CN106732649A - A kind of preparation method of alkaline oxygen evolution reaction elctro-catalyst - Google Patents

A kind of preparation method of alkaline oxygen evolution reaction elctro-catalyst Download PDF

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CN106732649A
CN106732649A CN201710090574.6A CN201710090574A CN106732649A CN 106732649 A CN106732649 A CN 106732649A CN 201710090574 A CN201710090574 A CN 201710090574A CN 106732649 A CN106732649 A CN 106732649A
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cobalt
manganese
catalyst
array
conductive substrates
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罗俊
吴朝文
章立寒
刘熙俊
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Tianjin University of Technology
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    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • B01J23/8892—Manganese
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • B01J37/088—Decomposition of a metal salt
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
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Abstract

The invention discloses a kind of preparation method of alkaline oxygen evolution reaction elctro-catalyst, first conductive substrates are cleaned by ultrasonic, the aqueous solution with soluble cobalt, soluble manganese salt, ammonium fluoride and urea is prepared again, in reactor, vertical-growth manganese cobalt subcarbonate nano-array multilevel hierarchy on the surface of the substrate；The aqueous solution with water soluble alkali, reducing agent is reconfigured at, after-treatment is carried out, structure and performance optimization are carried out to manganese cobalt subcarbonate multi-stage nano array；It is last, under nitrogen or argon gas atmosphere, to be calcined at a temperature of 200~1000 DEG C in tube furnace, the alkaline oxygen evolution reaction elctro-catalyst of the cobalt oxide nano-array multilevel hierarchy for mixing manganese is obtained.Present invention employs the method for simple Hydrothermal Synthesiss/calcination processing, process is simple, it is easy to regulate and control, resulting product excellent performance is a kind of elctro-catalyst with fine prospect in the application process of alkaline decomposition water.

Description

A kind of preparation method of alkaline oxygen evolution reaction elctro-catalyst
Technical field
The present invention be on elctro-catalyst, it is more particularly to a kind of transient metal doped with nano-array multilevel hierarchy Alkaline oxygen evolution reaction elctro-catalyst preparation method.
Background technology
New energy simultaneously has no lack of, but really to realize the output of new energy, also there are many problems.Come from water decomposition Hydrogen Energy has good development prospect, but it is critical only that the dynamic process of the oxygen evolution reaction (OER) of water splitting processes is slow, sternly The whole efficiency for producing hydrogen process is hindered again, therefore, develop an urgent demand that efficient oxygen evolution reaction catalysts are human survivals. There are a large amount of researchs on OER catalyst before this, mostly concentrated on metal-air battery, fuel cell etc., or even conduct Bifunctional catalyst is applied in lithium battery and above-mentioned energy storage and production capacity device, and wherein cobalt and manganese oxide material is also studied for Photochemical catalyzing field.The state of research object is also of all kinds, there is powder, nano particle, nanocrystal, nanoporous Structure etc., is to prepare the novel material of high surface area, structure to expose more avtive spots, finding new reaction machine mostly System is with more preferable guiding experiment.The noble metal based compound such as ruthenium, iridium is current most efficient oxygen-separating catalyst, yet with too high Cost and scarcity of resources, limit their application and popularization.Another point need to arouse attention, the battery of business electrolysis water Current potential (1.8-2.0V) is higher by 570-770mV than minimum overpotential (1.23V) in theory, and catalyst stability is poor.Cause This, exploitation stability and high efficiency, aboundresources and cheap oxygen-separating catalyst are particularly important.
The content of the invention
The purpose of the present invention, primarily to solving existing oxygen evolution reaction catalysts during water is catalytically decomposed, is present Catalysis overpotential it is higher, the problems such as stability difference, there is provided a kind of transient metal doped with nano-array multilevel hierarchy Alkaline oxygen evolution reaction elctro-catalyst, significantly reduces the overpotential of oxygen evolution reaction and plays spike potential, and improve catalytic reaction Stability, for decompose aqueous systems oxygen-separating catalyst functional direction design with performance optimization provide new thinking and plan Slightly.
The present invention is achieved by following technical solution.
A kind of preparation method of alkaline oxygen evolution reaction elctro-catalyst, comprises the following steps that：
(1) conductive substrates are cleaned by ultrasonic 5~20 minutes in the hydrochloric acid of 1~5 mol/L, are then transferred to acetone molten It is cleaned by ultrasonic 5~20 minutes in liquid, transfers in ethanol solution and be cleaned by ultrasonic 5~20 minutes, it is finally abundant with deionized water Conductive substrates are rinsed, then is put into 50~80 DEG C of baking oven and is dried；
(2) prepare precursor solution, the precursor solution comprising concentration for 0.01-0.04 mol/Ls soluble cobalt, Concentration is the soluble manganese salt of 0.001-0.04 mol/Ls, concentration for the ammonium fluoride and concentration of 0.01-1 mol/Ls are 0.01-1 The total ion concentration of the aqueous solution of the urea of mol/L, manganese ion and cobalt ions maintains 0.047 mol/L；
Above-mentioned precursor solution magnetic agitation is transferred in reactor after 5~40 minutes, then by after step (1) treatment Conductive substrates are inclined and are put into reactor, are then covered reactor and are tightened, and are placed in drying box and are warming up to 80 DEG C~200 DEG C, Set of time is 5~20 hours, brings it about hydro-thermal reaction, and whole course of reaction causes that vertical-growth goes out on conductive substrates surface Manganese cobalt subcarbonate nano-array；
(3) conductive substrates after hydro-thermal reaction in step (2) terminates are taken out, by sufficient deionized water rinsing it Afterwards, it is placed in 30~80 DEG C of drying box and is dried, drying time is 60~180 minutes；
(4) configuration has water soluble alkali, concentration of the concentration for 0-5 mol/Ls for the reducing agent of 0-5 mol/Ls is water-soluble Liquid, and water soluble alkali is not simultaneously 0, magnetic agitation 5~30 minutes with the concentration of reducing agent；
And magnetic agitation 5~30 minutes；
The conductive substrates that step (3) is obtained incline the small burning for being put into and filling above-mentioned water soluble alkali, reducing agent aqueous solution In cup, and 0.1-10 hours in solution is not stood under normal temperature, bring it about reaction so that above-mentioned manganese cobalt basic carbonate There is alkaline etching and reduction reaction on salt nano-array surface, so as to change product structure and increase its Lacking oxygen, formative The excellent manganese cobalt subcarbonate nano-array multilevel hierarchy of energy；
(5) conductive substrates after the middle immersion of step (4) are taken out again and a large amount of deionized water rinsings are used, after fully rinsing It is placed in 30~80 DEG C of vacuum drying chamber and dries 60~180 minutes；
(6) step (5) dried conductive substrates are horizontally placed on magnetic boat, then this magnetic boat is placed in the quartz ampoule of tube furnace Center section, calcines 0.5~10 hour in atmosphere stable in properties, at a temperature of 100~1000 DEG C, is cooled to room Temperature, manganese cobalt subcarbonate nano-array multilevel hierarchy is changed into the alkalescence analysis of the cobalt/cobalt oxide nano-array multilevel hierarchy for mixing manganese Oxygen reacts elctro-catalyst.
The conductive substrates of the step (1) are any one of nickel foam or carbon cloth.
The soluble cobalt and manganese salt of the step (2) are any one of nitrate, sulfate or acetate.
The water soluble alkali of the step (4) is the highly basic of alkali metal containing, and reducing agent is sodium borohydride.
The atmosphere stable in properties of the step (6) is nitrogen or argon gas atmosphere.
Beneficial effects of the present invention are as follows：
The preparation method is made up of simple hydro-thermal reaction and low temperature calcination treatment, and step is simple, the reaction time is short, operation Convenient, repeatability extremely friendly to environment is strong；Material of the invention is fabulous elctro-catalyst in alkaline oxygen evolution reaction, When current density is 10mA/cm2When, reaction overpotential is 0.31V, considerably beyond the 0.44V of business Ir/C catalyst, and stabilization Property is fabulous.By will introduce other transition metals in material, doping effect brings a series of benefits to the present invention, not only favorably In OH-Absorption, and the potential barrier of oxygen evolution reaction can be reduced, and super thin vapor interface is formed between solid-liquid two-phase so that Oxygen is easily desorbed, so as to promote the generation of oxygen evolution reaction.In addition, nano-array multilevel hierarchy significantly increases electrode activity material The specific surface area of material, can provide more avtive spots for reaction, and the collaboration of this series of factors enhances the material in alkalescence Electro-catalysis ability in oxygen evolution reaction.
Brief description of the drawings
Fig. 1 is the CONSTRUCTED SPECIFICATION figure (SEM) of the material shown in comparative example；
Fig. 2 a are the scanning electron microscope (SEM) photographs (SEM) of the low power of the material shown in comparative example；Fig. 2 b, c are comparative examples 2 Shown in material high power scanning electron microscope (SEM) photograph (SEM)；Fig. 2 d are the Energy disperaive quantitative analysis of the material shown in comparative example 2 Figure (EDS)；
Fig. 3 is the low power scanning electron microscope (SEM) photograph (SEM) of the material shown in embodiment 1；
Fig. 4 is times scanning electron microscope (SEM) photograph (SEM) in material shown in embodiment 1；
Fig. 5 is the high power scanning electron microscope (SEM) photograph (SEM) of the material shown in embodiment 1
Fig. 6 is the Energy disperaive quantitative analysis figure (EDS) of the material shown in embodiment 1；
Fig. 7 is the x-ray photoelectron energy spectrum diagram (XPS) of the cobalt element of the material shown in embodiment 1；
Fig. 8 is the x-ray photoelectron energy spectrum diagram (XPS) of the manganese element of the material shown in embodiment 1；
Fig. 9 is the x-ray photoelectron energy spectrum diagram (XPS) of the oxygen element of the material shown in embodiment 1；
Figure 10 is that the material and embodiment 4 shown in embodiment 1, the material shown in embodiment 5 are analysed in the basic conditions Polarization curve (LSV) comparison diagram of oxygen reaction, reference electrode is saturated calomel electrode；
Figure 11 is the material and embodiment 2 shown in embodiment 1, the material shown in embodiment 3, comparative example in alkali Polarization curve (LSV) comparison diagram of oxygen evolution reaction under the conditions of property, reference electrode is saturated calomel electrode；
Figure 12 is the constant-pressure stable test chart that material shown in embodiment 1 carries out oxygen evolution reaction in the basic conditions.
Specific embodiment
Below by specific embodiment, the invention will be further described, what embodiment was merely exemplary, and unrestricted Property.
Embodiment 1
Conductive substrates are nickel foam, and cobalt source is cobalt nitrate, and reducing agent is sodium borohydride.
(1) it is cleaned by ultrasonic nickel foam as conductive substrates 10 minutes in the hydrochloric acid of 5 mol/Ls, is then transferred to third It is cleaned by ultrasonic 10 minutes in ketone solution, transfers in ethanol solution and be cleaned by ultrasonic 10 minutes, is finally fully rushed with deionized water Conductive substrates are washed, is then put into 60 DEG C of baking oven and is dried.
(2) preparation precursor solution, the cobalt nitrate comprising 0.03516 mol/L, the manganese nitrate of 0.01172 mol/L, The ammonium fluoride of 0.2 mol/L, the urea of 0.25 mol/L.The solution magnetic agitation is transferred in reactor after 10 minutes, The nickel foam after step (1) treatment is inclined again is put into reactor, then reactor covered and is tightened, be placed in drying box and rise To 100 DEG C, set of time is 10 hours to temperature, brings it about hydro-thermal reaction, and whole course of reaction causes to be hung down on conductive substrates surface Growing straight grows manganese cobalt subcarbonate nano-array；
(3) conductive substrates after hydro-thermal reaction in step (2) terminates are taken out, by sufficient deionized water rinsing it Afterwards, it is placed in 60 DEG C of drying box and dries 180 minutes；
(4) sodium borohydride solution of NaOH of the configuration containing 3 mol/Ls and 1 mol/L, in 10 points of magnetic agitation After clock, nickel foam that step (3) is obtained is tilting to be put into the small beaker for filling configuration solution and will not in solution, normal temperature It is lower to stand 1 hour, bring it about reaction so that alkaline etching occurs on above-mentioned manganese cobalt subcarbonate nano-array surface and goes back Original reaction, so as to change product structure and increase its Lacking oxygen, the excellent manganese cobalt subcarbonate nano-array of forming properties is more Level structure；
(5) nickel foam after the middle immersion of step (4) is taken out again and uses a large amount of deionized water rinsings, will after fully rinsing It is placed in 60 DEG C of vacuum drying chamber and dries 180 minutes；
(6) being placed in the nickel foam obtained in step (5) carries out low-temperature treatment in tube furnace.It is horizontally placed on magnetic boat, This magnetic boat is placed in quartz ampoule center section again, is calcined 3 hours in argon gas, at a temperature of 250 DEG C, be cooled to room temperature, Manganese cobalt subcarbonate nano-array multilevel hierarchy is changed into the alkalescence analysis oxygen of the cobalt/cobalt oxide nano-array multilevel hierarchy for mixing manganese Reaction elctro-catalyst, is named as NaOH＆NaBH4@MnxCo3-xO4-1:3。
Using three-electrode system, the performance to the material in the electrolyte of the potassium hydroxide solution of 0.1 mol/L is entered Row analysis oxygen performance test.Wherein, to electrode it is platinized platinum, reference electrode is saturated calomel electrode, and sweep speed is 5mV/s.
Fig. 3 is the scanning electron microscope (SEM) photograph (SEM) of the low power of the material shown in embodiment 1, it can be seen that NaOH＆NaBH4@ MnxCo3-xO4-1:3 are uniformly adhered to substrate surface；
Fig. 4 is times scanning electron microscope (SEM) photograph (SEM) in material shown in embodiment 1, it can be seen that the material is long on piece The nano-array multilevel hierarchy of line.
Fig. 5 is the high power scanning electron microscope (SEM) photograph (SEM) of the material shown in embodiment 1, can be seen compared with comparative example Go out, by after alkali and sodium borohydride treatment, it is coarse that the nanowire surface of array multilevel hierarchy becomes；
Fig. 6 is the Energy disperaive quantitative analysis figure (EDS) of the material shown in embodiment 1, and power spectrum shows the peak of manganese, cobalt, oxygen, Can be concluded that synthesized material is NaOH＆NaBH4@MnxCo3-xO4-1:3, and ratio approximate 1：2：4, the energy with comparative example Spectrum is consistent substantially；
Fig. 7 is the x-ray photoelectron energy spectrum diagram (XPS) of the cobalt element of the material shown in embodiment 1, it is known that the valence state of cobalt Have+3 and+2；
Fig. 8 is the x-ray photoelectron energy spectrum diagram (XPS) of the manganese element of the material shown in embodiment 1, it is known that manganese valence Have+3 and+2；
Fig. 9 is the x-ray photoelectron energy spectrum diagram (XPS) of the oxygen element of the material shown in embodiment 1, it is known that embodiment 1 Shown in material contain oxygen element；
Figure 10 is that the material and embodiment 4 shown in embodiment 1, the material shown in embodiment 5 are analysed in the basic conditions Oxygen reaction polarization curve (LSV) comparison diagram, by performance comparison it can be seen that in embodiment step (4) NaOH and boron hydrogen The consumption for changing sodium can be such that the analysis oxygen performance of the material reaches most preferably, and reference electrode is saturated calomel electrode；
Figure 11 is the material and embodiment 2 shown in embodiment 1, the material shown in embodiment 3, comparative example in alkali Polarization curve (LSV) comparison diagram of oxygen evolution reaction under the conditions of property, reference electrode is saturated calomel electrode, institute in embodiment 1,2,3 The analysis oxygen performance of the material for showing is superior to material and business Ir/C catalyst shown in comparative example, and in embodiment 1 Shown material is NaOH＆NaBH4@MnxCo3-xO4-1:3 performance is the most excellent, is much better than business Ir/C, and it is drawn through conversion The overpotential of oxygen evolution reaction process, contrast situation refers to table 1.
Table 1
Figure 12 is the constant-pressure stable test chart that material shown in embodiment 1 carries out oxygen evolution reaction in the basic conditions, Understand under the voltage of 0.66V (relative to saturation calomel), tested by the constant pressures of 15 hours, the electric current that the material is produced keeps In 92.2% higher level.
Embodiment 2
The preparation method of the electrocatalysis material is substantially the same manner as Example 1, and difference is：Hydroxide in step (4) Sodium is different with the consumption of sodium borohydride, respectively 3M and 0M, is NaOH@Mn by the material designationxCo3-xO4-1:3.The energy of embodiment 2 Enough reach goal of the invention.
Embodiment 3
The preparation method of the electrocatalysis material is substantially the same manner as Example 1, and difference is：Hydroxide in step (4) Sodium is different with the consumption of sodium borohydride, and the material designation is NaBH by respectively 0M and 1M4@MnxCo3-xO4-1:3.The energy of embodiment 3 Enough reach goal of the invention.
Embodiment 4
The preparation method of the electrocatalysis material is substantially the same manner as Example 1, and difference is：Hydroxide in step (4) Sodium is different with the consumption of sodium borohydride, respectively 1M and 1M.Embodiment 4 can reach goal of the invention.
Embodiment 5
The preparation method of the electrocatalysis material is substantially the same manner as Example 1, and difference is：Hydroxide in step (4) Sodium is different with the consumption of sodium borohydride, respectively 5M and 1M.Embodiment 5 can reach goal of the invention.
Embodiment 6
The preparation method of the electrocatalysis material is substantially the same manner as Example 1, and difference is：By leading in step (1) Electric substrate is changed to carbon cloth, and acquired results equally can reach invention effect.Embodiment 6 can reach goal of the invention.
Embodiment 7
The preparation method of the electrocatalysis material is substantially the same manner as Example 1, and difference is：By argon gas in step (6) Atmosphere is changed to nitrogen atmosphere, and acquired results equally can reach invention effect.Embodiment 7 can reach goal of the invention.
Comparative example
The comparative example is prior art, and preparation method is with the difference of embodiment 1：By step (3) water Step (6) low-temperature treatment is directly carried out after thermally grown, lacks step of the invention (4) and (5), according to manganese cobalt charge ratio 1:3, It is Mn by the material designationxCo3-xO4-1:3。
Fig. 1 is the CONSTRUCTED SPECIFICATION figure (SEM) of the material shown in comparative example, it can be clearly seen that the material is on piece The nanometer hierarchical structure of line long.
Fig. 2 a are the scanning electron microscope (SEM) photographs (SEM) of the low power of the material shown in comparative example, it can be seen that generation material is equal Even is attached to substrate surface；Fig. 2 b, c are the high power scanning electron microscope (SEM) photographs (SEM) of the material shown in comparative example 2, are schemed by b With c figures it can be seen that the material that base surface is uniformly adhered to is the nano-array multilevel hierarchy of line long on piece, and nano wire Surface smoother；Fig. 2 d are the Energy disperaive quantitative analysis figures (EDS) of the material shown in comparative example 2, wherein containing manganese, Cobalt, oxygen element, and its ratio approximate 1：2：4, it is known that generation material is MnxCo3-xO4-1:3.Its performance far away from embodiment 1, Reference can be made to shown in Fig. 8 and Biao 1.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned implementation method Detail, in range of the technology design of the invention, various simple variants can be carried out to technical scheme, this A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can The combination of energy is no longer separately illustrated.
Additionally, can also be combined between a variety of implementation methods of the invention, as long as it is without prejudice to originally The thought of invention, it should equally be considered as content disclosed in this invention.

Claims (5)

1. a kind of preparation method of alkaline oxygen evolution reaction elctro-catalyst, comprises the following steps that：
(1) conductive substrates are cleaned by ultrasonic 5~20 minutes in the hydrochloric acid of 1~5 mol/L, are then transferred in acetone soln It is cleaned by ultrasonic 5~20 minutes, transfers in ethanol solution and be cleaned by ultrasonic 5~20 minutes, is finally fully rinsed with deionized water Conductive substrates, then be put into 50~80 DEG C of baking oven and be dried；
(2) precursor solution is prepared, the precursor solution is soluble cobalt, the concentration of 0.01-0.04 mol/Ls comprising concentration For the soluble manganese salt of 0.001-0.04 mol/Ls, concentration for the ammonium fluoride and concentration of 0.01-1 mol/Ls rub for 0.01-1 You/liter urea the aqueous solution, the total ion concentration of manganese ion and cobalt ions maintains 0.047 mol/L；
Above-mentioned precursor solution magnetic agitation is transferred in reactor after 5~40 minutes, then by the conduction after step (1) treatment Substrate tilt is put into reactor, is then covered reactor and is tightened, be placed in drying box be warming up to 80 DEG C~200 DEG C, time It is set to 5~20 hours, brings it about hydro-thermal reaction, whole course of reaction causes that vertical-growth goes out manganese cobalt on conductive substrates surface Subcarbonate nano-array；
(3) conductive substrates after hydro-thermal reaction terminates in taking-up step (2), after by sufficient deionized water rinsing, will It is placed in 30~80 DEG C of drying box and is dried, and drying time is 60~180 minutes；
(4) configuration is the aqueous solution of the reducing agent of 0-5 mol/Ls with the water soluble alkali, concentration that concentration is 0-5 mol/Ls, and Water soluble alkali is not simultaneously 0, magnetic agitation 5~30 minutes with the concentration of reducing agent；
The conductive substrates that step (3) is obtained are inclined and are put into the small beaker for filling above-mentioned water soluble alkali, reducing agent aqueous solution, And not in solution, 0.1-10 hours is stood under normal temperature, bring it about reaction so that above-mentioned manganese cobalt subcarbonate nanometer There is alkaline etching and reduction reaction in array surface, so as to change product structure and increase its Lacking oxygen, forming properties are excellent Manganese cobalt subcarbonate nano-array multilevel hierarchy；
(5) conductive substrates after the middle immersion of step (4) are taken out again and a large amount of deionized water rinsings are used, by it after fully rinsing It is placed in 30~80 DEG C of vacuum drying chamber and dries 60~180 minutes；
(6) step (5) dried conductive substrates are horizontally placed on magnetic boat, then this magnetic boat is placed in the middle of the quartz ampoule of tube furnace Part, calcines 0.5~10 hour in atmosphere stable in properties, at a temperature of 100~1000 DEG C, is cooled to room temperature, manganese The alkalescence analysis oxygen that cobalt subcarbonate nano-array multilevel hierarchy is changed into the cobalt/cobalt oxide nano-array multilevel hierarchy for mixing manganese is anti- Answer elctro-catalyst.
2. a kind of preparation method of alkaline oxygen evolution reaction elctro-catalyst according to claim 1, it is characterised in that the step Suddenly the conductive substrates of (1) are any one of nickel foam or carbon cloth.
3. a kind of preparation method of alkaline oxygen evolution reaction elctro-catalyst according to claim 1, it is characterised in that the step Suddenly the soluble cobalt and manganese salt of (2) are any one of nitrate, sulfate or acetate.
4. a kind of preparation method of alkaline oxygen evolution reaction elctro-catalyst according to claim 1, it is characterised in that the step Suddenly the water soluble alkali of (4) is the highly basic of alkali metal containing, and reducing agent is sodium borohydride.
5. a kind of preparation method of alkaline oxygen evolution reaction elctro-catalyst according to claim 1, it is characterised in that the step Suddenly the atmosphere stable in properties of (6) is nitrogen or argon gas atmosphere.
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