CN117987861A - High-activity nano porous electrolyzed water catalyst and preparation method and application thereof - Google Patents
High-activity nano porous electrolyzed water catalyst and preparation method and application thereof Download PDFInfo
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- 239000000203 mixture Substances 0.000 claims abstract description 5
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 30
- 239000001257 hydrogen Substances 0.000 claims description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
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- 229910052760 oxygen Inorganic materials 0.000 claims description 11
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- 239000011148 porous material Substances 0.000 claims description 4
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- C25B11/042—Electrodes formed of a single material
- C25B11/046—Alloys
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a high-activity nano porous electrolyzed water catalyst, a preparation method thereof and application thereof in electrolyzed water. The main active components of the catalyst have the chemical composition of Fe aCobNicZrdPte and a, b, c, d, e which represent atomic ratio, wherein a is more than or equal to 25 and less than or equal to 35, b is more than or equal to 3 and less than or equal to 9, c is more than or equal to 4 and less than or equal to 10, d is more than or equal to 2 and less than or equal to 7, e is more than or equal to 48 and less than or equal to 60, and a+b+c+d+e=100; the main active component has a nano-porous structure and comprises face-centered cubic phase nanocrystals. The preparation method comprises the following steps: proportioning according to a chemical formula of a precursor, and smelting uniformly to prepare master alloy; the chemical formula of the precursor is Fe a'Cob'Nic'Zrd'Pte', a ', b', c ', d', e 'represent atomic ratio, and a' is 60-70,8-13, c '13, d' 12,0< e '10, a' +b '+c' +d '+e' =100; after melting the master alloy, spraying the master alloy onto the surface of a rotating copper roller to obtain an amorphous alloy strip precursor; and adding the amorphous alloy strip precursor into etching liquid for etching treatment to obtain the nano porous electrolyzed water catalyst.
Description
Technical Field
The invention relates to the field of electrolytic water catalysts, in particular to a high-activity nano porous electrolytic water catalyst, a preparation method and application thereof.
Background
Hydrogen energy is environmentally friendly and can be developed continuously, and is a zero-carbon energy carrier which is widely concerned.
The existing clean hydrogen production methods comprise biomass hydrogen production, photochemical hydrogen production, electrolytic water hydrogen production and the like, wherein the electrolytic water hydrogen production has been widely paid attention to due to the advantages of being renewable, high in gas purity and the like.
Electrochemical hydrolysis consists of cathodic and anodic Hydrogen Evolution Reactions (HER) and Oxygen Evolution Reactions (OER), respectively, and efficient hydrolysis can be achieved by using an efficient electrocatalyst. The applicant previously applied for the invention patent with the publication number of CN116254561A, wherein a nano-porous dual-function full-hydropower catalyst is introduced, in particular a phase-splitting structure Fe aCobNicZrdPe (non-pure metal) consisting of metal phosphide and a matrix, wherein a is more than or equal to 10 and less than or equal to 13, b is more than or equal to 22 and less than or equal to 25, c is more than or equal to 20 and less than or equal to 23, d is more than or equal to 24 and less than or equal to 24, e is more than or equal to 11 and less than or equal to 24, d+e is more than or equal to 35, a+b+c+e=100, which is obtained by etching Cu and part of Fe, ni, co, zr through mixed acid of concentrated hydrochloric acid and concentrated nitric acid by precursor high-entropy crystal alloy [ (FeNiCo) 0.6Cu0.3Zr0.1]100-xPx (0 at% < x is less than or equal to 10 at%), fe, ni, co and the like molar ratio is less than 20 percent, and the whole is crystalline.
Currently known metals such as Pt, ru, ir, etc. exhibit excellent electrocatalytic activity due to high intrinsic activity, but these noble metals are scarce and costly, and it is difficult to meet practical production requirements. It is therefore a great challenge to develop catalysts with low cost and high performance.
A few researches show that partial non-noble metal catalysts such as multi-component alloys have better hydrogen evolution performance, but the materials have the common problems of poor stability, few active site numbers, slow catalytic dynamics and the like. And the addition of a small amount of noble metal can improve the number of active sites of the catalyst while reducing the cost, and the catalytic capability of the catalyst is obviously enhanced by the cooperation of multiple elements.
The amorphous alloy has wide component regulation and control range, the elements in the alloy are uniformly distributed, the problems of segregation and the like are avoided, and the amorphous alloy has excellent mechanical properties, so that the amorphous alloy gradually enters a public view as an integrated electrode material with self-supporting performance.
The active sites in the amorphous alloy are generally connected through chemical bonds, so that the amorphous alloy has strong stability, and the electronic structure of the metal active sites can be regulated and controlled more easily through the synergistic effect between elements. Therefore, doping elements with excellent catalytic performance such as Pt on the amorphous alloy is convenient for regulating and controlling the electronic structure of Pt, and the performance of the catalyst is improved.
In order to further improve the activity of the catalyst, optimize the electronic structure of the active site Pt and improve the number of the active sites, a three-dimensional nano porous structure can be constructed on the amorphous surface by a dealloying mode (active elements are selectively dissolved in the alloy), which is important for accelerating the water decomposition reaction process and improving the catalytic reaction activity of the catalyst. Some electrocatalysts with electronic structural control of the active sites have been applied to the water electrolysis process, but currently investigated such catalysts are essentially not cost effective and are still stable at large current densities of the industrial scale (500 mA/cm 2).
Therefore, the components of the amorphous alloy are regulated and controlled, the electronic structure of the active site is optimized, and meanwhile, the low-cost water electrolysis catalyst which can efficiently and stably work under the high current density is prepared by adding a small amount of noble metal, so that the industrial application of the catalyst is facilitated.
Disclosure of Invention
Aiming at the technical problems and the defects existing in the field, the invention provides a high-activity nano porous electrolyzed water catalyst which is used as an electrocatalyst and has excellent hydrogen evolution and oxygen evolution performances, and can realize rapid and efficient electrolysis of water and stable electrolysis of water under high current density.
The specific technical scheme is as follows:
the chemical composition of the main active component of the high-activity nano porous electrolyzed water catalyst is Fe aCobNicZrdPte, wherein a, b, c, d, e represents an atomic ratio, a is more than or equal to 25 and less than or equal to 35, b is more than or equal to 3 and less than or equal to 9, c is more than or equal to 4 and less than or equal to 10, d is more than or equal to 2 and less than or equal to 7, e is more than or equal to 48 and less than or equal to 60, and a+b+c+d+e=100;
the primary active component has a nanoporous structure comprising Face Centered Cubic (FCC) phase nanocrystals.
In the high-activity nano porous electrolyzed water catalyst, pt subjected to electronic structure optimization is directly exposed on the surface of the multi-stage nano porous structure, so that Pt element can be fully used as a catalytic reaction active site, and more efficient electrocatalysis is realized. Compared with the existing Pt/C and other C-supported catalysts, the catalyst has higher reactivity and stability, and meanwhile, the preparation process of the sample is simple and the cost is low.
In the high-activity nano porous electrolyzed water catalyst, pt atoms are confined in the catalyst by stable metal bonds (Pt is taken as a main active site, and is not easy to fall off and high in stability), so that the catalyst can still keep excellent catalytic performance after long-time reaction under the high current density of more than 500mA/cm 2.
In one embodiment, the high activity nanoporous electrolyzed water catalyst comprises a matrix phase of amorphous structure and a main active component located on the surface layer of the matrix phase and having a nanoporous structure composed of amorphous and face centered cubic phase nanocrystals (composite phase). Under the condition that the nano porous structure is formed by the composite surface layer nano crystals with the specific atomic proportion and the whole amorphous structure, fe, ni, co, zr elements provide a large amount of electrons for Pt element, regulate and control the electronic structure of Pt, optimize the reactivity of Pt and enable the catalyst to efficiently perform an electrocatalytic process. Further, the thickness of the primary active ingredient may be 1 to 2 microns.
In one embodiment, the pore diameter of the nano porous structure of the high-activity nano porous electrolyzed water catalyst is 20-60 nm, and further 20-40 nm.
The invention also provides a preparation method of the high-activity nano porous electrolyzed water catalyst, which comprises the following steps:
Firstly, proportioning according to the chemical formula of a precursor, and smelting uniformly to prepare a master alloy; the chemical formula of the precursor is Fe a'Cob'Nic'Zrd'Pte', wherein a ', b', c ', d', e 'represent atomic ratios, and a' is 60-70,8-13, c '13, d' 12,0< e '10, a' +b '+c' +d '+e' =100;
step two, after melting the master alloy, spraying the master alloy onto the surface of a rotating copper roller to obtain an amorphous alloy strip precursor;
And thirdly, adding the amorphous alloy strip precursor into etching liquid for etching treatment to obtain the nano porous electrolyzed water catalyst.
In order to obtain the amorphous alloy in the second step, the preparation method of the invention needs to prepare the master alloy according to the chemical formula in the first step.
According to the invention, fe is largely corroded by the etching solution, co, ni and Zr are partially corroded, so that a porous structure is formed, the catalyst consists of an amorphous structure of a bulk phase and a stable face-centered cubic phase nanocrystalline porous layer, and active sites in crystal grains are connected by metal bonds due to the stability of the nanocrystalline structure, so that the prepared catalyst has higher stability. The etching effect of the etching liquid can rearrange the electronic structure of each element, promote the transfer of electrons from Fe, co, ni and Zr to Pt elements, optimize the catalytic activity of Pt, and accelerate the catalytic reaction kinetics.
In one embodiment, in step one, the feedstock used in the formulation has a purity of no less than 99wt%.
In one embodiment, in step one, the smelting is performed under an inert atmosphere. The inert atmosphere may be a rare gas such as argon.
In one embodiment, in the second step, the rotating speed of the copper roller is 40-45 m/s.
In one embodiment, in the third step, the etching solution is a sulfuric acid solution with a concentration of 1.5-2.5 mol/L.
In an embodiment, in the third step, the etching treatment time is 1-8 min.
In one embodiment, in the third step, the etching treatment is further followed by washing and drying operations.
The specific steps of the washing can be as follows: and repeatedly flushing the etched product with deionized water and ethanol in sequence.
The temperature of the drying can be 20-30 ℃ and the time can be 10-30 min.
The invention also provides application of the high-activity nano porous electrolyzed water catalyst in electrolyzed water.
As a general inventive concept, the invention also provides a method for electrolyzing water, which uses the high-activity nano porous electrolyzed water catalyst as a hydrogen evolution and/or oxygen evolution reaction catalyst to electrolyze water.
In one embodiment, the high activity nanoporous electrolyzed water catalyst is used directly as a working electrode.
The electrolyzed water may be conducted in an alkaline, neutral, acid wash environment.
In one embodiment, the electrolyzed water has an operating current density of not less than 500mA/cm 2.
The high-activity nano porous electrolyzed water catalyst has good hydrogen evolution and oxygen evolution reaction activities, has good stability, and can effectively realize stable and efficient electrolyzed water. The high-activity nano porous electrolytic water catalyst has self-supporting property and can be directly used as a working electrode.
Compared with the prior art, the invention has the beneficial effects that:
1) According to the invention, the amorphous alloy is formed by adopting a master alloy melt-spun formed by combining specific element proportions, and Fe, ni, co, zr provides more electrons for Pt element through a dealloying process on the basis, so that the electronic structure of the Pt element in the catalyst provided by the invention is optimized, the reactivity of the catalyst serving as an active site is improved, and meanwhile, the nano porous electrolyzed water catalyst has excellent electrolyzed water performance by more exposed Pt element in the nano porous electrolyzed water catalyst.
2) The high-activity nano porous electrolyzed water catalyst provided by the invention has the advantages that the pore diameter of the nano porous structure is uniformly distributed, the electrochemical activity specific surface area is large, the active reaction sites are increased, and the catalytic activity is superior to that of a noble metal Pt/C catalyst.
3) According to the preparation method provided by the invention, the sulfuric acid etching liquid is used for corroding the metal elements, so that as much Pt as possible is exposed to the outside, the preparation cost of raw materials is greatly reduced, better catalytic performance can be achieved by using less Pt, and the catalyst preparation process is simple.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of a nano-porous electrolyzed water catalyst prepared in comparative example 1 according to the present invention;
FIG. 2 is a photograph of a microscopic cross-section of a Scanning Electron Microscope (SEM) of the nano-porous electrolyzed water catalyst prepared in example 1 of the present invention;
FIG. 3 is a photograph of SEM surface micro-morphology of the nano-porous electrolyzed water catalyst prepared in example 1 of the present invention;
FIG. 4 is a photograph of the microscopic morphology of a Transmission Electron Microscope (TEM) nanoporous layer of the nanoporous electrolyzed water catalyst prepared in example 1 of the present invention;
FIG. 5 is a graph showing photoelectron spectroscopy of the nano-porous electrolyzed water catalyst prepared in example 1 of the present invention;
FIG. 6 is a graph showing the results of the test of hydrogen evolution performance of electrolyzed water of the electrocatalysts prepared in example 1 (FeCoNiZrPt after etching), comparative example 1 (FeCoNiZrPt) and comparative example 2 (Pt/C) according to the present invention, respectively;
FIG. 7 is a graph showing the results of the oxygen evolution performance test of the electrolytic water of the electrocatalysts prepared in example 1 (FeCoNiZrPt after etching) and comparative example 1 (FeCoNiZrPt) according to the present invention;
FIG. 8 is a graph showing the results of the stability test of hydrogen evolution CV cycle of the high-efficiency nano-porous electrolyzed water catalyst prepared in example 1 of the present invention;
FIG. 9 is a graph showing the results of a long-time hydrogen evolution stability test of the high-efficiency nano-porous electrolyzed water catalyst prepared in example 1 of the present invention.
Detailed Description
The invention will be further elucidated with reference to the drawings and to specific embodiments. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention.
Example 1
The embodiment provides a preparation method of a high-activity nano porous electrolyzed water catalyst, which comprises the following steps:
(1) And (3) selecting Fe, co, ni, zr, pt metal simple substances with purity of more than 99.9 weight percent, proportioning according to Fe 67Co10Ni10Zr10Pt3, carrying out arc melting on alloy elements in the proportion in an argon (Ar) protective atmosphere, uniformly mixing the elements, and cooling to obtain a master alloy ingot.
(2) And then, utilizing vacuum melt-spinning equipment to perform induction remelting on the master alloy cast ingot in a quartz tube, and then spraying the master alloy cast ingot onto a copper roller with the linear speed of 45m/s through an instantaneous pressure difference of 0.05MPa, so as to obtain an amorphous alloy strip precursor. The thickness of the strip is 45-60 mu m, the width is 1-2 mm, and the strip has metallic luster.
(3) The alloy strip precursor was immersed in a fresh sulfuric acid solution (the mass concentration of the substance is 2 mol/L) for corrosion treatment, and the treatment was carried out at room temperature for 2min. And after etching treatment, repeatedly washing the obtained alloy electrocatalyst with deionized water and absolute ethyl alcohol for at least three times, and drying in an oven for 20min at the temperature of 30 ℃ to obtain the high-activity nano porous electrolyzed water catalyst.
Example 2
The embodiment provides a preparation method of a high-activity nano porous electrolyzed water catalyst, which comprises the following steps:
(1) Fe, co, ni, zr, pt metal simple substances with purity of more than 99.9 weight percent are selected, the alloy elements with the proportion are mixed according to Fe 65Co10Ni10Zr10Pt5, arc melting is carried out on the alloy elements with the proportion in Ar protective atmosphere, the elements are uniformly mixed, and a master alloy cast ingot is obtained after cooling.
(2) And then, utilizing vacuum melt-spinning equipment to perform induction remelting on the master alloy cast ingot in a quartz tube, and then spraying the master alloy cast ingot onto a copper roller with the linear speed of 45m/s through an instantaneous pressure difference of 0.05MPa, so as to obtain an amorphous alloy strip precursor. The thickness of the strip is 45-60 mu m, the width is 1-2 mm, and the strip has metallic luster.
(3) The alloy strip precursor was immersed in a fresh sulfuric acid solution (the mass concentration of the substance is 2 mol/L) for corrosion treatment, and the treatment was carried out at room temperature for 3min. And after etching treatment, repeatedly washing the obtained alloy electrocatalyst with deionized water and absolute ethyl alcohol for at least three times, and drying in an oven for 20min at the temperature of 30 ℃ to obtain the high-activity nano porous electrolyzed water catalyst.
Comparative example 1
The difference from example 1 is that step (3) is not performed, and the rest is the same, namely, the amorphous alloy strip precursor obtained in step (2) is directly used as the nano-porous electrolyzed water catalyst.
Comparative example 2
The catalyst provided in this comparative example is a Pt/C catalyst, and the method for preparing a working electrode of the Pt/C catalyst comprises the steps of:
(1) Fe, co, ni, zr metal simple substances with purity of more than 99.9 weight percent are selected, the alloy elements with the proportion are mixed according to Fe 70Co10Ni10Zr10, arc melting is carried out on the alloy elements with the proportion in Ar protective atmosphere, the elements are uniformly mixed, and a master alloy cast ingot is obtained after cooling.
(2) And then, utilizing vacuum melt-spinning equipment to perform induction remelting on the master alloy cast ingot in a quartz tube, and then spraying the master alloy cast ingot onto a copper roller with the linear speed of 40m/s through an instantaneous pressure difference of 0.05MPa, so as to obtain an amorphous alloy strip precursor. The thickness of the strip is 40-60 mu m, the width is 1-2 mm, and the strip has metallic luster.
(3) The amorphous alloy strip precursor is immersed into a fresh sulfuric acid solution (the concentration is 2 mol/L) for corrosion treatment, and the amorphous alloy strip precursor is treated for 1.5h under the room temperature condition (the amorphous alloy strip precursor in the comparative example is not easy to etch). After etching treatment, repeatedly washing the obtained alloy with deionized water and absolute ethyl alcohol for at least three times, and drying in an oven for 20min at 30 ℃.
(4) 5Mg of commercial Pt/C powder catalyst (containing 20wt% Pt) was dispersed in a mixture of 1000. Mu.L ethanol and 50. Mu.L Nafion, and then sonicated for 30min to form a uniform catalyst suspension. Transferring 10 mu L of catalyst suspension to (3) etched Fe 70Co10Ni10Zr10 sample (0.16 cm 2), and drying at room temperature to obtain Pt/C working electrode (i.e. electrocatalyst), wherein the loading of Pt/C powder catalyst is 0.298mg/cm 2.
Performance analysis
As shown in fig. 1, the FeCoNiZrPt alloy precursor (i.e., the catalyst body of example 1) prepared in comparative example 1 has an amorphous structure.
As shown in fig. 2, the nano-porous electrolyzed water catalyst prepared in example 1 has a composite structure of porous layer-amorphous layer-porous layer.
As shown in FIG. 3, the nano-porous electrolyzed water catalyst prepared in the embodiment 1 has uniform nano-porous morphology and pore diameter of 20-40 nm.
As shown in fig. 4, in example 1, after the etching solution is added, a nanoporous structure is formed; fe is largely corroded, co, ni, zr is partially corroded, pt is exposed on the catalyst surface and forms an FCC platinum-rich nanocrystalline phase with the remaining metal atoms at the ligaments of the nanoporous layer.
As shown in fig. 5, electron transfer to Pt element of Fe, co, ni, zr in the catalyst of example 1 was obtained by photoelectron spectroscopy, and Pt 4f spectroscopy showed that electron orbitals shift to a lower binding energy direction, indicating that Pt element has more electrons, improving electrocatalytic efficiency.
The invention uses Zahner Zennium electrochemical workstation, adopts three electrode system: the catalyst samples prepared in example 1 and comparative example 2 were used as working electrodes, ag/AgCl was used as reference electrode, and carbon rod was used as auxiliary electrode, and a Linear Sweep Voltammetry (LSV) test was performed in 1mol/L KOH electrolyte. And (3) performing hydrogen evolution performance test under the test potential window of 0 to-0.9V (corresponding to the reversible hydrogen electrode), wherein the scanning speed is 3mV/s, and converting the current into current density. The test results are shown in fig. 6, with the experimental data being iR compensated. The relation between the current density and the overpotential is used for hydrogen evolution activity analysis, and the higher the absolute value of the current density is, the lower the overpotential is, the better the catalytic reaction performance is. Compared to the amorphous alloy ribbon precursor FeCoNiZrPt of comparative example 1, the etched nanoporous sample of example 1 exhibited a low overpotential, approximately 19mV when driven at a current density of 10mA/cm 2, approximately 181mV when driven at a current density of 1000mA/cm 2, far exceeding commercial Pt/C electrocatalyst performance.
The oxygen evolution performance test provided by the invention is consistent with the hydrogen evolution test method, and the catalyst samples prepared in the example 1 and the comparative example 1 are taken as working electrode test windows of 0-0.6V (corresponding to reversible hydrogen electrodes). The oxygen evolution activity analysis is performed by using the relation between the current density and the overpotential, and the higher the absolute value of the current density is, the lower the overpotential is, the better the oxygen evolution catalytic reaction performance is. The test results are shown in FIG. 7, and compared to the alloy strip precursor FeCoNiZrPt of comparative example 1, the nanoporous electrolyzed water catalyst of example 1 after etching exhibited a low overpotential, about 280mV at a current density of 10mA/cm 2 and about 406mV at a current density of 1000mA/cm 2.
Hydrogen evolution stability test of the nano-porous electrolyzed water catalyst: the hydrogen evolution stability test of the nanoporous electrolyzed water catalyst was performed by Cyclic Voltammetry (CV) and chronoamperometry (I-t curve) in 1mol/L KOH electrolyte using Zahner Zennium electrochemical workstation using the same three electrode test system as described above. 2000 cyclic voltammetry tests were performed at a voltage ranging from 0 to-0.9V (relative to the reversible hydrogen electrode) to characterize the durability of the electrocatalyst. The sweep rate was 50mV/s, and after 2000 cycles of sweep, the hydrogen evolution polarization curves were each tested at a sweep rate of 3mV/s, and compared with the polarization curves before 2000 times, the results are shown in FIG. 8. The nanoporous electrolyzed water catalyst was tested for long-term stability of hydrogen evolution by a chronoamperometry test curve at a constant current of 80mA, the results of which are shown in figure 8. The operation of hydrogen evolution of the nano-porous electrode is stable, and the potential at the position of the current density of 1000mA/cm 2 rises to less than 2mV after 2000 times of circulation; and the voltage remained almost unchanged in 80 hours under constant current test, and the drop was small (as shown in fig. 9). The above shows excellent hydrogen evolution stability of the nanoporous electrolyzed water catalyst.
The embodiment and the comparative example show that the high-efficiency nano porous electrolyzed water catalyst has high-activity hydrogen evolution and oxygen evolution performance and good stability, and can realize stable and high-efficiency electric hydrolysis in alkaline electrolyte. The preparation method of the catalytic electrode is simple and effective, low in cost and expandable, and the prepared nano porous structure has the advantages of increased active sites, regular morphology, stable structure and excellent performance.
The electrochemical activity specific surface areas of the electrolyzed water catalysts prepared in example 1 (3 at%) and example 2 (5 at%) are shown in table 1.
TABLE 1 electrochemical Activity specific surface area parameters of electrolyzed Water catalysts ECSA with different platinum content
As can be seen from table 1, the nano-porous electrolyzed water catalysts prepared from amorphous alloy strip precursors having different platinum content (i.e., after etching) have significantly larger specific surface area and more reactive sites exposed on the catalyst surface than the precursor (immediately before etching).
The element contents of the surface nanoporous layer (main active component) of the nanoporous electrolyzed water catalyst prepared in example 1 (3 at%) and example 2 (5 at%) are shown in table 2.
TABLE 2 content of elements of nanoporous layers of electrolyzed water catalysts with different platinum contents
As can be seen from table 2, the etched porous layer Pt of the nano-porous electrolyzed water catalyst prepared from amorphous alloy strip precursors having different platinum contents is enriched, so that the catalyst has high intrinsic activity.
The hydrogen evolution and oxygen evolution properties of the nanoporous electrolyzed water catalysts prepared in example 1 (3 at.%) and example 2 (5 at.%) are shown in table 3.
TABLE 3 nanoporous electrolyzed water catalysts with varying platinum content related performance parameters
As can be seen from table 3, the nano porous electrolyzed water catalysts prepared from the alloy strip precursors with different platinum contents all have good electrolyzed water performance, and can realize rapid hydrogen evolution reaction with high current density, which proves the universality of the preparation mode of the electrolyzed water catalysts.
In conclusion, the porous layer disclosed by the invention has a stable structure and exposes a large number of active sites, so that the nano-porous electrolyzed water catalyst has excellent catalytic activity and stability, and can stabilize electrolyzed water under the industrial-grade current density of more than 500mA/cm 2. The preparation method provided by the invention can obtain high catalytic performance by using a small amount of Pt, is simple, has low cost, and is expected to realize industrial-grade application.
Further, it is to be understood that various changes and modifications of the present application may be made by those skilled in the art after reading the above description of the application, and that such equivalents are intended to fall within the scope of the application as defined in the appended claims.
Claims (10)
1. The high-activity nano porous electrolyzed water catalyst is characterized in that the chemical composition of the main active component of the high-activity nano porous electrolyzed water catalyst is Fe aCobNicZrdPte, wherein a, b, c, d, e represents the atomic ratio, a is more than or equal to 25 and less than or equal to 35, b is more than or equal to 3 and less than or equal to 9, c is more than or equal to 4 and less than or equal to 10, d is more than or equal to 2 and less than or equal to 7, e is more than or equal to 48 and less than or equal to 60, and a+b+c+d+e=100;
the primary active component has a nanoporous structure comprising face-centered cubic phase nanocrystals.
2. The high activity nanoporous electrolyzed water catalyst according to claim 1, comprising a matrix phase of amorphous structure and a main active component having a nanoporous structure consisting of amorphous and face centered cubic phase nanocrystals on a surface layer of the matrix phase.
3. The high activity nanoporous electrolyzed water catalyst according to claim 1 or 2, wherein the pore size of the nanoporous structure is 20-60 nm.
4. A method for preparing a high activity nano-porous electrolyzed water catalyst according to any one of claims 1 to 3, comprising:
Firstly, proportioning according to the chemical formula of a precursor, and smelting uniformly to prepare a master alloy; the chemical formula of the precursor is Fe a'Cob'Nic'Zrd'Pte', wherein a ', b', c ', d', e 'represent atomic ratios, and a' is 60-70,8-13, c '13, d' 12,0< e '10, a' +b '+c' +d '+e' =100;
step two, after melting the master alloy, spraying the master alloy onto the surface of a rotating copper roller to obtain an amorphous alloy strip precursor;
And thirdly, adding the amorphous alloy strip precursor into etching liquid for etching treatment to obtain the nano porous electrolyzed water catalyst.
5. The method according to claim 4, wherein in the first step, the melting is performed under an inert atmosphere.
6. The method according to claim 4, wherein in the second step, the rotational speed of the copper roller is 40 to 45m/s.
7. The method according to claim 4, wherein in the third step, the etching solution is a sulfuric acid solution of 1.5-2.5 mol/L, and the etching treatment time is 1-8 min.
8. Use of the high-activity nano-porous electrolyzed water catalyst according to any one of claims 1 to 3 in the electrolysis of water.
9. A method for electrolyzing water, characterized in that the high-activity nano-porous electrolyzed water catalyst according to any one of claims 1 to 3 is used as a hydrogen evolution and/or oxygen evolution reaction catalyst for electrolyzing water.
10. The method of claim 9, wherein the high activity nanoporous electrolyzed water catalyst is directly used as a working electrode.
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