CN109806888A - 1T-MoS2Hollow dodecahedron nanocomposite of modified ZnCoS solid solution and the preparation method and application thereof - Google Patents
1T-MoS2Hollow dodecahedron nanocomposite of modified ZnCoS solid solution and the preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a kind of 1T-MoS2Hollow dodecahedron nanocomposite of modified ZnCoS solid solution and the preparation method and application thereof, first ZnCo-MOF obtain its derivative by high-temperature calcination, and derivative and molybdate are then carried out hydro-thermal vulcanization reaction and obtain MoS2/ ZnCoS nanocomposite, the ZnCo-MOF is bimetallic organic framework material, and by cobalt acetate, zinc acetate and methylimidazole react to obtain.It is template that the present invention, which utilizes the bimetallic organic framework material with high specific surface area and three stable bit space structures, ZnCo bimetallic oxide derivative is obtained by high-temperature calcination, obtains the transient metal sulfide nano material with high catalytic activity finally by the mixture that hydro-thermal method vulcanizes the derivative and molybdate.Prepared hollow polyhedral MoS2/ ZnCoS nanocomposite photocatalytic water splitting with higher produces the performance of hydrogen.
Description
Technical field
The invention belongs to photocatalysis nano material technical fields, and in particular to one kind is based on 1T-MoS2Modified ZnCoS is solid
Hollow dodecahedron nanocomposite of solution and the preparation method and application thereof.
Background technique
In recent years, since global energy shortage and problem of environmental pollution become increasingly conspicuous, develop new green energy resource and technology
Extremely urgent, light-catalysed research is just come into being.Photocatalysis refer to catalyst there are under the action of, utilize the luminous energy of nature
As energy source, it is easy to get some or cheap chemicals is decomposed into the substance or the energy of highly efficient cleaning and environmental protection
Product.Photocatalysis is exactly that energy consumption rate is low with the difference that other are catalyzed, only just using the sunlight of nature as the energy
Supply just can be carried out catalysis reaction.Sunlight is also to belong to renewable resource simultaneously, so it has greatly met green catalysis reason
Read this environmental protection, low consumed chemical technology characteristic.Hydrogen energy source has for alleviating current energy shortage and solving environmental problem
Important researching value, one of the hot spot even more studied in recent years using photocatalytic water splitting hydrogen manufacturing.
Zinc sulphide as a kind of one of typical photocatalyst material, no matter range or in depth it is all extensive
Research.Although ZnS has very high catalytic activity and preferable application prospect, due to its wider forbidden bandwidth (3.2eV),
It is typically only capable to by ultraviolet excitation, and its light induced electron and hole can be quickly compound, this just makes it in photocatalysis field
Using being limited by very large.Therefore being modified to zinc sulphide applies it in visible-range and further increases it
Photocatalysis performance is the hot spot studied at present.The main path for improving material light catalysis property is modified to it, modified
Means mainly include element doping, co-catalyst, hetero-junctions, pattern control and noble metal decorated etc..Wherein introduce co-catalyst
Catalytic performance can be greatly improved, the forbidden bandwidth of semiconductor material, the tune of pattern can effectively be adjusted by forming heterojunction structure
Control can enhance the utilization rate of light, therefore the combination of effective various method of modifying is modified method most popular at present.
Photochemical catalyst derived from bimetallic organic framework material usually shows in energy-related application superior
Activity, therefore use bimetallic organic framework material that can significantly enhance the suction of light as the advanced catalysis material of templated synthesis
Receive the separation and transfer with electronics.We more stable have using ZnCo-MOF as template by calcining ZnCo-MOF and being formed
The derivative ZnO-Co of cavity structure3O4, vulcanize to form hollow polyhedral MoS finally by high temperature hydro-thermal method2/ZnCoS.Due to
Transition metal sulfide M oS2With with hydrogen adsorption energy similar in precious metals pt, therefore be applied to by the substitute as noble metal
In light-catalyzed reaction, it is the more popular co-catalyst of current research, can significantly improves photocatalytic water splitting H2-producing capacity.
Therefore in last sulfurating stage, by the way that molybdate, derivative ZnO-Co is added3O4With one step high temperature hydro-thermal method of thioacetamide
Vulcanization obtains MoS2The nanocomposite MoS of modified ZnCoS hollow polyhedral2/ZnCoS。
Summary of the invention
The present invention existing photochemical catalyst there are aiming at the problem that, provide it is a kind of have that catalytic activity is high, large specific surface area,
Stability is good, high to the utilization rate of light source, and nano composite photo-catalyst, that is, 1T- of stable hollow polyhedral at low cost
MoS2The hollow dodecahedron nanocomposite of modified ZnCoS solid solution, while additionally providing preparation method and application.
In order to achieve the goal above, the technical solution adopted by the present invention is as follows.
1T-MoS2The preparation method of the hollow dodecahedron nanocomposite of modified ZnCoS solid solution, including walk as follows
It is rapid:
(1) under room temperature, cobalt acetate and zinc acetate is dissolved in methyl alcohol, solution A is obtained；
(2) under room temperature, in methyl alcohol by methylimidazole dissolution, B solution is obtained；
(3) under room temperature, solution A is stirred, B solution is added in solution A, is persistently stirred after being added to B solution, it is quiet
It sets, filters, washing obtains bimetallic organic framework material ZnCo-MOF；
(4) ZnCo-MOF that step (3) obtain is dried, then calcines, obtains bimetallic organic framework material and spread out
Biological ZnO-Co3O4；
(5) the bimetallic organic framework material derivative ZnO-Co for obtaining step (4)3O4, molybdate and thioacetamide
It is dispersed in water, carries out hydro-thermal reaction, post-processed after the hydro-thermal reaction, obtain 1T-MoS2Modified ZnCoS solid solution
The hollow dodecahedron nanocomposite of body, i.e. MoS2/ ZnCoS nanocomposite.
Preferably, the mass ratio of the material of the cobalt acetate and zinc acetate are as follows: 1:9-9:1, in the solution A methanol volume with
The ratio of the amount of the total substance of both cobalt acetate and zinc acetate is 10-50ml/mmol；The amount and step of the substance of the methylimidazole
Suddenly the ratio of the amount of both cobalt acetate and zinc acetate total material is 4-8:1 in (1), the volume and methylimidazole of methanol in B solution
Substance amount ratio be 5-30ml/mmol.
Preferably, B solution persistently stirs 20-24h after being added, and stands 4-6h.
Preferably, 8-12h is dried at 60-80 DEG C in ZnCo-MOF in step (4).
Preferably, the technological parameter of the calcining are as follows: under air atmosphere, calcination temperature is 350-400 DEG C, heating rate
For 2-5 DEG C/min, after being raised to 350-400 DEG C, 350-400 DEG C at a temperature of keep 4-8h after, with the cooling speed of 2-5 DEG C/min
Rate is reduced to room temperature.
Preferably, it is one such to be selected from water-soluble sodium molybdate, ammonium molybdate for the molybdate.
Preferably, in molybdate described in step (5) molybdenum quality and ZnO-Co3O4Mass ratio be 1-5:100, it is described
ZnO-Co3O4It is 1:3-5 with the gross mass of both molybdates and the mass ratio of thioacetamide.
Preferably, described by ZnO-Co3O4, molybdate and thioacetamide three carry out hydro-thermal reaction and obtain MoS2/
The step of ZnCoS nanocomposite includes:
1) by ZnO-Co3O4, molybdate and thioacetamide three be scattered in the container for filling 30-60ml distilled water, and
It stirs evenly, obtains mixed solution；
2) mixed solution in container is transferred in 60-100ml polytetrafluoroethyllining lining reaction kettle, which is reacted
Kettle is sealed in stainless steel autoclave, is put into baking oven and is heated to 160-220 DEG C of reaction temperature, and heating rate is 1-3 DEG C/
Min, then 160-220 DEG C at a temperature of keep constant temperature 18-24h reacted；
3) after cooled to room temperature, open liner reaction kettle, be then filtered processing, and with distilled water and ethyl alcohol according to
Secondary washing, dry 8-12h, obtains polyhedron MoS in 60-80 DEG C of vacuum oven2/ ZnCoS nanocomposite.
The present invention also provides the 1T-MoS of preparation method preparation2The modified hollow dodecahedron of ZnCoS solid solution is received
Nano composite material and its application in photocatalytic water splitting production hydrogen.
Compared with prior art, the present invention has the advantage that
Using bimetallic organic framework material as template, calcining obtains the derivative with hollow structure in air atmosphere,
Vulcanize to have obtained finally by one step hydro thermal method and there is large specific surface area, stable hollow polyhedral sulfide M oS2/ZnCoS
Nanocomposite.Big specific surface area is capable of providing more active sites, and solid solution ZnCoS has suitable forbidden band wide
Degree, wide in range light abstraction width is to improve the utilization rate of light；Cavity is conducive to light and multiple reflections occurs in material internal, into one
Step improves the utilization rate of light, co-catalyst MoS2As noble metal substitute, its doping can significantly improve photocatalysis water
H2-producing capacity is decomposed, with semiconductor 2H-MoS2It compares, the metal 1T phase MoS with unordered octahedral structure2Due at edge and
There is active site abundant and higher electronic conductivity on basal plane, thus show better photocatalytic activity.The nanometer
Composite material can be synthesized simply, and have better photocatalytic water splitting H2-producing capacity, stabilization for ZnS
Property and light utilization efficiency, and synthesis material is cheap, and preparation process is simple.
Detailed description of the invention
Fig. 1 is Zn0.5Co0.5The XRD diagram of-MOF material；
Fig. 2 is Zn0.5Co0.5The SEM of-MOF schemes；
Fig. 3 is ZnO-Co3O4XRD diagram；
Fig. 4 is ZnO-Co3O4TEM figure；
Fig. 5 is nanocomposite 2%MoS2/Zn0.5Co0.5The XRD diagram of S；
Fig. 6 is nanocomposite 2%MoS2/Zn0.5Co0.5The SEM of S schemes；
Fig. 7 is nanocomposite 2%MoS2/Zn0.5Co0.5The TEM of S schemes；
Fig. 8 is nanocomposite 2%MoS2/Zn0.5Co0.5The nitrogen adsorption desorption curve graph of S；
Fig. 9 is nanocomposite 2%MoS2/Zn0.5Co0.5The Raman of S schemes；
Figure 10 is nanocomposite 2%MoS2/Zn0.5Co0.5The photocatalysis performance figure of S.
Specific embodiment
Technical solution of the present invention is described in further detail below in conjunction with specific embodiments and drawings but this hair
Bright range and embodiment is without being limited thereto.
In specific implementation, the experiment reagent and raw material of use commercially obtain unless otherwise specified.
Embodiment 1
1T-MoS2The preparation method of the hollow dodecahedron nanocomposite of modified ZnCoS solid solution, specific steps are such as
Under:
(1) preparation of metal-organic framework materials ZnCo-MOF:
It weighs 184mg zinc acetate (1mmol) and 177mg cobalt acetate (1mmol) is dissolved in 50ml methanol solution, stir at room temperature
It mixes to solute and is completely dissolved, obtain the mixed solution of two kinds of metal salts, enable as solution A.Weigh 414mg methylimidazole
(8mmol) is dissolved in 40ml methanol solution, stirs to solute be completely dissolved at room temperature, obtains B solution.At room temperature, B solution is delayed
It is slow to be added in solution A, and be stirred continuously, 6h is stood after persistently stirring 20h, reaction product is separated by filtering, and is then used
Distillation water washing 3 times, ethanol washing 3 times, subsequent product is placed in 60 DEG C of vacuum drying ovens dry 8h, obtains Zn0.5Co0.5-MOF。
Fig. 1 is Zn0.5Co0.5The XRD diagram of-MOF material has preferable crystal form, Fig. 2 Zn0.5Co0.5The SEM of-MOF schemes, Cong Tuke with
Find out and has synthesized the very uniform Zn of size0.5Co0.5- MOF material.
(2) derivative ZnO-Co3O4Preparation:
Weigh the Zn of a certain amount of above-mentioned synthesis0.5Co0.5- MOF material is placed in high-temperature calcination stove and calcines in quartz boat,
Under air atmosphere, 350 DEG C, calcining at constant temperature 8h are risen to the heating rate of 2 DEG C/min, room is reduced to the rate of temperature fall of 2 DEG C/min
Temperature obtains derivative ZnO-Co3O4.Fig. 3 is ZnO-Co3O4XRD diagram, as can be seen from Fig. absolutely not MOF peak exist,
Illustrate Zn0.5Co0.5- MOF is completely successful to be oxidized to ZnO-Co3O4.Fig. 4 is derivative ZnO-Co3O4TEM figure, You Tuke
To find out calcined derivative ZnO-Co3O4The structure of the granatohedron remained intact, and form cavity structure.
(3) nanocomposite 2%MoS2/Zn0.5Co0.5The preparation of S:
Weigh 10mg Na2MoO4·2H2O, 525mg CH3CSNH2With 160mg said derivative ZnO-Co3O4It is gone in 50ml
It in ionized water, stirs evenly, finely dispersed solution is transferred in 100ml polytetrafluoroethylene (PTFE) pyroreaction kettle at room temperature then
It in lining, seals lid and is placed into stainless steel cauldron, 180 DEG C are warming up in thermostatic drying chamber, 2 DEG C/min of heating rate is held
Continuous reaction 20h, cooled to room temperature take out reaction kettle, and reaction product is separated by filtering, is washed with water 3 times, then use
Ethanol washing 3 times, finally place the product in 8h dry in 80 DEG C of vacuum drying ovens, obtain black powder, the as mass fraction of molybdenum
For 2% nanocomposite 2%MoS2/Zn0.5Co0.5S.Fig. 5 is nano composite photocatalytic material 2%MoS2/Zn0.5Co0.5S
XRD diagram, oxide ZnO-Co as can be seen from Fig.3O4Peak completely disappear, illustrate oxide ZnO-Co3O4It is converted completely
For sulfide.Fig. 6,7 be respectively nanocomposite 2%MoS2/Zn0.5Co0.5The SEM and TEM of S schemes, as seen from the figure water
The structure for the hollow dodecahedron that nanocomposite after thermal response remains intact.Fig. 8 is 2%MoS2/Zn0.5Co0.5S is compound
The nitrogen adsorption desorption curve graph of material, specific surface area 70m2g-1.Fig. 9 is nanocomposite 2%MoS2/Zn0.5Co0.5S
Raman figure, 2%MoS as can be seen from Figure 92/Zn0.5Co0.5Contain metal 1T phase MoS in S composite material2.Figure 10 is 2%
MoS2/Zn0.5Co0.5S,Zn0.5Co0.5The photocatalytic water splitting H2-producing capacity of S and ZnS compares, and hydrogen output is respectively
15.5mmol/g/h, 6.12mmol/g/h and 0.98mmol/g/h.
Embodiment 2
1T-MoS2The preparation method of the hollow dodecahedron nanocomposite of modified ZnCoS solid solution, specific steps are such as
Under:
(1) preparation of metal-organic framework materials ZnCo-MOF:
It weighs 184mg zinc acetate (1mmol) and 1.593g cobalt acetate (9mmol) is dissolved in 100ml methanol solution, at room temperature
Stirring is completely dissolved to solute, is obtained the mixed solution of two kinds of metal salts, is enabled as solution A.Weigh 4.144g methylimidazole
(80mmol) is dissolved in 1600ml methanol solution, stirs to solute be completely dissolved at room temperature, obtains B solution.At room temperature, B is molten
Liquid is slowly added in solution A, and is stirred continuously, and lasting stirring stands 6h afterwards for 24 hours, and reaction product is separated by filtering, with
After be washed with distilled water 3 times, ethanol washing 3 times, subsequent product is placed in 80 DEG C of vacuum drying ovens dry 8h, obtains Zn0.1Co0.9-
MOF。
(2) derivative ZnO-Co3O4Preparation:
Weigh the Zn of a certain amount of above-mentioned synthesis0.1Co0.9- MOF material is placed in high-temperature calcination stove and calcines in quartz boat,
Under air atmosphere, 400 DEG C, calcining at constant temperature 4h are risen to the heating rate of 5 DEG C/min, room is reduced to the rate of temperature fall of 5 DEG C/min
Temperature obtains derivative ZnO-Co3O4。
(3) nanocomposite 5%MoS2/Zn0.1Co0.9The preparation of S:
Weigh 20mg Na2MoO4·2H2O, 549mg CH3CSNH2With 160mg derivative ZnO-Co3O4In 50ml deionization
It in water, stirs evenly at room temperature, finely dispersed solution is then transferred to 100ml polytetrafluoroethylene (PTFE) pyroreaction kettle liner
In, it seals lid and is placed into stainless steel cauldron, 160 DEG C, 1 DEG C/min of heating rate are warming up in thermostatic drying chamber, continue
For 24 hours, cooled to room temperature takes out reaction kettle, and reaction product is separated by filtering, is washed with water 3 times, then use second for reaction
Alcohol washs 3 times, finally place the product in 8h dry in 80 DEG C of vacuum drying ovens, obtain molybdenum mass fraction be 5% it is nano combined
Material 5%MoS2/Zn0.1Co0.9S, this nanocomposite 5%MoS2/Zn0.1Co0.9The photocatalytic water splitting H2-producing capacity of S is
11.5mmol/g/h。
Embodiment 3
1T-MoS2The preparation method of the hollow dodecahedron nanocomposite of modified ZnCoS solid solution, specific steps are such as
Under:
(1) preparation of metal-organic framework materials ZnCo-MOF:
It weighs 1.656mg zinc acetate (9mmol) and 177mg cobalt acetate (1mmol) is dissolved in 500ml methanol solution, room temperature
Lower stirring is completely dissolved to solute, is obtained the mixed solution of two kinds of metal salts, is enabled as solution A.Weigh 3.108g methylimidazole
(60mmol) is dissolved in 1800ml methanol solution, stirs to solute be completely dissolved at room temperature, obtains B solution.At room temperature, B is molten
Liquid is slowly added in solution A, and is stirred continuously, and lasting stirring stands 8h afterwards for 24 hours, and reaction product is separated by filtering, with
After be washed with distilled water 3 times, ethanol washing 3 times, subsequent product is placed in 80 DEG C of vacuum drying ovens dry 12h, obtains Zn0.9Co0.1-
MOF
(2) derivative ZnO-Co3O4Preparation:
Weigh the Zn of a certain amount of above-mentioned synthesis0.9Co0.1- MOF material is placed in high-temperature calcination stove and calcines in quartz boat,
Under air atmosphere, 400 DEG C, calcining at constant temperature 6h are risen to the heating rate of 3 DEG C/min, room is reduced to the rate of temperature fall of 3 DEG C/min
Temperature obtains derivative ZnO-Co3O4。
(3) nanocomposite 0.5%MoS2/Zn0.9Co0.1The preparation of S:
Weigh 5mg Na2MoO4·2H2O, 495mg CH3CSNH2With 160mg derivative ZnO-Co3O4In 50ml deionization
It in water, stirs evenly at room temperature, finely dispersed solution is then transferred to 100ml polytetrafluoroethylene (PTFE) pyroreaction kettle liner
In, it seals lid and is placed into stainless steel cauldron, 220 DEG C, 3 DEG C/min of heating rate are warming up in thermostatic drying chamber, continue
18h is reacted, cooled to room temperature takes out reaction kettle, and reaction product is separated by filtering, is washed with water 3 times, then use second
Alcohol washs 3 times, and finally place the product in 8h dry in 80 DEG C of vacuum drying ovens, the nanometer that the mass fraction for obtaining molybdenum is 0.5% is multiple
Condensation material 0.5%MoS2/Zn0.9Co0.1S, this nanocomposite 0.5%MoS2/Zn0.9Co0.1The photocatalytic water splitting of S produces hydrogen
Performance is 9.4mmol/g/h.
The ZnCo-MOF and ZnO-Co prepared in embodiment 2 and 33O4Respective performances can refer to the attached drawing in embodiment 1.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1.1T-MoS2The preparation method of the hollow dodecahedron nanocomposite of modified ZnCoS solid solution, which is characterized in that packet
Include following steps:
(1) under room temperature, cobalt acetate and zinc acetate is dissolved in methyl alcohol, solution A is obtained；
(2) under room temperature, in methyl alcohol by methylimidazole dissolution, B solution is obtained；
(3) under room temperature, solution A is stirred, B solution is added in solution A, is persistently stirred after being added to B solution, is stood, is taken out
Filter, washing, obtains bimetallic organic framework material ZnCo-MOF；
(4) ZnCo-MOF that step (3) obtain is dried, then calcines, obtains bimetallic organic framework material derivative
ZnO-Co3O4；
(5) the bimetallic organic framework material derivative ZnO-Co for obtaining step (4)3O4, molybdate and thioacetamide dispersion
Yu Shuizhong carries out hydro-thermal reaction, is post-processed after the hydro-thermal reaction, obtain 1T-MoS2Modified ZnCoS solid solution is empty
Heart dodecahedron nanocomposite, i.e. MoS2/ ZnCoS nanocomposite.
2. 1T-MoS according to claim 12The system of the hollow dodecahedron nanocomposite of modified ZnCoS solid solution
Preparation Method, which is characterized in that the mass ratio of the material of the cobalt acetate and zinc acetate are as follows: 1:9-9:1, methanol body in the solution A
The long-pending ratio with the amount of the total substance of both cobalt acetate and zinc acetate is 10-50 ml/mmol；The substance of the methylimidazole
The ratio of amount and the amount of both cobalt acetate and zinc acetate total material is 4-8:1, the volume of methanol and the object of methylimidazole in B solution
The ratio of the amount of matter is 5-30 ml/mmol.
3. 1T-MoS according to claim 12The system of the hollow dodecahedron nanocomposite of modified ZnCoS solid solution
Preparation Method, which is characterized in that B solution persistently stirs 20-24 h after being added, stand 4-6 h.
4. 1T-MoS according to claim 12The system of the hollow dodecahedron nanocomposite of modified ZnCoS solid solution
Preparation Method, which is characterized in that 8-12 h is dried in ZnCo-MOF at 60-80 DEG C in step (4).
5. 1T-MoS according to claim 12The system of the hollow dodecahedron nanocomposite of modified ZnCoS solid solution
Preparation Method, which is characterized in that the technological parameter of the calcining are as follows: under air atmosphere, calcination temperature is 350-400 DEG C, heating
Rate be 2-5 DEG C/min, after being raised to 350-400 DEG C, 350-400 DEG C at a temperature of keep 4-8 h after, with 2-5 DEG C/
The rate of temperature fall of min is reduced to room temperature.
6. 1T-MoS according to claim 12The system of the hollow dodecahedron nanocomposite of modified ZnCoS solid solution
Preparation Method, which is characterized in that it is one such that the molybdate is selected from water-soluble sodium molybdate, ammonium molybdate.
7. 1T-MoS according to claim 12The system of the hollow dodecahedron nanocomposite of modified ZnCoS solid solution
Preparation Method, which is characterized in that the quality and ZnO-Co of molybdenum in molybdate described in step (5)3O4Mass ratio be 1-5:100, institute
State ZnO-Co3O4It is 1:3-5 with the gross mass of both molybdates and the mass ratio of thioacetamide.
8. 1T-MoS according to claim 12The system of the hollow dodecahedron nanocomposite of modified ZnCoS solid solution
Preparation Method, which is characterized in that described by ZnO-Co3O4, molybdate and thioacetamide three carry out hydro-thermal reaction and obtain
MoS2The step of/ZnCoS nanocomposite includes:
1) by ZnO-Co3O4, molybdate and thioacetamide three be scattered in the container for filling 30-60 ml distilled water, and stir
It mixes uniformly, obtains mixed solution；
2) mixed solution in container is transferred in 60-100 ml polytetrafluoroethyllining lining reaction kettle, by the liner reaction kettle
It being sealed in stainless steel autoclave, is put into baking oven and is heated to 160-220 DEG C of reaction temperature, heating rate is 1-3 DEG C/
Min, then 160-220 DEG C at a temperature of keep constant temperature 18-24 h reacted；
3) after cooled to room temperature, liner reaction kettle is opened, is then filtered processing, and successively washed with distilled water and ethyl alcohol
It washs, dry 8-12 h, obtains polyhedron MoS in 60-80 DEG C of vacuum oven2/ ZnCoS nanocomposite.
9. the 1T-MoS of preparation method preparation as described in claim 12The hollow dodecahedron nanometer of modified ZnCoS solid solution is multiple
Condensation material.
10. 1T-MoS as claimed in claim 92The hollow dodecahedron nanocomposite of modified ZnCoS solid solution is urged in light
Change the application in water decomposition production hydrogen.
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