursor of the ferronickel-based catalytic material in step 1), can be added before the ion exchange in the process in the ion exchange step in step 2), or can be added without activation in the activation step in step 3);
the conductive material accounts for 2% -20% of the total mass of precursor reactants of metallic ferric salt, metallic nickel salt and ferricyanide, the conductive material is one or more of acetylene black, carbon fiber, carbon nanotube, X72 Carbon powder and Ketjen black, and Ketjen black EC300J, ketjenblackEC JD, carbon ECP or Carbon ECP600JD.
17. An activated active electrolyzed water oxygen evolution catalyst material obtained by the process of claim 1.
18. Use of an activated active electrolyzed water oxygen evolution catalyst material according to claim 17, characterized in that: it can be used in the electrocatalytic oxygen evolution reaction of electrolytic water anode reaction or the catalytic reaction of water oxidation reaction.
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