CN109208029A - A kind of stratiform vanadium base MAX phase compound V4AlC3Application and method - Google Patents

A kind of stratiform vanadium base MAX phase compound V4AlC3Application and method Download PDF

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CN109208029A
CN109208029A CN201811277381.2A CN201811277381A CN109208029A CN 109208029 A CN109208029 A CN 109208029A CN 201811277381 A CN201811277381 A CN 201811277381A CN 109208029 A CN109208029 A CN 109208029A
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蔺帅
童海云
黄亚楠
童鹏
赵邦传
宋文海
戴建明
朱雪斌
孙玉平
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Hefei Institutes of Physical Science of CAS
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Abstract

The invention discloses a kind of stratiform vanadium base MAX phase compound V4AlC3Application as electrolysis water oxygen-separating catalyst.The invention discloses the method for above-mentioned application, include the following steps: stratiform vanadium base MAX phase compound V4AlC3It is distributed in solution, then drop coating obtains working electrode in current collector material surface, vacuum drying；Working electrode is placed in alkaline medium, uses carbon paper for electrode, saturation silver chloride electrode is reference electrode, carries out electro-catalysis oxygen evolution reaction: being 10mA/cm in current density2When, overpotential is only 253mV, and under the above conditions can continuous work be more than that 110h catalytic performance is unattenuated.In addition, compared with conventional transition metal oxide/hydroxide oxygen-separating catalyst, stratiform vanadium base MAX phase compound V4AlC3With better electric conductivity and higher intrinsic catalytic activity, there is lower overpotential and higher stability as electrolysis water oxygen-separating catalyst in alkaline medium, while preparation method is simple, repeatability is high, is advantageously implemented industrialized production.

Description

A kind of stratiform vanadium base MAX phase compound V4AlC3Application and method
Technical field
The present invention relates to elctro-catalyst technical field more particularly to a kind of stratiform vanadium base MAX phase compound V4AlC3As electricity Solve application and the application method of elutriation VPO catalysts.
Background technique
With the fast development of global economy, the mankind are continuously increased the consumption of fossil energy, and energy crisis and environment are dirty The problems such as dye, is increasingly prominent, therefore develops the theme of clear energy sources and new technology as future world energy technology.Currently, new energy The research in source mainly has nuclear energy, solar energy, wind energy, geothermal energy, tide energy and Hydrogen Energy etc..Wherein, from the hydrogen of water decomposition It can be concerned due to good development prospect, but key is that the oxygen evolution reaction (OER) in water splitting processes is related to four The transmitting of a electronics, overpotential with higher, while dynamic process is slow, seriously limits the efficiency of electrolysis water.
The overpotential of OER can be effectively reduced in the use of catalyst, accelerates its kinetic reaction.Up to the present, Ir and The oxide of Ru is the OER catalyst that performance and stability are best in alkaline system, but due to its in the content of the earth few, valence Lattice are expensive, greatly limit their commercialized applications.Furthermore scientist and related technical personnel try to explore a series of non-expensive Metal elctro-catalyst, such as transition metal oxide, hydroxide, sulphur/selenides, phosphide, nitride, boride, it is expected that Above-mentioned precious metal oxide catalyst can be substituted.In above-mentioned most research, researchers are urged by nanosizing to increase The active sites points of agent improve dispersion degree, to improve catalytic performance, finally realize the oxygen that its catalytic performance is better than Ir or Ru Compound.However, the oxygen-separating catalyst that gained is had excellent performance is mostly nano material, preparation process is more complicated, and is not easy Carry out industrial volume production.Therefore, high catalytic performance, high stability and cheap, preparation process is developed simply to be easy to industrialize The OER catalyst of volume production has great importance.
Summary of the invention
Technical problems based on background technology, the invention proposes a kind of stratiform vanadium base MAX phase compound V4AlC3Make For the application of electrolysis water oxygen-separating catalyst, stratiform vanadium base MAX phase compound V4AlC3It can be used as regeneratable fuel cell, chargeable The elctro-catalyst of the fields such as metal-air battery, electrolysis water oxygen.
The applicant applies for the Chinese patent " one of a Patent No. CN201810335280.X on April 10th, 2018 The electrode material for super capacitor of the kind excellent cyclical stability of height ratio capacity " (publication date is on August 31st, 2018, publication number: CN108470633A), it is disclosed that stratiform vanadium base MAX phase compound V4AlC3And preparation method thereof, mainly for the preparation of super Capacitor electrode material.
The applicant is again to stratiform vanadium base MAX phase compound V afterwards4AlC3Carry out research discovery: stratiform vanadium base MAX phase Close object V4AlC3Belong to stratiform transition metal carbide, compared to transiting metal oxidation/hydroxide have better electric conductivity and Higher intrinsic catalytic activity has the excellent of low overpotential and high stability as electrolysis water oxygen-separating catalyst in alkaline medium Point, while preparation process is simple, repeatability is high, is advantageously implemented industrialized production.
A kind of stratiform vanadium base MAX phase compound V proposed by the present invention4AlC3Application as electrolysis water oxygen-separating catalyst.
Specifically, above-mentioned stratiform vanadium base MAX phase compound V4AlC3As the application method of electrolysis water oxygen-separating catalyst, packet Include following steps:
S1, by stratiform vanadium base MAX phase compound V4AlC3It is distributed in solution, then drop coating is in current collector material surface, very Sky is dried to obtain working electrode；
S2, working electrode is placed in alkaline medium, uses carbon paper for electrode, being saturated silver chloride electrode is reference electricity Pole carries out electro-catalysis oxygen evolution reaction.
Preferably, in S1, stratiform vanadium base MAX phase compound V4AlC3The granularity of powder is less than 35 μm.
Preferably, the solution of S1 includes ethyl alcohol, deionized water and Nafion solution；The preferably quality of Nafion solution point Counting is 4.5-5.5wt%, while the proportion of solution are as follows: ethyl alcohol: deionized water: Nafion=25:25:2-8.
Preferably, in S1, by stratiform vanadium base MAX phase compound V4AlC3It is distributed in solution, ultrasonic disperse, ultrasonic disperse Time is greater than 30min.
Preferably, in S1, current collector material is at least one of nickel foam, charcoal cloth, carbon paper, glass carbon；Preferably, collector Material is nickel foam.
Preferably, in S1, vacuum drying temperature is 45-55 DEG C.
Preferably, in S2, alkaline medium is at least one of sodium hydroxide solution, potassium hydroxide solution, ammonium hydroxide, and alkalinity is situated between The concentration of matter is 0.1-10mol/L.
Above-mentioned stratiform vanadium base MAX phase compound V4AlC3The preparation method of powder, includes the following steps:
I, vanadium powder, aluminium powder, graphite powder are mixed, uniformly, tabletting is subsequently placed in the tube furnace of flowing argon gas and burns for grinding Knot, cooling obtain sheet MAX phase compound V4AlC3；
II, by sheet MAX phase compound V4AlC3It is crushed, ball milling, starvation and steam in mechanical milling process are dried to obtain Stratiform vanadium base MAX phase compound V4AlC3Powder.
Preferably, in step I, vanadium, aluminium element, carbon molar ratio be 4:1-1.5:3.
Preferably, in step I, vanadium powder, aluminium powder, graphite powder granularity be greater than 200 mesh.
Preferably, in step I, milling time 5-35min.
Preferably, in step I, tabletting pressure is more than or equal to 1GPa.
Preferably, in step I, the tubular type furnace parameters for flowing argon gas are as follows: ar pressure is greater than 0.01MPa, argon flow More than or equal to 10mL/min.
Preferably, in step I, sintering concrete operations are as follows: rising to 1300-1600 with the heating rate of 5-12 DEG C/min DEG C, soaking time is more than or equal to 2h.
Preferably, in step I, the type of cooling is to be furnace-cooled to room temperature.
Preferably, in step II, by sheet MAX phase compound V4AlC3It is crushed using mortar.
Preferably, the concrete operations of starvation and steam are as follows in the mechanical milling process of step II: will be equipped with broken rear piece Shape MAX phase compound V4AlC3Ball grinder be put into glove box, abrading-ball and dispersing agent are then added into ball grinder, then will Ball grinder sealing, takes out ball grinder from glove box, uses planetary type ball-milling instrument ball milling at least 5h later, and rotational speed of ball-mill is greater than 300r/min。
Preferably, in the glove box of step II, oxygen content is less than or equal to 0.1ppm, and moisture content is less than or equal to 0.1ppm。
Preferably, in the ball grinder of step II, ball material mass ratio is 10-20:1.
Preferably, in step II, dispersing agent is alcohol.
Preferably, in step II, using vacuum drying mode, drying temperature is 45-55 DEG C.
Above-mentioned stratiform vanadium base MAX phase compound V4AlC3As electro-catalysis oxygen evolution reaction catalysts, the table in alkaline electrolyte Reveal excellent catalytic performance: being 10mA/cm in current density2When, overpotential is only 253mV, lower than analysis oxygen catalytic at present The optimal IrO of energy2、RuO2Overpotential, show fabulous electro catalytic activity；Meanwhile in above-mentioned current density and overpotential Under, sustainable work at least 110h and performance is unattenuated, have fabulous stability.It the composite can be widely applied to renewable combustion Expect the fields such as battery, rechargeable metal, electrolysis water.
The present invention compares the prior art and has the advantage that
(1) present invention is used as analysis oxygen elctro-catalyst using transition metal carbide, compared to transiting metal oxidation/hydroxide Object, which analyses oxygen elctro-catalyst, has better electric conductivity and higher intrinsic catalytic activity；
(2) above-mentioned stratiform vanadium base MAX phase compound V4AlC3With fabulous electro catalytic activity and surely in alkaline electrolyte It is qualitative: current density 10mA/cm2When, required overpotential is only 253mV, and electrocatalytic decomposition water under the above conditions, Stability can replace precious metal oxide catalyst, promote electrocatalytic decomposition water commercial applications up at least 110h；
(3) above-mentioned stratiform vanadium base MAX phase compound V4AlC3Synthesis material rich reserves, cheap, preparation method letter Single, controllable, short preparation period is reproducible, it can be achieved that large-scale production.
Detailed description of the invention
Fig. 1 is 1 gained sheet MAX phase compound V of embodiment4AlC3Room temperature X-ray diffractogram.
Fig. 2 is 1 gained stratiform vanadium base MAX phase compound V of embodiment4AlC3The scanning electron microscope (SEM) photograph of powder；Wherein 2A is stratiform Vanadium base MAX phase compound V4AlC3The low power number scanning electron microscope (SEM) photograph of powder, 2B are stratiform vanadium base MAX phase compound V4AlC3Powder High magnification numbe scanning electron microscope (SEM) photograph.
Fig. 3 is 1 gained stratiform vanadium base MAX phase compound V of embodiment4AlC3The transmission electron microscope picture of powder；Wherein 3a is stratiform Vanadium base MAX phase compound V4AlC3The low power number transmission electron microscope picture of powder, 3b are stratiform vanadium base MAX phase compound V4AlC3Powder Section high-resolution-ration transmission electric-lens figure, 3c be stratiform vanadium base MAX phase compound V4AlC3The surface high-resolution-ration transmission electric-lens of powder Figure.
Fig. 4 is 1 gained stratiform vanadium base MAX phase compound V of embodiment4AlC3X-ray photoelectron spectroscopy (XPS) figure of powder； Wherein 4A is x-ray photoelectron spectroscopy score, and 4B is Al 2p spectrum, and 4C is C 1s spectrum, and 4D is V 2p spectrum.
Fig. 5 is 1 gained stratiform vanadium base MAX phase compound V of embodiment4AlC3Powder in 1mol/L potassium hydroxide solution into The correlation curve of row electro-catalysis analysis oxygen (OER) performance test；Wherein 5a is linear sweep voltammetry curve, and 5b is in constant current Density is 10mA/cm2Lower progress potential-time graph scanning figure.
Specific embodiment
In the following, technical solution of the present invention is described in detail by specific embodiment.
Embodiment 1
The preparation method of a kind of low overpotential, high stability analysis oxygen elctro-catalyst, includes the following steps:
I, granularity is all larger than to the vanadium powder, aluminium powder and graphite powder mixed grinding 35min of 200 mesh, vanadium, aluminium element, The molar ratio of carbon is 4:1.5:3；Tabletting, tabletting pressure are 1.5GPa；It is subsequently placed in the tube furnace of flowing argon gas with 10 DEG C/heating rate of min rises to 1500 DEG C and is sintered, soaking time 2h, wherein the tubular type furnace parameters of flowing argon gas are as follows: Ar pressure is 0.025MPa, argon flow 10mL/min in furnace, is furnace-cooled to room temperature and obtains sheet MAX phase compound V4AlC3；
II, by sheet MAX phase compound V4AlC3It is broken using mortar, it then places it in and is put into ball grinder in glove box In, the oxygen content in glove box is 0.1ppm, and the moisture content in glove box is 0.1ppm, is added by ball material mass ratio for 20:1 Enter abrading-ball, add alcohol, then seal ball grinder, then take out ball grinder from glove box, is being turned by ball milling instrument Speed is ball milling 5-45h under 500r/min, takes out V later4AlC3It is small to obtain dry granularity in 50 DEG C of vacuum drying 12h for powder In 35 μm of stratiform vanadium base MAX phase compound V4AlC3Powder, i.e., low overpotential, high stability analyse oxygen elctro-catalyst.
By sheet MAX phase compound V obtained by step I4AlC3X-ray diffraction test is carried out, as shown in Figure 1；By gained particle The stratiform vanadium base MAX phase compound V that degree is 1-5 μm4AlC3Powder carries out electron microscope scanning, as shown in Figure 2；It will be resulting Stratiform vanadium base MAX phase compound V4AlC3Powder carries out electron microscopic transmissioning electric mirror test, as shown in Figure 3；By resulting stratiform vanadium Base MAX phase compound V4AlC3Powder carries out x-ray photoelectron spectroscopy detection, as shown in Figure 4.
Embodiment 2
1 gained stratiform vanadium base MAX phase compound V of embodiment4AlC3As the application method of electrolysis water oxygen-separating catalyst, packet Include following steps:
S1, the stratiform vanadium base MAX phase compound V for being 1-5 μm by granularity4AlC3It is 5wt% that powder, which is distributed to mass fraction, In the mixed aqueous solution of Nafion, solution ratio are as follows: ethyl alcohol: deionized water: Nafion=25:25:4；Ultrasonic disperse is uniform, so Drop coating obtains working electrode in 1cm × 1.5cm foam nickel surface, 50 DEG C of vacuum drying afterwards；
S2, working electrode is placed in the potassium hydroxide electrolyte of concentration 1mol/L, uses carbon paper to be saturated chlorine to electrode Change silver electrode is reference electrode, carries out electro-catalysis oxygen evolution reaction.
Electro-catalysis analysis oxygen performance carries out on occasion China CHI660E electrochemical workstation, and potassium hydroxide electrolyte is logical before testing Enter high pure oxygen and carry out saturated process, test temperature is 25 DEG C.Specific test is as follows: linear sweep voltammetry curve test, scanning speed Rate is 5mV/s, gives 90% resnstance transformer, and is converted into the electrode potential relative to reversible hydrogen electrode (RHE), is calculated public Formula are as follows: E(RHE)=EAg/AgCl+0.197+0.0591×pH；Catalyst stability test: being 10mA/cm in constant current density2 Lower progress potential-time graph scanning.
As shown in Figure 5 a, Fig. 5 a is that linear sweep voltammetry (LSV) song in oxygen (OER) performance test is analysed in above-mentioned electro-catalysis Line, i.e. 1 gained stratiform vanadium base MAX phase compound V of embodiment4AlC3Oxygen is analysed in powder electro-catalysis in 1mol/L potassium hydroxide solution Polarization curve.Referring to Fig. 5 a, it is known that it is 10mA/cm that the present invention, which reaches current density when overpotential is 253mV,2。
As shown in Figure 5 b, it in constant current density is 10mA/ that Fig. 5 b, which is that above-mentioned electro-catalysis analyses in oxygen (OER) performance test, cm2Lower progress potential-time graph scanning figure, i.e. 1 gained stratiform vanadium base MAX phase compound V of embodiment4AlC3Powder exists The stability curve of electro-catalysis analysis oxygen in 1mol/L potassium hydroxide solution.Referring to Fig. 5 b, it is known that the present invention is in current density 10mA/ cm2Lower overpotential is stablized in 253mV, sustainable work 110h and catalytic performance is unattenuated.Oxygen performance test is analysed in above-mentioned electro-catalysis The result shows that stratiform vanadium base MAX phase compound V4AlC3With fabulous catalytic activity and stability.
Embodiment 3
1 gained stratiform vanadium base MAX phase compound V of embodiment4AlC3As the application method of electrolysis water oxygen-separating catalyst, packet Include following steps:
S1, the stratiform vanadium base MAX phase compound V for being 25-30 μm by granularity4AlC3Powder is distributed to mass fraction In the mixed solution of 5wt%Nafion solution, solution ratio are as follows: ethyl alcohol: deionized water: Nafion=25:25:2；Ultrasonic disperse Uniformly, it is then added dropwise in charcoal cloth surface, 48 DEG C of vacuum drying obtain the working electrode having a size of 1cm × 1.5cm；
S2, working electrode is placed in the potassium hydroxide solution of concentration 10mol/L, uses carbon paper to be saturated chlorine to electrode Change silver electrode is reference electrode, carries out electro-catalysis oxygen evolution reaction.
Embodiment 4
1 gained stratiform vanadium base MAX phase compound V of embodiment4AlC3As the application method of electrolysis water oxygen-separating catalyst, packet Include following steps:
S1, the stratiform vanadium base MAX phase compound V for being 20-25 μm by granularity4AlC3Powder is distributed to isopropanol and quality Score is solution ratio are as follows: ethyl alcohol: deionized water: Nafion=25:25:6 in the mixed solution of 5wt%Nafion solution；It is super Sound is uniformly dispersed, and is then added dropwise in carbon paper surface, 50 DEG C of vacuum drying obtain the working electrode having a size of 1cm × 1.5cm；
S2, working electrode is placed in the ammonium hydroxide of concentration 1mol/L, uses carbon paper for electrode, being saturated silver chloride electrode is Reference electrode carries out electro-catalysis oxygen evolution reaction.
Embodiment 5
1 gained stratiform vanadium base MAX phase compound V of embodiment4AlC3As the application method of electrolysis water oxygen-separating catalyst, packet Include following steps:
S1, the stratiform vanadium base MAX phase compound V for being 20-25 μm by granularity4AlC3Powder is distributed to isopropanol and quality Score is solution ratio are as follows: ethyl alcohol: deionized water: Nafion=25:25:8 in the mixed solution of 5wt%Nafion solution；It is super Sound is uniformly dispersed, and is then added dropwise in carbon paper surface, and 50 DEG C of vacuum drying obtain the working electrode having a size of 1cm × 1.5cm；
S2, working electrode is placed in the potassium hydroxide solution of concentration 8mol/L, uses carbon paper to be saturated chlorination to electrode Silver electrode is reference electrode, carries out electro-catalysis oxygen evolution reaction.
Embodiment 6
1 gained stratiform vanadium base MAX phase compound V of embodiment4AlC3As the application method of electrolysis water oxygen-separating catalyst, packet Include following steps:
S1, the stratiform vanadium base MAX phase compound V for being 15-20 μm by granularity4AlC3Powder is distributed to isopropanol and quality Score is solution ratio are as follows: ethyl alcohol: deionized water: Nafion=25:25:4 in the mixed solution of 5wt%Nafion solution；It is super Sound is uniformly dispersed, and is then added dropwise in glass carbon surface, 50 DEG C of vacuum drying obtain the working electrode having a size of 1cm × 1.5cm；
S2, working electrode is placed in the sodium hydroxide solution of concentration 6mol/L,
It uses carbon paper for electrode, saturation silver chloride electrode is reference electrode, carries out electro-catalysis oxygen evolution reaction.
Embodiment 7
1 gained stratiform vanadium base MAX phase compound V of embodiment4AlC3As the application method of electrolysis water oxygen-separating catalyst, packet Include following steps:
S1, the stratiform vanadium base MAX phase compound V for being 10-15 μm by granularity4AlC3Powder is distributed to isopropanol and quality Score is solution ratio are as follows: ethyl alcohol: deionized water: Nafion=25:25:4 in the mixed solution of 5wt%Nafion solution；It is super Sound is uniformly dispersed, and is then added dropwise in glass carbon surface, 50 DEG C of vacuum drying obtain the working electrode having a size of 1cm × 1.5cm；
S2, working electrode is placed in the ammonium hydroxide of concentration 2mol/L, uses carbon paper for electrode, being saturated silver chloride electrode is Reference electrode carries out electro-catalysis oxygen evolution reaction.
Embodiment 8
1 gained stratiform vanadium base MAX phase compound V of embodiment4AlC3As the application method of electrolysis water oxygen-separating catalyst, packet Include following steps:
S1, the stratiform vanadium base MAX phase compound V for being 5-10 μm by granularity4AlC3Powder is distributed to isopropanol and quality point Number is solution ratio are as follows: ethyl alcohol: deionized water: Nafion=25:25:4 in the mixed solution of 5wt%Nafion solution；Ultrasound It is uniformly dispersed, is then added dropwise in foam nickel surface, 50 DEG C of vacuum drying obtain the working electrode having a size of 1cm × 1.5cm；
S2, working electrode is placed in the sodium hydroxide solution of concentration 4mol/L, uses carbon paper to be saturated chlorination to electrode Silver electrode is reference electrode, carries out electro-catalysis oxygen evolution reaction.
Embodiment 9
By 1 gained stratiform vanadium base MAX phase compound V of embodiment4AlC3Electro-catalysis analysis is carried out in standard three electrode electrolytic cell Oxygen (OER) performance test:
S1, the stratiform vanadium base MAX phase compound V for being 1-5 μm by granularity4AlC3Powder is distributed to isopropanol and quality point Number is solution ratio are as follows: ethyl alcohol: deionized water: Nafion=25:25:4 in the mixed solution of 5wt%Nafion solution；Ultrasound 30min makes it be uniformly dispersed to obtain catalyst pulp, is then added dropwise in foam nickel surface, 50 DEG C of vacuum drying obtain having a size of The working electrode of 1cm × 1.5cm；
S2, working electrode is placed in the potassium hydroxide solution of concentration 0.1mol/L, uses carbon paper to be saturated chlorine to electrode Change silver electrode is reference electrode, carries out electro-catalysis oxygen evolution reaction.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto, Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.

Claims (8)

1. a kind of stratiform vanadium base MAX phase compound V4AlC3Application as electrolysis water oxygen-separating catalyst.
2. the method that one kind is applied as described in claim 1, which comprises the steps of:
S1, by stratiform vanadium base MAX phase compound V4AlC3It is distributed in solution, then for drop coating in current collector material surface, vacuum is dry It is dry to obtain working electrode；
S2, working electrode is placed in alkaline medium, uses carbon paper for electrode, saturation silver chloride electrode is reference electrode, into Row electro-catalysis oxygen evolution reaction.
3. the method applied according to claim 2, which is characterized in that in S1, stratiform vanadium base MAX phase compound V4AlC3Powder Last granularity is less than 35 μm.
4. the method applied according to Claims 2 or 3, which is characterized in that the solution of S1 include deionized water, ethyl alcohol and Nafion solution；Preferably, the mass fraction of Nafion solution is 4.5-5.5wt%, deionized water, ethyl alcohol and Nafion solution Volume ratio be 25:25:2-8.
5. according to the method for any one of the claim 2-4 application, which is characterized in that in S1, by stratiform vanadium base MAX phase chemical combination Object V4AlC3It is distributed in solution, ultrasonic disperse；Preferably, the ultrasonic disperse time is greater than 30min.
6. according to the method for any one of the claim 2-5 application, which is characterized in that in S1, current collector material be nickel foam, At least one of charcoal cloth, carbon paper, glass carbon；Preferably, current collector material is nickel foam.
7. according to the method for any one of the claim 2-6 application, which is characterized in that in S1, vacuum drying temperature 45-55 ℃。
8. according to the method for any one of the claim 2-7 application, which is characterized in that in S2, alkaline medium is sodium hydroxide At least one of solution, potassium hydroxide solution, ammonium hydroxide；Preferably, the concentration 0.1-10mol/L of alkaline medium.
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