CN114289021A - 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 a nickel-iron-based catalytic material (NiFe)m(OOH)1+m) The material is obtained by further activating a synthesized Prussian blue analogue precursor after ion exchange under an alkaline condition. The material structure is nickel-iron oxyhydroxide, and is applied to the anode electrocatalytic oxygen evolution reaction of the electrolytic water reaction. The invention greatly reduces the overpotential (which reaches 10 mAcm) of the anodic oxygen evolution reaction in the electrolyzed water‑2The current density of (a) is only 263mV over-potential, and TaphenanthreneThe molar slope is also only 35mV dec‑1) Obviously improves the catalyst performance and is obviously superior to commercial noble metal RuO2The catalyst is better than the NiFe-based hydroxide catalyst generated by the conventional method. Can effectively reduce the cost of hydrogen production by electrolyzing water and completely meet the requirement 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 nickel-iron-based catalyst for an electro-catalytic oxygen evolution reaction (water oxidation reaction) of an electrolytic water anode.
Background
The scarcity and increasing environmental concerns of non-renewable fossil energy sources has forced people to seek alternative new energy sources. Hydrogen gas has attracted attention as a new energy source having high efficiency and no pollution in the field of new energy sources such as fuel cells. But the production of high purity hydrogen suffers from high costs and is 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 merged into a power grid as energy, and high-purity hydrogen and oxygen are directly generated to meet the requirements of a new energy market.
The anodic oxygen evolution reaction for hydrogen production by water electrolysis is a four-electron step, has higher overpotential compared with the cathodic hydrogen evolution reaction, is the main reason for overlarge overall bias of the water electrolysis, and is a main factor for restricting the commercialization of the water electrolysis. Therefore, it is necessary to develop a catalyst for electrocatalytic oxygen evolution reaction with high efficiency. However, most of the current commercialized electrocatalytic oxygen evolution catalysts are Ru-based noble metal catalysts, and the development of the electrocatalytic oxygen evolution catalysts is restricted due to low reserves and high price in nature. 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 to provide an effective solution for the problems. The NiFe-based non-noble metal catalyst not only can effectively reduce the overpotential of oxygen evolution reaction and greatly reduce the energy consumption of water electrolysis reaction, but also has rich raw materials in nature, thus providing wide prospect for large-scale commercial application of the NiFe-based non-noble metal catalyst.
Through optimization, the NiFe-based catalyst NiFe prepared by taking Prussian blue as a precursorm(OOH)1+mNot only has high electrocatalytic oxygen evolution reaction activity, but also reaches 10mA cm when the oxygen evolution reaction is tested on a glassy carbon electrode-2Has higher catalytic performance with the over potential of only 263mV, which is obviously superior to that of commercial noble metal RuO2The catalyst is also far superior to NiFe directly generated by conventional metal salt in alkaline solutionm(OH)2+3mA catalyst. In addition, the catalyst was used at 100mA cm-2High current density ofThe electrocatalytic oxygen evolution activity of the catalyst is hardly reduced after the catalyst is operated for 100 hours in an electrolyzed water experiment, the overall performance of the catalyst is superior to that of the existing catalyst, and the catalyst has huge commercial application potential.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation and application of a novel electrolytic water anode electrocatalytic oxygen evolution reaction catalyst, Prussian blue analogue is taken as a precursor to perform ion exchange with alkali liquor at normal temperature, and NiFe is generated after further electrochemical activationm(OOH)1+mThe 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 nickel-iron-based oxyhydroxide is generated after ion exchange at room temperature, the synthesis method is simple and suitable for batch production, wherein the synthesis precursor is generated by direct coprecipitation of metal salt and potassium ferricyanide, the molar ratio of iron salt to nickel salt is 0.01-0.5, and the amount of the ferricyanate and the total amount of the metal salt conform to NiFem[Fe(CN)6](m+2/3)Molecular formula stoichiometric ratio. The conductive material (accounting for 2% -20% of the total mass of reactants) can be added during the synthesis of the precursor, or the conductive material (accounting for the non-activated NiFe) can be added during the preparation of the catalyst alkali liquorm(OH)2+3m5% -50% of the sample
The preparation method of the electrocatalytic oxygen evolution catalytic material comprises the following steps: preparing a precursor by a coprecipitation method according to a certain proportion by using metal salt, potassium ferricyanide and a conductive carbon material, then adding the dispersed precursor into strong alkali liquor to perform ion exchange, centrifugally drying to obtain a catalytic material, and generating a high-activity NiFe-based catalytic material NiFe after the material is electrochemically activatedm(OOH)1+m。
The metal salt is nickel salt and iron salt; the conductive Carbon material is acetylene black, Carbon fiber, Carbon nanotube, X72 Carbon powder, Ketjenblack (Ketjenblack EC300J, Ketjenblack EC600JD, 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 carried out at room temperature.
The application of the anode electrocatalytic oxygen evolution catalyst for water electrolysis is applied to the water decomposition anode O2Gas of which O2The generated electrode is loaded with a NiFe-based catalytic material, and the weight of the electrolyzed water catalytic material loaded on the electrode is 0.1-10 mg cm-1(ii) a Wherein the electrode is carbon paper, glassy carbon, foamed nickel or carbon fiber.
O of the anode electrocatalytic oxygen evolution reaction catalytic material of the electrolyzed water2The preparation method of the gas generating electrode comprises the following steps: dispersing a catalytic material into a mixed solution of isopropanol and water, adding 1-10 wt% of perfluorinated sulfonic acid resin Nafion solution, stirring to obtain a mixed solution, coating the mixed solution on a working electrode, and drying.
Isopropanol in the mixed solution of isopropanol and water: the water is 1: 5-5: 1; the ratio of the metal/carbon material to the mixed solution of isopropanol and water is 0.5-20 mg: 1 mL; the ratio of the 1-10 wt% of perfluorinated sulfonic acid resin Nafion solution to the mixed solution of isopropanol and water is 1: 100-1: 10; the drying condition is vacuum drying at 25-60 ℃.
The invention synthesizes non-activated NiFe by precursor ion exchangem(OH)2+3mThe NiFe can be regulated and controlled by changing the type and proportion of the synthesized precursor and the concentration of the alkali liquor in the synthesis processm(OH)2+3mThe amorphous degree, the proportion of metal elements and other parameters, and further adjust the catalytic activity point position, and the synthesized NiFem(OH)2+3mAfter simple activation, the NiFe-based NiFe with high activity can be generatedm(OOH)1+mA catalyst. Meanwhile, the catalytic material is rich in raw materials, simple in synthesis method and excellent in catalytic activity and stability, so that the catalyst is suitable for large-scale commercial application.
Activated NiFe produced by this patentm(OOH)1+mThe catalyst has high activity of electrolyzing water to separate out oxygen. Phase thereofFor conventional synthetic means: NiFe obtained by directly reacting metal salt with alkaline solutionm(OH)2+3mThe catalyst has better catalytic activity and oxygen evolution reaction performance which is not possessed by the conventional NiFe catalyst (attached figure 10 and figure 24). Activated NiFe prepared by the methodm-OxHyCatalyst activity is also significantly high-zone RuO2Catalyst (FIG. 10, FIG. 11, FIG. 24 and FIG. 25), and it was at 100mA cm-2The activity was hardly decreased by the stability test for 100 hours at a high current density (FIG. 14 and FIG. 28), and the commercial production requirements were completely satisfied.
The nickel-iron-based catalytic material NiFem(OH)2+3mAfter the working electrode is coated, the electrochemical activation can be directly carried out to obtain the high-performance nickel-iron-based catalytic material NiFem-OxHyIt can be applied to the catalytic reaction of electrocatalytic oxygen evolution reaction (water oxidation reaction), and can obviously reduce the overpotential of the electrolytic water oxygen evolution reaction (the overpotential reaches 10mA cm)-2The current density of (a) is only 263mV over-potential and the Tafel slope is also only 35mV dec-1) Its activity and stability are obviously superior to those of commercial RuO2Catalyst (which is up to 10mA cm-2The current density of (a) is only 288mV over-potential, and the Tafel slope is also 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 (which reaches 10mA cm)-2The current density of (a) is only 263mV over-potential and the Tafel slope is also only 35mV dec-1) Obviously improves the catalyst performance and is obviously superior to commercial noble metal RuO2The catalyst can effectively reduce the cost of preparing high-purity hydrogen by electrolyzing water, and the concentration of the catalyst is 100mA cm-2The high-current-density-based catalyst still has high stability under high current density, the activity is hardly reduced in a stability test of 100h, and the requirement of commercial production is completely met.
Drawings
FIG. 1 shows the precursor NiFe in example 10.2Scanning Electron Microscopy (SEM) of the Fe PBA sample, ScaleThe ruler is 100 nm.
FIG. 2 shows NiFe in example 10.2(OH)2.6Scanning Electron Microscopy (SEM) of the sample, with a 100nm scale.
FIG. 3 shows NiFe in example 10.2(OH)2.6Elemental distribution (SEM-EDS) of the sample with 4 μm scale.
FIG. 4 shows the precursor NiFe in example 10.2-Fe PBA sample with standard Ni3[Fe(CN)6]2·10H2X-ray diffraction (XRD) pattern of O card.
FIG. 5 shows NiFe in example 10.2(OH)2.6Sample and Standard alpha-Ni (OH)2X-ray diffraction (XRD) pattern of the card.
FIG. 6 shows the precursor NiFe in example 10.2Mossbauer spectra of the Fe PBA samples.
FIG. 7 shows NiFe in example 10.2(OH)2.6Mossbauer spectra of the samples.
FIG. 8 shows NiFe in example 10.2(OH)2.6Sample and Standard alpha-Ni (OH)2Raman spectrum of the sample.
FIG. 9 NiFe in example 10.2(OH)2.6Sample and NiFe (OOH) produced after activation1.2The cyclic voltammetry curve is obtained by testing a sample in an electrocatalytic oxygen evolution reaction, the initial potential of the scanning range in the test is 0.02V, the end potential of the scanning is 0.5V, and the scanning rate is 10mV s-1。
FIG. 10 shows the NiFe obtained after activation in example 10.2(OOH)1.2Sample, commercial RuO2Sample, conventional metal salts (nickel and iron salts) in strongly alkaline solution (2mol L)-1KOH solution) directly generated NiFe0.2(OH)2.6Comparison graph of electrocatalytic oxygen evolution reaction performance of the sample.
FIG. 11 shows the NiFe obtained after activation in example 10.2(OOH)1.2Sample, commercial RuO2The sample is subjected to electrocatalytic oxygen evolution reaction to obtain a line scanning voltammetry curve.
FIG. 12 shows a composition of example 1 consisting of NiFe0.2(OOH)1.2Samples, merchantsIndustrialized RuO2Line sweep voltammogram obtained for the sample (FIG. 11).
FIG. 13 shows the NiFe-based catalyst NiFe in example 10.2(OOH)1.2And commercialized RuO2Reaching 10mA cm in the electrolytic water oxygen evolution reaction-2An overpotential at a current density of (a).
FIG. 14 shows NiFe in example 10.2(OOH)1.2The stability test of the sample in the electrocatalytic oxygen evolution reaction shows that the loading amount of the catalyst in the test is 0.16mg cm-2Current density of 100mA cm-2The stability test time is 100 h.
FIG. 15 shows the precursor NiFe in example 20.25Scanning Electron Microscopy (SEM) of Fe PBA samples with a scale of 100 nm.
FIG. 16 shows NiFe in example 20.25(OH)2.75Scanning Electron Microscopy (SEM) of the sample, with a 100nm scale.
FIG. 17 shows NiFe in example 20.25(OH)2.75Elemental distribution (SEM-EDS) of the sample with 7 μm scale.
FIG. 18 shows the precursor NiFe in example 20.25-Fe PBA sample with standard Ni3[Fe(CN)6]2·10H2X-ray diffraction (XRD) pattern of O card.
FIG. 19 shows NiFe in example 20.25(OH)2.75Sample and Standard alpha-Ni (OH)2X-ray diffraction (XRD) pattern of the card.
FIG. 20 shows the precursor NiFe in example 20.25Mossbauer spectra of the Fe PBA samples.
FIG. 21 is a NiFe sample of example 20.25(OH)2.75Mossbauer spectra of the samples.
FIG. 22 shows NiFe in example 20.25(OH)2.75Sample and Standard alpha-Ni (OH)2Raman spectrum of the sample.
FIG. 23 shows NiFe in example 20.25(OH)2.75Sample and NiFe (OOH) produced after activation1.25The cyclic voltammetry curve is obtained by testing before and after activation in the electrocatalytic oxygen evolution reaction。
FIG. 24 shows the high activity of NiFe after activation in example 20.25(OOH)1.25Sample, commercial RuO2Sample, conventional metal salt (nickel salt, iron salt) in strong alkaline solution (2mol L)-1KOH solution) directly generated NiFe0.25(OH)2.75Comparison graph of electrocatalytic oxygen evolution reaction performance of the sample.
FIG. 25 shows the high activity of NiFe after activation in example 20.25(OOH)1.25Sample, commercial RuO2The linear scanning voltammetry curve of the sample obtained in the electrocatalytic oxygen evolution reaction test.
FIG. 26 shows a composition of example 2 consisting of NiFe0.25(OOH)1.25Sample, commercial RuO2Line sweep voltammogram obtained for the sample (FIG. 25).
FIG. 27 shows the NiFe-based catalyst NiFe in example 20.25(OOH)1.25And commercialized RuO2Reaching 10mA cm in electrocatalytic oxygen evolution reaction-2An overpotential at a current density of (a).
FIG. 28 is a representation of NiFe in example 20.2-OxHyThe stability test of the sample in the electrocatalytic oxygen evolution reaction shows that the loading amount of the catalyst in the test is 0.16mg cm-2Current density of 100mA cm-2The stability test time is 100 h.
FIG. 29 shows NiFe in example 10.2(OOH)1.2NiFe in example 20.25(OOH)1.25NiFe in example 30.11(OOH)1.11NiFe in example 40.29(OOH)1.29And commercial RuO2The activity of the active samples in the electrocatalytic oxygen evolution reaction is compared.
FIG. 30 shows NiFe in example 10.2(OOH)1.2NiFe in example 20.25(OOH)1.25NiFe in example 30.11(OOH)1.11NiFe in example 40.29(OOH)1.29And commercial RuO2The tafel slope curve graph of the active sample obtained in the electrocatalytic oxygen evolution reaction.
FIG. 31 shows NiFe in example 10.2(OOH)1.2NiFe in example 20.25(OOH)1.25NiFe in example 30.11(OOH)1.11NiFe in example 40.29(OOH)1.29And commercial RuO2The active sample is in the electrocatalytic oxygen evolution reaction at 10mA cm-2Overpotential value measured at current density.
Detailed Description
Example 1 high Performance NiFe-based electrocatalytic oxygen evolution catalyst NiFe0.2(OOH)1.2Preparation and electrocatalytic oxygen evolution test of
1) Precursor NiFe0.2Preparation of-Fe PBA
Firstly, 987.8mg of K is taken3[Fe(CN)3]Dissolved in a beaker containing 300mL of ultrapure water in a volume of 500mL (10mol L)-1) Ultrasonic treatment is carried out to fully dissolve the mixture; then according to Ni3+(molar amount of nickel ion in metallic nickel salt): fe3+(molar amount of iron ion in metallic iron salt): [ Fe (CN)6]3+(molar weight of iron cyanide in ferricyanate) 1: m (m +2/3), wherein m is 0.2, and NiCl is prepared2·6H2O and FeCl3·6H2O, namely 822.8mg of NiCl are taken respectively2·6H2O and 300mg of 197.1mg FeCl3·6H2O was dissolved in a 1L beaker containing 300mL of ultrapure water, and the reactant (K) was added3[Fe(CN)3]、NiCl2·6H2O and FeCl3·6H2O) total mass 8% (of NiCl)2·6H2O and FeCl3·6H215.7 percent of the total mass of the O metal salt) of 161mg of conductive material (carbon nano tube with the outer diameter of 10-20 mu m and the length of 5-15 mu m) and vigorously stirred to form a solution in which the conductive material is uniformly mixed with the NiFe metal salt; then the configured K3[Fe(CN)3]Solution (10mol L)-1)300mL of the mixed metal salt is added dropwise and stirred; after the dripping is finished, continuously stirring for 30min and aging for 20 h; finally centrifuging, and drying the solid product at the constant temperature of 60 ℃ for 12h to obtain a precursor NiFe0.2-Fe PBA。
2)NiFe0.2(OH)2.6Preparation of samples
To the NiFe prepared0.2Taking a Fe-PBA precursor as a raw material, dispersing 200mg of the Fe-PBA precursor in a beaker with the volume of 500mL and filled with 100mL of ultrapure water, stirring by intense magnetic force, adding 200mL of 2mol L of PBA precursor after the Fe-PBA precursor is uniformly dispersed-1KOH, vigorously stirred for 15min, centrifuged, washed with ultrapure water for 3 times, centrifuged with ethanol for 1 time, and dried the obtained precipitate at 60 ℃ for 12h to obtain NiFe0.2(OH)2.6And (3) sampling.
3) High performance NiFe0.2(OOH)1.2Electrode preparation of catalyst
Taking the synthesized NiFe0.2(OH)2.6Sample 4mg was added to 1mL of the dispersion (490. mu.L of ultrapure water H)20(18.2M omega), 490 mu L of isopropanol and 20 mu L of nafion solution) are dispersed by ultrasonic (more than or equal to 6 h); the catalyst slurry was then uniformly coated onto a commercial glassy carbon electrode 5mm in diameter as the working electrode (0.2 mg cm loading)-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-1And KOH is used as electrolyte and is connected to an electrochemical workstation for activation. Specifically setting parameters and steps for activation of the electrochemical workstation: activating by cyclic voltammetry, wherein the scanning voltage range is 0.02-0.5V; the sweeping speed is 10mV s-1(ii) a The number of scanning turns is 200 turns, and the scanning is forward scanning. Cyclic voltammetry curves before and after sample activation (FIG. 9), it can be seen that NiFe is generated after activation0.2(OOH)1.2The activity is obviously improved.
4) Commercial RuO for reference2Electrode preparation of electrocatalytic oxygen evolution catalyst
Commercial RuO to direct purchase2Sample 4mg was added to 1mL of the dispersion (490. mu.L of ultrapure water H)20(18.2M omega), 490 mu L of isopropanol and 20 mu L of nafion solution) are dispersed by ultrasonic (more than or equal to 6 h); the catalyst slurry was then uniformly coated onto a commercial glassy carbon electrode 5mm in diameter as the working electrode (0.2 mg cm loading)-2)。
5) NiFe produced by conventional methods for reference0.2(OH)2.6Preparation of electrodes
Respectively taking 82.3mg NiCl2·6H2O and 300mg of 19.7mg FeCl3·6H2O was dissolved in a 500m L beaker containing 100mL of ultrapure water, and NiCl was taken2·6H2O and FeCl3·6H2O in NiCl2·6H2O and FeCl3·6H215.7 percent (the same proportion as that in the step 3) of conductive material (16.1 mg, the outer diameter of which is 10-20 mu m, and the length of which is 5-15 mu m) of the total mass of the O metal salt is vigorously stirred, and 200mL of 2mol L of conductive material is added after the conductive material is uniformly dispersed-1KOH, vigorously stirred for 15min, centrifuged, washed with ultrapure water for 3 times, and centrifuged with ethanol for 1 time to obtain precipitate which is NiFe generated conventionally0.2(OH)2.6The sample is dried in a constant temperature drying oven at 60 ℃ for 12 h.
Taking NiFe doped with conductive material generated conventionally after drying0.2(OH)2.6Sample 4mg was added to 1mL of the dispersion (490. mu.L of ultrapure water H)20(18.2M omega), 490 mu L of isopropanol and 20 mu L of nafion solution) are dispersed by ultrasonic (more than or equal to 6 h); the catalyst slurry was then uniformly coated onto a commercial glassy carbon electrode 5mm in diameter as the working electrode (0.2 mg cm loading)-2)。
6) High-activity NiFe prepared in step 3) of example 10.2(OOH)1.2RuO commercialized in step 4)2NiFe produced by the conventional method in step 5)0.2(OH)2.6And (5) comparing the activity.
Respectively taking the working electrode prepared in the steps 3), 4) and 5), respectively taking a saturated calomel electrode and a carbon rod with the diameter of 6mm as a reference electrode and a counter electrode to form a three-electrode system, and using 1mol L of the working electrode-1And KOH is used as electrolyte and is connected to an electrochemical workstation to carry out electrochemical test. The reaction activity of the strain is evaluated by adopting a linear scanning voltammetry curve, wherein the scanning mode is positive scanning, and the scanning speed is 5mV s-1The scanning start potential is 0.02V, and the scanning end potential is 0.5V. The results are shown in FIG. 10.
7) Example 1 step 3) NiFe0.2(OOH)1.2And RuO in step 4)2Catalyst performance and tafel slope comparison.
Respectively obtained in example 1Step 3) and step 4) are carried out to obtain the working electrode, 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 a linear voltammetry curve (shown in figure 11) is obtained by slow scanning, wherein the scanning rate is 1mV s-1The scanning start voltage is 0.02V, and the end voltage is 0.05V. Then, the logarithm of the curve is derived to obtain the Tafel slope curve (FIG. 12), and the curve of the logarithm of the curve of the logarithm of the curve of the logarithm of the curve of the logarithm of the curve of the logarithm of the curve of-2Overpotential at current density (fig. 13). (the results were all converted to a standard hydrogen electrode (vs. rhe)).
8)NiFe0.2(OOH)1.2And (5) testing the stability of the sample.
Taking the synthesized NiFe0.2(OH)2.6Sample 4mg was added to 1mL of the dispersion (490. mu.L of ultrapure water H)20(18.2M omega), 490 mu L of isopropanol and 20 mu L of nafion solution) are dispersed by ultrasonic (more than or equal to 6 h); then the catalyst slurry was uniformly coated on a foamed nickel having a length of 2cm and a width of 1cm as a working electrode (loading amount 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-1And (3) connecting KOH serving as electrolyte to an electrochemical workstation for activation, wherein the activation process is the same as that in 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-2And a stability test is carried out for 100h, and the result shows that the activity of the product is hardly reduced in the stability test for 100h, and the excellent stability completely meets the requirement of commercialization.
Example 2 high Performance NiFe-based electrocatalytic oxygen evolution catalyst NiFe0.25(OOH)1.25Preparation and electrocatalytic oxygen evolution test of
1) Precursor NiFe0.25Preparation of-Fe PBAs
Firstly, 987.8mg of K is taken3[Fe(CN)3]Dissolved in a beaker containing 300mL of ultrapure water in a volume of 500mL (10mol L)-1) Ultrasonic treatment is carried out to fully dissolve the mixture; then according to Ni3+(molar amount of nickel ion in metallic nickel salt): fe3+(molarity of iron ion in metallic iron saltMolar amount): [ Fe (CN)6]3+(molar weight of iron cyanide in ferricyanate) 1: m (m +2/3), wherein m is 0.2, and NiCl is prepared2·6H2O and FeCl3·6H2O, namely 777.9mg of NiCl are taken respectively2·6H2O and 300mg of 221.2mg FeCl3·6H2O was dissolved in a 1L beaker containing 300mL of ultrapure water, and the reactant (K) was added3[Fe(CN)3]、NiCl2·6H2O and FeCl3·6H2O) total mass 8% (of NiCl)2·6H2O and FeCl3·6H215.9% of the total mass of the O metal salt) 159.0mg of conductive material (carbon nano tube with the outer diameter of 10-20 μm and the length of 5-15 μm) and stirred vigorously to form a solution in which the conductive material and the NiFe metal salt are mixed uniformly; then the configured K3[Fe(CN)3]Solution (10mol L)-1)300mL of the mixed metal salt is added dropwise and stirred; after the dripping is finished, continuously stirring for 30min and aging for 20 h; finally centrifuging, and drying the solid product at the constant temperature of 60 ℃ for 12h to obtain a precursor NiFe0.25-Fe PBAs。
2)NiFe0.25(OH)2.75Preparation of samples
To the NiFe prepared0.25Taking a Fe-PBA precursor as a raw material, dispersing 200mg of the Fe-PBA precursor in a beaker with the volume of 500mL and filled with 100mL of ultrapure water, stirring by intense magnetic force, adding 200mL of 2mol L of PBA precursor after the Fe-PBA precursor is uniformly dispersed-1KOH, vigorously stirred for 15min, centrifuged, washed with ultrapure water for 3 times, centrifuged with ethanol for 1 time, and dried the obtained precipitate at 60 ℃ for 12h to obtain NiFe0.25(OH)2.75And (3) sampling.
3) High performance NiFe0.25(OOH)1.25Electrode preparation of catalyst
Taking the synthesized NiFe0.25(OH)2.75Sample 4mg was added to 1mL of the dispersion (490. mu.L of ultrapure water H)20(18.2M omega), 490 mu L of isopropanol and 20 mu L of nafion solution) are dispersed by ultrasonic (more than or equal to 6 h); the catalyst slurry was then uniformly coated onto a commercial glassy carbon electrode 5mm in diameter as the working electrode (0.2 mg cm loading)-2) Simultaneous saturation of calomel electrode and diameter 6A 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 carbon rod is used-1And KOH is used as electrolyte and is connected to an electrochemical workstation for activation. Specifically setting parameters and steps for activation of the electrochemical workstation: activating by cyclic voltammetry, wherein the scanning voltage range is 0.02-0.5V; the sweeping speed is 10mV s-1(ii) a The number of scanning turns is 200 turns, and the scanning is forward scanning. The cyclic voltammograms before and after sample activation are shown in FIG. 9, and it can be seen that NiFe is generated after activation0.25(OOH)1.25The activity is obviously improved.
4) Commercial RuO for reference2Electrode preparation of electrocatalytic oxygen evolution catalyst
Commercial RuO to direct purchase2Sample 4mg was added to 1mL of the dispersion (490. mu.L of ultrapure water H)20(18.2M omega), 490 mu L of isopropanol and 20 mu L of nafion solution) are dispersed by ultrasonic (more than or equal to 6 h); the catalyst slurry was then uniformly coated onto a commercial glassy carbon electrode 5mm in diameter as the working electrode (0.2 mg cm loading)-2)。
5) NiFe produced by conventional methods for reference0.25(OH)2.75Preparation of electrodes
77.8mg of NiCl are respectively taken2·6H2O and 300mg of 22.1mg FeCl3·6H2O was dissolved in a 500m L beaker containing 100mL of ultrapure water, and NiCl was taken2·6H2O and FeCl3·6H2O and (in NiCl)2·6H2O and FeCl3·6H215.9 percent (same as the proportion in the step 3)) of conductive material (15.9 mg (carbon nano tube with the outer diameter of 10-20 mu m and the length of 5-15 mu m) of the total mass of the O metal salt is vigorously stirred, and 200mL of 2mol L of conductive material is added after the conductive material is uniformly dispersed-1KOH, vigorously stirred for 15min, centrifuged, washed with ultrapure water for 3 times, and centrifuged with ethanol for 1 time to obtain precipitate which is NiFe generated conventionally0.25(OH)2.75The sample was then dried in a constant temperature oven at 60 ℃.
Taking NiFe doped with conductive material generated conventionally after drying0.25(OH)2.75Sample 4mg was added to 1mL of the dispersion (490. mu.L of ultrapure water H)20(18.2 M.OMEGA.), 490. mu.L isopropanol20 mu L of nafion solution) ultrasonic (more than or equal to 6h) dispersion; the catalyst slurry was then uniformly coated onto a commercial glassy carbon electrode 5mm in diameter as the working electrode (0.2 mg cm loading)-2)。
6) High-activity NiFe prepared in step 3) of example 20.25(OOH)1.25RuO commercialized in step 4)2NiFe produced by the conventional method in step 5)0.25(OH)2.75And (5) comparing the activity.
Respectively taking the working electrode prepared in the steps 3), 4) and 5), respectively taking a saturated calomel electrode and a carbon rod with the diameter of 6mm as a reference electrode and a counter electrode to form a three-electrode system, and using 1mol L of the working electrode-1And KOH is used as electrolyte and is connected to an electrochemical workstation to carry out electrochemical test. The reaction activity of the strain is evaluated by adopting a linear scanning voltammetry curve, wherein the scanning mode is positive scanning, and the scanning speed is 5mV s-1The scanning start potential is 0.02V, and the scanning end potential is 0.5V. The results are shown in FIG. 24.
7) Example 2 step 3) NiFe0.25(OOH)1.25And RuO in step 4)2Catalyst performance and tafel slope comparison.
Taking the working electrode prepared in the step 3) and the step 4) in the example 2 respectively, taking a saturated calomel electrode and a carbon rod with the diameter of 6mm as a reference electrode and a counter electrode respectively to form a three-electrode system, and obtaining a linear voltammetry curve graph (25) of the working electrode through slow scanning, wherein the scanning speed is 1mV s-1The scanning start voltage is 0.02V, and the end voltage is 0.05V. Then, the logarithm of the obtained product is derived to obtain the Tafel slope curve (FIG. 26), and the two curves at 10mA cm can be obtained from FIG. 11-2Overpotential at current density (fig. 27). (the results were all converted to a standard hydrogen electrode (vs. rhe)).
8)NiFe0.25(OOH)1.25And (5) testing the stability of the sample.
Taking the synthesized NiFe0.25(OH)2.75The sample was added to 1mL of the dispersion (490. mu.L of ultrapure water H)20(18.2M omega), 490 mu L of isopropanol and 20 mu L of nafion solution) are dispersed by ultrasonic (more than or equal to 6 h); then uniformly coating the catalyst slurry on a bubble with the length of 2cm, the width of 1cm and the thickness of 0.3mmThe nickel foam is used as a working electrode (the load is 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-1And (3) connecting KOH serving as electrolyte to an electrochemical workstation for activation, wherein the activation process is the same as that in 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-2The stability test was carried out for 100h (FIG. 28), and the results showed almost no reduction in activity in the stability test for up to 100h, and the excellent stability was fully satisfactory for commercialization.
Example 3 high Performance NiFe-based electrocatalytic oxygen evolution catalyst NiFe0.11(OOH)1.11Preparation and electrocatalytic oxygen evolution test of
Example 3 removal of NiFe precursor0.11Ni reactant in the Synthesis of Fe PBA3+(molar amount of nickel ion in metallic nickel salt): fe3+(molar amount of iron ion in metallic iron salt): [ Fe (CN)6]3+(molar amount of ferricyanide in ferricyanate): 1: m (m +2/3) in a ratio different from that in example 1, the procedure was the same as in example 1 (K)3[Fe(CN)3]The amount used was unchanged). In this embodiment, the value m is 0.11.
Example 4 high Performance NiFe-based electrocatalytic oxygen evolution catalyst NiFe0.29(OOH)1.29Preparation and electrocatalytic oxygen evolution test of
Example 4 removal of NiFe precursor0.29Ni reactant in the Synthesis of Fe PBA3+(molar amount of nickel ion in metallic nickel salt): fe3+(molar amount of iron ion in metallic iron salt): [ Fe (CN)6]3+(molar amount of ferricyanide in ferricyanate): 1: m (m +2/3) in a ratio different from that in example 1, the procedure was the same as in example 1 (K)3[Fe(CN)3]The amount used was unchanged). The value of m in this example is 0.29, example 1, example 2, example 3 and example 4 and the commercial noble metal RuO2The activity pairs of (2) are shown in figure 29. During the test, the loading amounts of the catalysts on the glassy carbon electrodes in the three-electrode system are all 0.2mg cm-2The counter electrode is a carbon rod with the diameter of 6mm, and the reference electrode is a saturated calomel electrode. The scanning mode is as follows: line Sweep Voltammetry (LSV), negative sweep; scanning rate: 1mV s-1(ii) a Scanning initial voltage is 0.02V; the scan termination voltage is 0.5V. The results were converted to standard hydrogen electrodes (vs. rhe). Tafel slope plot from line sweep voltammogram and at 10mA cm-2The overpotential values obtained at the current density are shown in FIG. 30 and FIG. 31, respectively.
Claims (10)
1. A preparation method of a nickel-iron-based catalyst is characterized by comprising the following steps:
1) adding solution containing metal nickel salt and metal iron salt into iron cyanate solution at room temperature to directly synthesize Prussian blue analogue (NiFe)m[Fe(CN)6](m+2/3)Is denoted as NiFem-Fe PBAs, m represents NiFemThe molar counting ratio of the medium Fe ions) as a precursor of the catalytic material;
2) dispersing the precursor of the catalytic material in a solvent uniformly, and then adding an alkaline solution to perform ion exchange to obtain the non-activated nickel-iron-based catalytic material NiFem(OH)2+3m(nickel iron hydroxide);
3) nickel-iron base catalytic material NiFem(OH)2+3mObtaining NiFe after electrochemical pretreatment and activationm(OOH)1+m(nickel iron oxyhydroxide) electrocatalytic oxygen evolution catalyst.
2. The method for preparing a precursor of a nickel-iron based catalytic material according to claim 1, wherein: the ratio of the metal Fe ions and the metal Ni ions in the metal iron salt and the metal nickel salt in the step 1) is m (Fe)3+/Ni3+) 0.05-0.55, preferably 0.10-0.33, more preferably 0.15-0.25.
3. The method for preparing a precursor of a nickel-iron based catalytic material according to claim 1, wherein:
in the step 1), the metal ferric salt is one or more than two of ferric trichloride hexahydrate, anhydrous ferric trichloride, ferric sulfate and ferric nitrate; the metal nickel salt is one or more of anhydrous nickel nitrate, nickel nitrate hexahydrate, nickel chloride hexahydrate and nickel sulfate;
the ferricyanate in the precursor of the catalytic material is one or more than two of potassium ferricyanide and sodium ferricyanide;
in the step 1), the concentration of the iron cyanate in the iron cyanate solution is 0.0001-20 mol L-1Preferably 5 to 15mol L-1More preferably 9 to 12mol L-1；
Taking the molar concentration of the iron cyanate as a standard, adding metal nickel salt and iron salt in the reaction according to the concentration of the iron cyanate Ni3 +(concentration of nickel ions in metallic nickel salt): fe3+(concentration of iron ion in metallic iron salt): [ Fe (CN)6]3+(concentration of ferricyanide in ferricyanate) ═ 1: m (m + 2/3);
mixing uniformly according to Fe3+(concentration of iron ion in metallic iron salt): [ Fe (CN)6]3+(the concentration of ferricyanide in ferricyanate) is 1: m (m +2/3), the solution of metal nickel salt and metal iron salt is added into the potassium ferricyanide solution drop by drop, the mixture is stirred, after the solution is added, the stirring is continued for 10 to 120min (preferably 20 to 60min, more preferably 25 to 45min), the aging is carried out for 5 to 30h (preferably 8 to 20h, more preferably 10 to 15h) at room temperature, the solid-liquid separation and the solid drying are carried out, and the catalytic material precursor NiFe is obtainedm-Fe PBAs。
4. The production method 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;
dispersing the precursor of the catalytic material in solvent, adding alkali solution for ion exchange, wherein the alkali solution can be one or two of potassium hydroxide or sodium hydroxide, and the concentration of the alkali solution is 0.1-4.5 mol L-1Preferably 1.5 to 3.0mol L-1More preferably 1.6 to 2.3mol L-1。
5. The production method according to claim 1 or 4, characterized in that:
in step 2), the precursor 150-200 mg of NiFe is first addedmUniformly dispersing the-Fe PBAs precursor in 50-100 mL of solvent, adding 100-200 mL of alkaline solution, stirring for 5-30 min to fully perform ion exchange for topological transformation, centrifugally washing for 2-5 times by using ultrapure water after stirring, centrifugally washing for 1-3 times by using ethanol, and drying at the constant temperature of 40-130 ℃ for 8-24 h to obtain the unactivated NiFem(OH)(2+3m)And (3) sampling.
6. The process according to claim 1, characterized in that:
in the step 3), the electrochemical pretreatment activation can be carried out by using cyclic voltammetry or potentiostatic method;
specific cyclic voltammetry: taking saturated calomel electrode as reference, and scanning initial voltage is 0V-0.05V; the scanning termination voltage is 0.45V-0.55V; the scanning rate is 1-200 mV s-1All of them, preferably 1 to 50mV s-1More preferably 15-30 mV s-1(ii) a The number of scanning circles is 50-300 circles; the scanning direction is positive scanning or negative scanning;
activating by a potentiostatic method: applying potential of 0.4-0.6V (vs. SCE with saturated calomel electrode as reference) for 10-60 min.
7. The production method according to claim 1 or 6, characterized in that:
in the step 3), the step (c),
taking non-activated NiFe doped with conductive materialm(OxH)(2+3m)Dispersing the sample in the dispersing liquid uniformly, then coating or dropping the sample on the working electrode uniformly, drying, and obtaining NiFem(OxH)(2+3m)The loading capacity is 0.1-1 mg cm-2(ii) a Assembling into a three-electrode system to perform electrochemical activation;
the dispersion liquid is composed of a mixed solution of isopropanol and water added with a perfluorinated sulfonic acid resin binder; the volume ratio of isopropanol to water is 0.1:1 to 3.0:1, preferably 0.2:1 to 2:1, more preferably 0.5:1 to 1.5: 1; the amount of perfluorosulfonic acid resin binder in the dispersion is 0.1% to 20%, preferably 0.5% to 10%, more preferably 2% to 10% of the total volume of isopropanol and water;
the unactivated catalyst was dispersed in the dispersion ultrasonically to a homogeneous slurry (1-6 mg mL)-1)；
The working electrode is a foam nickel, carbon paper or glassy carbon electrode;
a commercial working electrode loaded with non-activated NiFe-based catalyst, a commercial counter electrode (a carbon rod or a platinum wire electrode) and a commercial reference electrode (a saturated calomel electrode, a silver chloride electrode or a mercury oxide electrode) form a three-electrode system, and 0.1-4 mol L of the three-electrode system is used-1KOH or NaOH solution is used as electrolyte, and is connected to an electrochemical workstation to carry out electrochemical activation, and a high-activity nickel-iron-based catalytic material NiFe for electrocatalytic oxygen evolution reaction is directly generated on an electrodem(OOH)1+m。
8. The production method according to any one of claims 1 to 7, characterized in that:
to obtain NiFem(OOH)(1+m)The active electrocatalytic oxygen evolution catalyst is doped with a conductive material;
the doped conductive material can be added in any one step or any two steps or three steps in the reaction process and the three steps;
namely, the precursor can be added before the reaction in the synthesis process of the nickel-iron-based catalytic material precursor in the step 1), or can be added before the ion exchange in the ion exchange step in the step 2), or can be added without activation in the activation step in the step 3);
the adding amount of the conductive material accounts for 2-20% of the total mass of precursor reactants (metal iron salt, metal nickel salt and ferricyanate), the conductive material is one or more of acetylene black, Carbon fiber, Carbon nano tube, X72 Carbon powder and Ketjenblack (Ketjenblack EC300J, Ketjenblack EC600JD, Carbon ECP and Carbon ECP600 JD).
9. An activated active electrolytic water oxygen evolution catalyst material obtained by the production method as set forth in any one of claims 1 to 8.
10. Use of the activated active electrolytic water oxygen evolution catalyst material of claim 9, characterized in that: it can be applied to the catalytic reaction of the electrocatalytic oxygen evolution reaction (or water oxidation reaction) of the electrolytic water anode reaction.
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