CN110195257A - A kind of nitride porous molybdenum single crystal material and its preparation method and application - Google Patents
A kind of nitride porous molybdenum single crystal material and its preparation method and application Download PDFInfo
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- CN110195257A CN110195257A CN201910559681.8A CN201910559681A CN110195257A CN 110195257 A CN110195257 A CN 110195257A CN 201910559681 A CN201910559681 A CN 201910559681A CN 110195257 A CN110195257 A CN 110195257A
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
- C30B23/02—Epitaxial-layer growth
- C30B23/025—Epitaxial-layer growth characterised by the substrate
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/38—Nitrides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
This application discloses a kind of nitride porous molybdenum single crystal material and preparation method thereof with nano pore structure, nitride porous molybdenum single crystal material have large scale, and there is presently no the methods that report prepares large-sized nitride porous molybdenum single crystal.Hole containing 10nm~1000nm in the nitride porous molybdenum single crystal material.The electrode material for super capacitor that nitride porous molybdenum single crystal of the invention can be used as novel catalysis material, have excellent performance.
Description
Technical field
The invention belongs to porous monocrystalline preparation fields, and in particular to a kind of preparation method of nitride porous molybdenum single crystal.
Background technique
Application and development with the electrode material with catalytic performance in clean energy resource field, clean energy resource are more next
The production and life of more change mankind.As people are higher and higher to environmental protection consciousness, the demand of clean energy resource is more next
It is bigger, but traditional precious metal catalyst electrode material significantly limits cleaning energy due at high cost, scarcity of resources etc.
The extensive use in source.Novel electro-catalytic electrode material with nitride, carbide etc. for representative has the electronics knot similar to platinum
Structure, thus have with performance as the precious metals such as platinum, palladium, such as it has similar to the good electric conductivity of platinum and excellent
Catalytic performance.
Such as containing the content and annelation of a large amount of heterocyclic compounds in petroleum, the presence of these heterocyclic compounds is not only right
The deep-processing process of oil product generates poisoning effect, and brings serious environmental pollution.In order to meet people to oil product
Sulfur-bearing, nitrogen content increasingly harsh requirement, the catalyst of the desulfurization, denitrogenation of developing novel environment-friendly type low energy consumption is increasingly
It has received universal attention.In recent years, the catalytic desulfurization of high-specific surface area molybdenum nitride and molybdenum carbide, nitrogen removal performance have caused people
Attention, it is early to the research of this kind of catalyst effective in the world.It has recently been demonstrated that metal nitride has for example
Nitride film has Faraday pseudo-capacitance, stable in aqueous solution to be not easily decomposed, and is easy preparation, is capable of providing similar to your gold
Belong to oxide RuO2Charge-discharge performance, be precious metal material RuO2Effective alternative materials, provided for the development of supercapacitor
New direction.
The nitride of molybdenum is one of numerous magnesium-yttrium-transition metal nitride, there is MoN, Mo2N、Mo3N2、Mo5N6Etc. a variety of nitrogen
Change state, the nitride of molybdenum is molybdenum oxide (MoO mostly3) prepared by the nitridation of ammonia, prepared material is non-porous polycrystalline
Material is unfavorable for the raising of the characterization and active site quantity of catalyst performance, poor as electrode material performance.Separately
Outside, it is easy to generate multiphase nitride in the nitridation process of Mo metal, is unfavorable for the preparation of pure phase product, also influence electrode material
Performance.The nitride of molybdenum is expected to become the potential new material for replacing noble metal, becomes non-precious metal catalyst of new generation, as resistance to
The electrode material of the highly stable supercapacitor of burn into has excellent specific capacitance, is expected to become the energy storage material haveing excellent performance
Material.
But there is presently no the methods that report prepares large-sized nitride porous molybdenum single crystal.
Summary of the invention
According to the one aspect of the application, a kind of nitride porous molybdenum single crystal material, nitride porous molybdenum single crystal material are provided
With large scale, there is presently no the methods that report prepares large-sized nitride porous molybdenum single crystal.
The nitride porous molybdenum single crystal material, which is characterized in that in the nitride porous molybdenum single crystal material containing 10nm~
The hole of 1000nm.
Optionally, the hole containing 10nm~500nm in the nitride porous molybdenum single crystal material.
Optionally, the hole containing 10nm~300nm in the nitride porous molybdenum single crystal material.
Optionally, the hole containing 10nm~200nm in the nitride porous molybdenum single crystal material.
Optionally, the hole containing 10nm~100nm in the nitride porous molybdenum single crystal material.
Optionally, the capacitor of the nitride porous molybdenum single crystal material is not less than 8.8F/cm2。
Optionally, the nitride porous molybdenum single crystal material includes porous MoN monocrystalline, porous Mo2N monocrystalline, porous Mo3N2It is single
Brilliant, porous Mo5N6At least one of monocrystalline.
Optionally, the nitride porous molybdenum single crystal material is porous MoN monocrystal material.
Optionally, the nitride porous molybdenum single crystal material is porous Mo2The hole N monocrystal material.
Optionally, the nitride porous molybdenum single crystal material is porous Mo3N2Monocrystal material.
Optionally, the nitride porous molybdenum single crystal material is porous Mo5N6Monocrystal material.
Optionally, the nitride porous molybdenum single crystal material is nitride porous molybdenum single crystal film and/or nitride porous molybdenum single crystal
Crystal.
Optionally, the surface of the nitride porous molybdenum single crystal film be (001) face of nitride porous molybdenum single crystal, (100) face,
(110) face, at least one side in (111) face.
Optionally, the surface of the nitride porous molybdenum single crystal crystal be (001) face of nitride porous molybdenum single crystal, (100) face,
(110) face, at least one side in (111) face.
Optionally, the nitride porous molybdenum single crystal material is nitride porous molybdenum single crystal film and/or nitride porous molybdenum single crystal
Crystal.
Optionally, the surface of the nitride porous molybdenum single crystal film be (001) face of nitride porous molybdenum single crystal, (100) face,
(110) face, at least one side in (111) face.
Optionally, the surface of the nitride porous molybdenum single crystal crystal be (001) face of nitride porous molybdenum single crystal, (100) face,
(110) face, at least one side in (111) face.
Optionally, the size of the nitride porous molybdenum single crystal crystal is 0.1cm~30cm；
The nitride porous molybdenum single crystal film with a thickness of 10nm~100 μm.
Optionally, the size of the nitride porous molybdenum single crystal crystal is 1cm~5cm.
Optionally, two o'clock is most on a surface of largest surface area in the outer surface of the nitride porous molybdenum single crystal crystal
Big linear distance is 0.1cm~30cm.
According to the another aspect of the application, a kind of preparation method of nitride porous molybdenum single crystal material, the method behaviour are provided
Make simple, reproducible, cheap, porous large-sized molybdenum nitride monocrystal material has been prepared, purity is high.
The preparation method of the nitride porous molybdenum single crystal material, which is characterized in that include at least: by molybdenum source and contain ammonia
Feed gas reaction, obtain the nitride porous molybdenum single crystal material；
Wherein, the molybdenum source is selected from least one of metal molybdate monocrystal material.
Optionally, the nitride porous molybdenum single crystal material is nitride porous object monocrystal material.
Optionally, the temperature of the reaction is 300~1700 DEG C；
The pressure of the reaction is 0.01Torr~760Torr；
The time of the reaction is 0.5min~300h.
Optionally, the temperature of the reaction is 600~1700 DEG C.
Optionally, the temperature upper limit of the reaction is selected from 1700 DEG C, 1680 DEG C, 1600 DEG C, 1500 DEG C, 1400 DEG C, 1350
℃、1300℃、1250℃、1200℃、1150℃、1100℃、1050℃、1000℃、900℃、800℃、750℃、600℃、
550 DEG C, 500 DEG C, 450 DEG C, 400 DEG C or 350 DEG C；Lower limit be selected from 1680 DEG C, 1600 DEG C, 1500 DEG C, 1400 DEG C, 1350 DEG C,
1300℃、1250℃、1200℃、1150℃、1100℃、1050℃、1000℃、900℃、800℃、750℃、600℃、550
DEG C, 500 DEG C, 450 DEG C, 400 DEG C, 350 DEG C or 300 DEG C.
Optionally, the upper pressure limit of the reaction be selected from 0.05Torr, 0.1Torr, 0.2Torr, 0.5Torr, 2Torr,
10Torr、20Torr、50Torr、100Torr、150Torr、200Torr、280Torr、300Torr、400Torr、500Torr、
600Torr, 650Torr, 700Torr or 760Torr；Lower limit be selected from 00.01Torr, 0.05Torr, 0.1Torr, 0.2Torr,
0.5Torr、2Torr、10Torr、20Torr、50Torr、100Torr、150Torr、200Torr、280Torr、300Torr、
400Torr, 500Torr, 600Torr, 650Torr or 700Torr.
Optionally, the time upper limit of the reaction be selected from 0.6min, 1min, 2min, 10min, 18min, 20min,
50min, 1h, 2h, 10h, 20h, 36min, 50h, 100h, 150h, 200h, 250h or 300h；Lower limit be selected from 0.5min,
0.6min、1min、2min、10min、18min、20min、50min、1h、2h、10h、20h、36min、50h、100h、150h、
200h or 250h.
Optionally, the temperature of the reaction is 600~1050 DEG C.
Optionally, the pressure of the reaction is 10Torr~300Torr.
Optionally, the temperature of the reaction is 700~1350 DEG C；
The pressure of the reaction is 50Torr~300Torr；
The time of the reaction is 1h~200h.
It optionally, include at least one of ammonia and nitrogen, argon gas, hydrogen in the unstripped gas containing ammonia；
Wherein, the flow of ammonia is denoted as a, and the flow of nitrogen is denoted as b, and the flow of argon gas is denoted as c, and the flow of hydrogen is denoted as d,
Meet:
0.05SLM≤a≤100SLM；
0SLM≤b≤100SLM；
0SLM≤c≤100SLM；
0SLM≤d≤100SLM。
Optionally, the range of flow upper limit of the ammonia be selected from 0.1SLM, 0.5SLM, 1SLM, 1.5SLM 2SLM, 3SLM,
4SLM、5SLM、6SLM、7SLM、8SLM、9SLM、10SLM、20SLM、30SLM、40SLM、50SLM、60SLM、70SLM、
80SLM, 90SLM or 100SLM；Lower limit be selected from 0.05SLM, 0.1SLM, 0.5SLM, 1SLM, 1.5SLM 2SLM, 3SLM, 4SLM,
5SLM, 6SLM, 7SLM, 8SLM, 9SLM, 10SLM, 20SLM, 30SLM, 40SLM, 50SLM, 60SLM, 70SLM, 80SLM or
90SLM。
Optionally, the range of flow upper limit of the nitrogen be selected from 0.01SLM, 0.1SLM, 0.2SLM, 0.5SLM, 0.8SLM,
1SLM, 2SLM, 5SLM, 10SLM, 20SLM, 50SLM, 80SLM or 100SLM；Lower limit be selected from 0SLM, 0.01SLM, 0.07SLM,
0.08SLM, 0.1SLM, 0.2SLM, 0.5SLM, 0.8SLM, 1SLM, 2SLM, 5SLM, 10SLM, 20SLM, 50SLM or 80SLM.
Optionally, the range of flow upper limit of the argon gas be selected from 0.01SLM, 0.1SLM, 0.2SLM, 0.5SLM, 0.8SLM,
1SLM, 2SLM, 5SLM, 10SLM, 20SLM, 50SLM, 80SLM or 100SLM；Lower limit be selected from 0SLM, 0.01SLM, 0.07SLM,
0.08SLM, 0.1SLM, 0.2SLM, 0.5SLM, 0.8SLM, 1SLM, 2SLM, 5SLM, 10SLM, 20SLM, 50SLM or 80SLM.
Optionally, the range of flow upper limit of the hydrogen be selected from 0.01SLM, 0.1SLM, 0.2SLM, 0.5SLM, 0.8SLM,
1SLM, 2SLM, 5SLM, 10SLM, 20SLM, 50SLM, 80SLM or 100SLM；Lower limit be selected from 0SLM, 0.01SLM, 0.1SLM,
0.2SLM, 0.5SLM, 0.8SLM, 1SLM, 2SLM, 5SLM, 10SLM, 20SLM, 50SLM or 80SLM.
Optionally,
0.3SLM≤a≤1SLM；
0.05SLM≤b≤1SLM；
0.05SLM≤c≤1SLM；
0.05SLM≤d≤0.5SLM。
Optionally, the size of the metal molybdate monocrystalline is 0.1~30cm.The size of monocrystalline is defined as: monocrystalline appearance
In face on a surface of largest surface area two o'clock maximum linear distance.
Optionally, the metal molybdate monocrystalline is selected from lead molybdate, bismuth molybdate, lithium molybdate monocrystalline, sodium molybdate monocrystalline, molybdic acid
At least one of potassium monocrystalline.
Optionally, the lead molybdate single crystal is selected from (001) face lead molybdate single crystal, (100) face lead molybdate single crystal, (110) face
At least one of lead molybdate single crystal, (111) face lead molybdate single crystal.
Optionally, the molybdic acid bismuth single crystal is selected from (001) face molybdic acid bismuth single crystal, (100) face molybdic acid bismuth single crystal, (110) face
At least one of molybdic acid bismuth single crystal, (111) face molybdic acid bismuth single crystal
Optionally, the lithium molybdate monocrystalline is selected from (001) face lithium molybdate monocrystalline, (100) face lithium molybdate monocrystalline, (110) face
At least one of lithium molybdate, (111) face lithium molybdate monocrystalline.
Optionally, the sodium molybdate monocrystalline is selected from (001) face sodium molybdate monocrystalline, (100) face sodium molybdate monocrystalline, (110) face
At least one of sodium molybdate monocrystalline, (111) face sodium molybdate monocrystalline.
Optionally, the potassium molybdate monocrystalline is selected from (001) face potassium molybdate monocrystalline, (100) face potassium molybdate monocrystalline, (110) face
At least one of potassium molybdate monocrystalline, (111) face potassium molybdate monocrystalline.
Optionally, the method includes at least: molybdenum source being reacted with the feed gas containing ammonia, molybdenum source partial nitridation
Conversion, reverse epitaxial growth nanoporous nitrogenize molybdenum single crystal, obtain nitride porous molybdenum single crystal film；Or
Molybdenum source is reacted with the feed gas containing ammonia, molybdenum source nitrogenizes conversion completely, and reverse epitaxial growth nanometer is more
Hole nitrogenizes molybdenum single crystal, obtains nitride porous molybdenum single crystal crystal.
Optionally, when the nitride porous molybdenum single crystal material is nitride porous molybdenum single crystal film, the molybdenum source and contain ammonia
The time range lower limit of the feed gas reaction of gas is selected from 1min, 20min, 30min, 1h or 2h；The upper limit be selected from 20min,
30min, 1h or 2h.
When the nitride porous molybdenum single crystal material of preparation is nitride porous molybdenum single crystal crystal, the haptoreaction time should meet and make
Molybdenum source is completely converted into nitride porous molybdenum single crystal material.
As an implementation, the application provides a kind of preparation method of nitride porous molybdenum single crystal, the method includes
Following steps:
It using metal molybdate monocrystalline as substrate, is placed in vapor phase epitaxial growth reaction chamber, is closed vapor phase epitaxial growth
Reaction chamber, vapor phase epitaxial growth reaction chamber are evacuated to 0.001Torr, are continually fed into toward vapor phase epitaxial growth reaction chamber containing ammonia
Body makes metal molybdate single crystalline substrate carry out the reverse epitaxial growth of nitridation conversion, obtains nitride porous molybdenum single crystal.
Optionally, the nano silicon nitride molybdenum single crystal is selected from nitride porous molybdenum single crystal film and/or nitride porous molybdenum single crystal is brilliant
One of body.
Optionally, the metal molybdate monocrystalline is selected from lead molybdate, bismuth molybdate, lithium molybdate monocrystalline, sour lithium sodium monocrystalline, sour lithium
At least one of potassium monocrystalline.
The lead molybdate single crystal is selected from (001) face lead molybdate single crystal, (100) face lead molybdate single crystal and (110) face lead molybdate
At least one of monocrystalline, (111) face lead molybdate.
Optionally, the molybdic acid bismuth single crystal be selected from (001) face molybdic acid bismuth single crystal, (100) face molybdic acid bismuth single crystal, (110) and
(111) at least one of face molybdic acid bismuth single crystal
Optionally, the lithium molybdate monocrystalline is selected from (001) face lithium molybdate monocrystalline, (100) face lithium molybdate monocrystalline and (110) face
At least one of lithium molybdate monocrystalline, (111) face lead molybdate.
Optionally, the sodium molybdate monocrystalline be selected from (001) face sodium molybdate monocrystalline, (100) face sodium molybdate monocrystalline, (110) and
(111) at least one of face sodium molybdate monocrystalline.
Optionally, the potassium molybdate monocrystalline be selected from (001) face potassium molybdate monocrystalline, (100) face potassium molybdate monocrystalline, (110) and
(111) at least one of face potassium molybdate monocrystalline.
Optionally, the size of the substrate is 0.1~30cm.The size of substrate is defined as: surface area in outer substrate surface
The maximum linear distance of two o'clock on a maximum surface.
Optionally, the ammonia-containing gas include gas below: the ammonia of a flow, the nitrogen of b flow, c flow argon gas
With the hydrogen of d flow, wherein a is 0.05~100SLM, and b is 0~100SLM, and c is 0~100SLM, and d is 0~100SLM.
Optionally, a is 0.3~1SLM, and the b is 0.05~1SLM, and the c is 0.05~1SLM, and the d is
0.05~0.5SLM.
Optionally, it is 600~1700 DEG C of temperature that the nitridation, which converts the condition of reverse epitaxial growth, 0.5 minute time~
300 hours, 0.01~760Torr of pressure.
Optionally, the temperature be 1050~1350 DEG C, the time be 1~200 hour, the pressure be 50~
300Torr。
The nitride porous molybdenum single crystal that preparation method described in any of the above-described embodiment is prepared.
Specifically, the present invention is placed in vapor phase epitaxial growth reaction chamber using metal molybdate monocrystalline as substrate, is closed
Vapor phase epitaxial growth reaction chamber, vapor phase epitaxial growth reaction chamber are evacuated to 0.001Torr, hold toward vapor phase epitaxial growth reaction chamber
The continuous ammonia-containing gas that are passed through make metal molybdate single crystalline substrate carry out the reverse epitaxial growth of nitridation conversion, obtain nitride porous molybdenum list
It is brilliant.The present invention can convert the reaction condition of reverse epitaxial growth by adjusting nitridation, obtain nitride porous molybdenum single crystal film or
Person's nitride porous molybdenum single crystal crystal.Nitride porous molybdenum single crystal of the invention can be used as novel electro catalytic electrode material, super
Capacitor electrode material.
In the application, " size of crystal " " size of substrate " each means one of largest surface area in crystal outer surface
The maximum linear distance of two o'clock on surface.
In the application, SLM is the abbreviation of Standard Litre Per Minute, indicates 1L/min under standard state
Flow.
According to the another aspect of the application, the nitride porous molybdenum single crystal material is provided, according to the method system
At least one of standby obtained nitride porous molybdenum single crystal material is in electro catalytic electrode material electrode material for super capacitor
Using.
According to the another aspect of the application, the nitride porous molybdenum single crystal material is provided, according to the method system
At least one of standby obtained nitride porous molybdenum single crystal material is in organic matter hydrodesulfurization catalytic, electro catalytic electrode material, super
Application in grade capacitor material.
According to the another aspect of the application, a kind of super capacitor material is provided.The super capacitor material
In the nitride porous molybdenum single crystal material being prepared including the nitride porous molybdenum single crystal material, according to the method at least
It is a kind of.
The beneficial effect that the application can generate includes:
1) nitride porous molybdenum single crystal material provided herein, utilizes alkali metal molybdate and molybdenum nitride single-crystal lattice knot
The characteristics of structure is close and Lattice Matching turns alkali metal molybdate single crystalline substrate and ammonia-containing gas by outer and inner nitridation at high temperature
Change reverse epitaxial growth molybdenum nitride crystal, remaining product volatilizees completely, and product purity is high；Such as utilize alkali metal molybdate crystal
With molybdenum nitride lattice structure the characteristics of close and Lattice Matching, make metal molybdate single crystalline substrate and ammonia-containing gas at high temperature by
Outer and inner nitridation converts reverse epitaxial growth MoN crystal, remaining product volatilizees completely, and product purity is high；
2) nitride porous molybdenum single crystal material provided herein utilizes the content of molybdenum in same volume metal molybdate crystal
Than the poor feature of molybdenum in molybdenum nitride crystal, using metal molybdate single crystalline substrate and ammonia-containing gas at high temperature by outer and
In nitridation convert reverse extension and generate nanoporous and nitrogenize molybdenum single crystal；
3) nitride porous molybdenum single crystal material provided herein, reports the porous nitrogen with nano pore structure for the first time
Change molybdenum single crystal, large scale (001) face nanoporous nitrogenizes molybdenum single crystal, large scale (100) face nitride porous molybdenum single crystal and large scale
(110) face and (111) nitride porous molybdenum single crystal；
4) nitride porous molybdenum single crystal material provided herein prepares the method operation letter of nanoporous nitridation molybdenum single crystal
It is single, reproducible, cheap；
5) nitride porous molybdenum single crystal material provided herein, it is reverse that metal molybdate single crystalline substrate carries out nitridation conversion
Epitaxial growth, nitridation is different, available monocrystal thin films or monocrystalline crystal.Metal molybdate single crystalline substrate nitrogenizes completely,
What is obtained is nitride porous molybdenum single crystal crystal；Metal molybdate single crystalline substrate partial nitridation, what is obtained is nanoporous molybdenum nitride
Monocrystal thin films；
6) nitride porous molybdenum provided by the present application, has good metallic conduction behavior, and big specific surface area can be used as electricity
Catalytic electrode material, for example, our monocrystalline for preparing are as the electrode material of supercapacitor its capacitor up to 8.8F/cm2, and
And cyclical stability with super strength.
Detailed description of the invention
Fig. 1 is the XRD diagram of substrate and porous MoN monocrystalline crystal in the application；Wherein, figure (a) is (001) face in embodiment
Lead molybdate single crystal substrate, (100) face lead molybdate single crystal substrate and (110) face lead molybdate single crystal substrate, figure (b) are in embodiment 1
The XRD diagram of the porous MoN monocrystalline crystal in (001) face of preparation.
Fig. 2 be longitudinal sectional (001) face of porous MoN monocrystalline crystal prepared in the embodiment of the present invention 1 high-resolution TEM figure and
Selective electron diffraction figure；Wherein (a) is selective electron diffraction figure；It (b) is High-Resolution Map.
Fig. 3 is the different crystal face substrates of the porous MoN monocrystalline crystal prepared in the embodiment of the present invention in different growth conditions
Under SEM figure；Wherein, figure (a) is the MoN monocrystalline pattern obtained after the nitridation of (110) crystal face lead molybdate in embodiment 2, and scale is
1.00 μm, the MoN monocrystalline pattern that figure (b) embodiment 3 (100) crystal face lead molybdate obtains after 750 DEG C of nitridations, scale is 1.00 μ
M, figure (c) are the MoN monocrystalline pattern obtained after the nitridation of (001) crystal face lead molybdate in embodiment 1, and scale is 1.00 μm, and figure (d) is
The MoN monocrystalline pattern that (100) crystal face lead molybdate obtains after 800 DEG C of nitridations in embodiment 4, scale are 1.00 μm.
Fig. 4 is the section SEM figure that the porous MoN monocrystal thin films in (001) face are prepared in the embodiment of the present invention 5.
Fig. 5 is the super electrical property figure in the KOH aqueous solution of 1M of porous MoN monocrystalline crystal prepared by embodiment 1；Wherein
A) be constant current charge-discharge diagram, c for cyclic voltammetry curve figure under different scanning speed, b)) be AC impedance spectroscopy, d) be capacitor with
The relational graph of cycle charge-discharge number, wherein illustration is that first time cyclic voltammetry curve is with the 10000th cyclic voltammetry curve e)
The linear relationship chart of scanning speed and electric current shows the fake capacitance behavior of MoN；It f) is area ratio capacitance map.
Fig. 6 is the H in 0.5M of porous MoN monocrystalline crystal prepared by embodiment 12SO4Super electrical property figure in aqueous solution；
Wherein a) it is cyclic voltammetry curve figure under different scanning speed, b) be constant current charge-discharge diagram, c) be AC impedance spectroscopy, d) it is electricity
Hold the relational graph with cycle charge-discharge number, wherein illustration is first time cyclic voltammetry curve and the 10000th cyclic voltammetry curve
E) it is the linear relationship chart of scanning speed and electric current, shows the fake capacitance behavior of MoN；It f) is area ratio capacitance map.
Specific embodiment
The application is described in detail below with reference to embodiment, but the application is not limited to these embodiments.
Unless otherwise instructed, the raw material in embodiments herein is bought by commercial sources.
In embodiment, lead molybdate single crystal is purchased from Jiaozhuo Jing Rui Photoelectric Co., Ltd., molybdic acid bismuth single crystal, lithium molybdate monocrystalline, molybdenum
This laboratory of sour sodium, potassium molybdate is grown by monocrystal growing furnace.
Growth conditions are as follows: bismuth molybdate list, lithium molybdate monocrystalline, sodium molybdate monocrystalline and potassium molybdate monocrystalline use Czochralski
Method preparation, revolving speed are 15~20r.p, and pulling rate is 0.5~1mm/, according to the different melt temperatures of material melting point in 705-925
℃。
Analysis method is as follows in embodiments herein:
In embodiment, the pattern of sample uses JEOL JSM 6330F type scanning electron microscope analysis.
In embodiment, the X-ray diffraction analysis of sample uses Bede D1 (UK, Bede Scientific；Cu-Kα
1radiation；operated at 40kV and 45mA；) type high-resolution X-ray diffraction analyzer.
In embodiment, the pattern of sample uses 30 Flied emission transmission electron microscope analysis of Tecnai.
The application provides a kind of nitride porous molybdenum single crystal material, in the nitride porous molybdenum single crystal material containing 10nm~
The hole of 1000nm.
As an implementation, the nitride porous molybdenum single crystal material includes porous MoN monocrystalline, porous Mo2N monocrystalline,
Porous Mo3N2Monocrystalline, porous Mo5N6At least one of monocrystalline.
As an implementation, the nitride porous molybdenum single crystal material is nitride porous molybdenum single crystal film and/or porous
Nitrogenize molybdenum single crystal crystal.
The application provides a kind of preparation method of nitride porous molybdenum single crystal material, includes at least: by molybdenum source and containing ammonia
Feed gas reaction, obtain the nitride porous molybdenum single crystal material；
Wherein, the molybdenum source is selected from least one of alkali metal molybdate monocrystal material.
As an implementation, the preparation method of porous MoN monocrystalline, using lead molybdate, bismuth molybdate and alkali metal molybdic acid
Single-crystal of salt is placed in vapor phase epitaxial growth reaction chamber as substrate, is closed vapor phase epitaxial growth reaction chamber, and vapor phase epitaxial growth is anti-
Room is answered to be evacuated to 0.001Torr, being continually fed into ammonia-containing gas toward vapor phase epitaxial growth reaction chamber serves as a contrast metal molybdate monocrystalline
Bottom carries out nitridation and converts reverse epitaxial growth, obtains nitride porous molybdenum single crystal.
Embodiment 1
Using (001) face lead molybdate single crystal as substrate, substrate dimension 0.5cm, substrate is placed in vapor phase epitaxial growth reaction chamber
In, it is closed vapor phase epitaxial growth reaction chamber, vapor phase epitaxial growth reaction chamber is evacuated to 0.001Torr, and vapor phase epitaxial growth is anti-
It answers room to be warming up to 750 DEG C, is passed through the ammonia that flow is 1SLM, the pressure of control vapor phase epitaxial growth reaction chamber is 100Torr, is held
Continuous to be passed through ammonia 20 hours, stopping is passed through ammonia, cools down, obtains the porous MoN monocrystalline crystal in (001) face.
Embodiment 2
Using (110) face lead molybdate single crystal as substrate, substrate dimension 0.5cm, substrate is placed in vapor phase epitaxial growth reaction chamber
In, it is closed vapor phase epitaxial growth reaction chamber, vapor phase epitaxial growth reaction chamber is evacuated to 0.001Torr, and vapor phase epitaxial growth is anti-
It answers room to be warming up to 750 DEG C, is passed through the ammonia that flow is 1SLM, the pressure of control vapor phase epitaxial growth reaction chamber is 100Torr, is held
Continuous to be passed through ammonia 20 hours, stopping is passed through ammonia, cools down, obtains the porous MoN monocrystalline crystal in (110) face.
Embodiment 3
Using (100) face lead molybdate single crystal as substrate, substrate dimension 0.5cm, substrate is placed in vapor phase epitaxial growth reaction chamber
In, it is closed vapor phase epitaxial growth reaction chamber, vapor phase epitaxial growth reaction chamber is evacuated to 0.001Torr, and vapor phase epitaxial growth is anti-
It answers room to be warming up to 750 DEG C, is passed through the ammonia that flow is 1SLM, the pressure of control vapor phase epitaxial growth reaction chamber is 100Torr, is held
Continuous to be passed through ammonia 20 hours, stopping is passed through ammonia, cools down, obtains the porous MoN monocrystalline crystal in (100) face.
Embodiment 4
Using (100) face lead molybdate single crystal as substrate, substrate dimension 0.5cm, substrate is placed in vapor phase epitaxial growth reaction chamber
In, it is closed vapor phase epitaxial growth reaction chamber, vapor phase epitaxial growth reaction chamber is evacuated to 0.001Torr, and vapor phase epitaxial growth is anti-
It answers room to be warming up to 800 DEG C, is passed through the ammonia that flow is 1SLM, the pressure of control vapor phase epitaxial growth reaction chamber is 100Torr, is held
Continuous to be passed through ammonia 20 hours, stopping is passed through ammonia, cools down, obtains the porous MoN monocrystalline crystal in (100) face.
Embodiment 5
Using (001) face lead molybdate single crystal as substrate, substrate dimension 0.5cm, substrate is placed in vapor phase epitaxial growth reaction chamber
In, it is closed vapor phase epitaxial growth reaction chamber, vapor phase epitaxial growth reaction chamber is evacuated to 0.001Torr, and vapor phase epitaxial growth is anti-
It answers room to be warming up to 750 DEG C, is passed through the ammonia that flow is 1SLM, the pressure of control vapor phase epitaxial growth reaction chamber is 100Torr, is held
Continuous to be passed through ammonia 5 hours, stopping is passed through ammonia, cools down, obtains the porous MoN monocrystal thin films in (001) face.
Embodiment 6
Using (100) face molybdic acid bismuth single crystal as substrate, substrate dimension 10cm, substrate is placed in vapor phase epitaxial growth reaction chamber
In, it is closed vapor phase epitaxial growth reaction chamber, vapor phase epitaxial growth reaction chamber is evacuated to 0.001Torr, and vapor phase epitaxial growth is anti-
It answers room to be warming up to 300 DEG C, is passed through the ammonia of flow 0.3SLM, the argon gas that the nitrogen that flow is 0.07SLM, flow are 0.08SLM
With the ammonia-containing gas for the hydrogen composition that flow is 0.07SLM, the pressure of control vapor phase epitaxial growth reaction chamber is 280Torr, is held
Continuous to be passed through ammonia-containing gas 100 hours, stopping is passed through ammonia-containing gas, cools down, obtains (100) face Mo2N monocrystalline crystal.
Embodiment 7
Using (001) face lithium molybdate monocrystalline as substrate, substrate dimension 0.5cm, substrate is placed in vapor phase epitaxial growth reaction chamber
In, it is closed vapor phase epitaxial growth reaction chamber, vapor phase epitaxial growth reaction chamber is evacuated to 0.001Torr, and vapor phase epitaxial growth is anti-
It answers room to be warming up to 600 DEG C, is passed through the ammonia that flow is 1SLM, the pressure of control vapor phase epitaxial growth reaction chamber is 50Torr, is held
Continuous to be passed through ammonia 200 hours, stopping is passed through ammonia, cools down, obtains (001) face nanoporous Mo3N2Monocrystalline crystal.
Embodiment 8
Using (100) face sodium molybdate monocrystalline as substrate, substrate dimension 10cm, substrate is placed in vapor phase epitaxial growth reaction chamber
In, it is closed vapor phase epitaxial growth reaction chamber, vapor phase epitaxial growth reaction chamber is evacuated to 0.001Torr, and vapor phase epitaxial growth is anti-
It answers room to be warming up to 1300 DEG C, is passed through the ammonia of flow 0.3SLM, the argon gas that the nitrogen that flow is 0.07SLM, flow are 0.08SLM
With the ammonia-containing gas for the hydrogen composition that flow is 0.07SLM, the pressure of control vapor phase epitaxial growth reaction chamber is 280Torr, is held
Continuous to be passed through ammonia-containing gas 100 hours, stopping is passed through ammonia-containing gas, cools down, obtains (100) face nanoporous Mo5N6Monocrystalline crystal.
Embodiment 9
Using (110) face lithium molybdate monocrystalline as substrate, substrate dimension 27cm, substrate is placed in vapor phase epitaxial growth reaction chamber
In, it is closed vapor phase epitaxial growth reaction chamber, vapor phase epitaxial growth reaction chamber is evacuated to 0.001Torr, and vapor phase epitaxial growth is anti-
It answers room to be warming up to 900 DEG C, is passed through argon gas and stream that nitrogen, flow that ammonia, flow that flow is 80SLM are 20SLM are 15SLM
The pressure of the ammonia-containing gas that the hydrogen that amount is 25SLM forms, control vapor phase epitaxial growth reaction chamber is 150Torr, is continually fed into
Ammonia-containing gas 300 hours, stopping was passed through ammonia-containing gas, cools down, obtains (110) face nanoporous MoN monocrystalline crystal.
Embodiment 10
Using (001) face lithium molybdate monocrystalline as substrate, substrate dimension 3cm, substrate is placed in vapor phase epitaxial growth reaction chamber,
It is closed vapor phase epitaxial growth reaction chamber, vapor phase epitaxial growth reaction chamber is evacuated to 0.001Torr, vapor phase epitaxial growth reaction chamber
550 DEG C are warming up to, the ammonia-containing gas of the ammonia that flow is 0.5SLM and the argon gas that flow is 0.05SLM composition is passed through, controls gas
The pressure of phase epitaxy growth response room is 760Torr, is continually fed into ammonia-containing gas 0.3 hour, and stopping is passed through ammonia-containing gas, is dropped
Temperature obtains (001) face nanoporous Mo3N2Monocrystal thin films.
Embodiment 11
Using (001) face potassium molybdate monocrystalline as substrate, substrate dimension 5cm, substrate is placed in vapor phase epitaxial growth reaction chamber,
It is closed vapor phase epitaxial growth reaction chamber, vapor phase epitaxial growth reaction chamber is evacuated to 0.001Torr, vapor phase epitaxial growth reaction chamber
550 DEG C are warming up to, the ammonia that flow is 3SLM is passed through, the pressure of control vapor phase epitaxial growth reaction chamber is 2Torr, is continually fed into
Ammonia 2 hours, stopping was passed through ammonia, cools down, obtains (001) face nanoporous Mo2N monocrystal thin films.
Embodiment 12
Using (100) face sodium molybdate monocrystalline as substrate, substrate dimension 16cm, substrate is placed in vapor phase epitaxial growth reaction chamber
In, it is closed vapor phase epitaxial growth reaction chamber, vapor phase epitaxial growth reaction chamber is evacuated to 0.001Torr, and vapor phase epitaxial growth is anti-
It answers room to be warming up to 1680 DEG C, is passed through argon gas and stream that nitrogen, flow that ammonia, flow that flow is 15SLM are 2SLM are 1SLM
The pressure of the ammonia-containing gas that the hydrogen that amount is 1SLM forms, control vapor phase epitaxial growth reaction chamber is 650Torr, is continually fed into and contains
Ammonia gas 0.6 minute, stopping was passed through ammonia-containing gas, cools down, obtains (100) face nanoporous Mo5N6Monocrystal thin films.
Embodiment 13
Using (110) face lithium molybdate monocrystalline as substrate, substrate dimension 14cm, substrate is placed in vapor phase epitaxial growth reaction chamber
In, it is closed vapor phase epitaxial growth reaction chamber, vapor phase epitaxial growth reaction chamber is evacuated to 0.001Torr, and vapor phase epitaxial growth is anti-
It answers room to be warming up to 1200 DEG C, is passed through argon gas and stream that nitrogen, flow that ammonia, flow that flow is 15SLM are 2SLM are 1SLM
The pressure of the ammonia-containing gas that the hydrogen that amount is 1SLM forms, control vapor phase epitaxial growth reaction chamber is 650Torr, is continually fed into and contains
Ammonia gas 10 minutes, stopping was passed through ammonia-containing gas, cools down, obtains (110) face nanoporous MoN monocrystal thin films.
Embodiment 14
Using (111) face lithium molybdate monocrystalline as substrate, substrate dimension 2cm, substrate is placed in vapor phase epitaxial growth reaction chamber,
It is closed vapor phase epitaxial growth reaction chamber, vapor phase epitaxial growth reaction chamber is evacuated to 0.001Torr, vapor phase epitaxial growth reaction chamber
1150 DEG C are warming up to, the ammonia that flow is 1SLM is passed through, the pressure of control vapor phase epitaxial growth reaction chamber is 50Torr, is persistently led to
Enter ammonia 200 hours, stopping is passed through ammonia, cools down, obtains (111) face nanoporous Mo2N monocrystalline crystal.
15 structural characterization of embodiment
The sample and its substrate progress structural characterization using the method for X-ray crystal diffraction prepared by embodiment 1~14.Knot
Fruit shows that corresponding molybdenum nitride monocrystal material is prepared in embodiment 1~14, and it is porous that (001) face has been prepared in embodiment 1
(110) face Mo has been prepared in MoN monocrystalline crystal, embodiment 22N monocrystalline crystal, embodiment 3 and embodiment 4 are prepared
(100) face Mo2(100) face Mo has been prepared in N monocrystalline crystal, embodiment 62N monocrystalline crystal, embodiment 7 are prepared
(001) face nanoporous Mo3N2(100) face nanoporous Mo has been prepared in monocrystalline crystal, embodiment 85N6Monocrystalline crystal, it is real
It applies example 9 (110) face nanoporous MoN monocrystalline crystal embodiment 14 has been prepared and (111) face nanoporous has been prepared
Mo2N monocrystalline crystal.The XRD spectra of monocrystal thin films prepared by embodiment 5, embodiment 10 to embodiment 13 shows, product it is equal
There is the diffraction maximum of corresponding nitrogen-molybdenum compound, but among film unreacted raw material crystal some can not show accordingly
The diffraction maximum of raw material is combined, it is known that it is monocrystal thin films with SEM figure.As shown in FIG. 1, FIG. 1 is the application for typical XRD spectrum
The XRD diagram of middle substrate and porous MoN monocrystalline crystal；Wherein, in Fig. 1 (a) be embodiment in (001) face lead molybdate single crystal substrate,
(100) face lead molybdate single crystal substrate and (110) face lead molybdate single crystal substrate, (b) is (001) face PbMoO in embodiment 1 in Fig. 14
The XRD diagram of single crystalline substrate and the porous MoN monocrystalline crystal in (001) face of preparation is (001) face MoN monocrystalline.
16 morphology characterization of embodiment
It is characterized using pattern of the scanning electron microscope to sample prepared by embodiment 1~14, the results show that embodiment 1
The sample of~14 preparations all has the hole of 10nm~1000nm.
Typical monocrystalline crystal SEM schemes the SEM as shown in figure 3, the porous MoN monocrystalline crystal prepared in corresponding embodiment 1
Figure.Examples 1 to 4, embodiment 6~9, the SEM spectrum of embodiment 14 are similar with Fig. 3, and being prepared porous has three
Tie up the MoN monocrystalline crystalline material of skeleton.
Typical monocrystal thin films SEM schemes the section as shown in figure 4, the porous MoN monocrystal thin films prepared in corresponding embodiment 5
SEM figure.SEM spectrum shows that the upper and lower surfaces of section are the porous MoN monocrystalline of porous nano, and middle section is molybdic acid
Lead monocrystalline.Nanoporous molybdenum nitride monocrystal thin films material has been prepared in embodiment 10~13, with what is prepared with embodiment 5
The similar section of sample.
It is characterized using pattern of the transmission electron microscope to sample prepared by embodiment 1~14, the results show that embodiment 1
The sample of~14 preparations is the monocrystal material of uniform pure phase.Typical TEM figure in corresponding embodiment 1 as shown in Fig. 2, prepare
The high-resolution TEM in longitudinal sectional (100) face of nanoporous MoN monocrystalline crystal schemes, and left is selective electron diffraction figure.TEM figure and electricity
Sub- diffraction pattern shows that integral material is monocrystalline.
17 performance test of embodiment
Capacity measurement is carried out to sample prepared by embodiment 1~14.
Test condition are as follows: three-electrode method test sample capacitor, molybdenum nitride are working electrode, and platinized platinum is to electrode, reference electricity
Extremely saturated calomel electrode, test platform are German Germany Zha Na (Zahner) electrochemical workstation, and test solution is respectively 1M
KOH and 0.5M H2SO4, all tests carry out at room temperature.
Fig. 5 and Fig. 6 is respectively the mono-crystal nitride molybdenum for preparing in embodiment 1 in KOH and H2SO4Super capacitor in aqueous solution
Property, sample shows fake capacitance property as seen from the figure, has great specific capacitance and high stability, 10,000 charge and discharge
Capacitor is afterwards almost without decaying.It is a kind of super capacitor material haveing excellent performance, the potential super capacitor as a new generation
Equipment material is to replace noble metal RuO2。
The above is only several embodiments of the application, not does any type of limitation to the application, although this Shen
Please disclosed as above with preferred embodiment, however not to limit the application, any person skilled in the art is not taking off
In the range of technical scheme, a little variation or modification are made using the technology contents of the disclosure above and is equal to
Case study on implementation is imitated, is belonged in technical proposal scope.
Claims (10)
1. a kind of nitride porous molybdenum single crystal material, which is characterized in that in the nitride porous molybdenum single crystal material containing 10nm~
The hole of 1000nm.
2. nitride porous molybdenum single crystal material according to claim 1, which is characterized in that the nitride porous molybdenum single crystal material
Including porous MoN monocrystalline, porous Mo2N monocrystalline, porous Mo3N2Monocrystalline, porous Mo5N6At least one of monocrystalline.
3. nitride porous molybdenum single crystal material according to claim 1, which is characterized in that the nitride porous molybdenum single crystal material
For nitride porous molybdenum single crystal film and/or nitride porous molybdenum single crystal crystal；
Preferably, the surface of the nitride porous molybdenum single crystal film be (001) face of nitride porous molybdenum single crystal, (100) face,
(110) face, at least one side in (111) face；
Preferably, the surface of the nitride porous molybdenum single crystal crystal be (001) face of nitride porous molybdenum single crystal, (100) face,
(110) face, at least one side in (111) face.
4. nitride porous molybdenum single crystal material according to claim 3, which is characterized in that the nitride porous molybdenum single crystal crystal
Size be 0.1cm~30cm；
The nitride porous molybdenum single crystal film with a thickness of 1nm~100 μm.
5. the preparation method of the described in any item nitride porous molybdenum single crystal materials of Claims 1-4, which is characterized in that at least wrap
It includes: molybdenum source being reacted with the feed gas containing ammonia, obtains the nitride porous molybdenum single crystal material；
Wherein, the molybdenum source is selected from least one of metal molybdate monocrystal material.
6. according to the method described in claim 5, it is characterized in that, the temperature of the reaction is 300~1700 DEG C；
The pressure of the reaction is 0.01Torr~760Torr；
The time of the reaction is 0.5min~300h.
7. according to the method described in claim 5, it is characterized in that, including ammonia and nitrogen in the unstripped gas containing ammonia
At least one of gas, argon gas, hydrogen；
Wherein, the flow of ammonia is denoted as a, and the flow of nitrogen is denoted as b, and the flow of argon gas is denoted as c, and the flow of hydrogen is denoted as d, full
Foot:
0.05SLM≤a≤100SLM；
0SLM≤b≤100SLM；
0SLM≤c≤100SLM；
0SLM≤d≤100SLM。
8. according to the method described in claim 5, it is characterized in that, the metal molybdate monocrystalline is selected from lead molybdate single crystal, molybdenum
At least one of sour bismuth single crystal, lithium molybdate monocrystalline, sodium molybdate monocrystalline, potassium molybdate monocrystalline；
Preferably, the lead molybdate single crystal is selected from (001) face lead molybdate single crystal, (100) face lead molybdate single crystal, (110) face molybdic acid
At least one of lead monocrystalline, (111) lead molybdate single crystal；
The molybdic acid bismuth single crystal is selected from (001) face molybdic acid bismuth single crystal, (100) face molybdic acid bismuth single crystal, (110) face bismuth molybdate, (111)
At least one of face molybdic acid bismuth single crystal；
The lithium molybdate monocrystalline be selected from (001) face lithium molybdate monocrystalline, (100) face lithium molybdate monocrystalline, (110) face lithium molybdate monocrystalline,
(111) at least one of face lithium molybdate monocrystalline；
The sodium molybdate monocrystalline be selected from (001) face sodium molybdate monocrystalline, (100) face molybdenum sodium monocrystalline, (110) face sodium molybdate monocrystalline,
(111) at least one of face sodium molybdate monocrystalline；
The potassium molybdate monocrystalline be selected from (001) face potassium molybdate monocrystalline, (100) face molybdenum sodium potassium monocrystalline, (110) face potassium molybdate monocrystalline,
(111) at least one of face potassium molybdate monocrystalline.
9. according to the method described in claim 5, it is characterized in that, the method includes at least:
Molybdenum source is reacted with the feed gas containing ammonia, the conversion of molybdenum source partial nitridation, reverse epitaxial growth nanoporous nitrogen
Change molybdenum single crystal, obtains nitride porous molybdenum single crystal film；Or
Molybdenum source is reacted with the feed gas containing ammonia, molybdenum source nitrogenizes conversion, reverse epitaxial growth nitride porous molybdenum completely
Monocrystalline obtains nitride porous molybdenum single crystal crystal.
10. described in any item nitride porous molybdenum single crystal materials of Claims 1-4, according to any one of claim 5 to 9
At least one of nitride porous molybdenum single crystal material that method is prepared is in organic matter hydrodesulfurization catalytic, electro catalytic electrode material
Application in material, super capacitor material.
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| CN112746319A (en) * | 2019-10-29 | 2021-05-04 | 中国科学院福建物质结构研究所 | Porous niobium nitride single crystal material and preparation method and application thereof |
| CN113718334A (en) * | 2020-05-25 | 2021-11-30 | 中国科学院福建物质结构研究所 | Porous gallium nitride single crystal material and preparation method and application thereof |
| CN114164492A (en) * | 2020-09-11 | 2022-03-11 | 中国科学院福建物质结构研究所 | Large-size meso/microporous tungsten nitride single crystal material and preparation method and application thereof |
| CN113502543A (en) * | 2020-12-28 | 2021-10-15 | 中国科学院福建物质结构研究所 | Porous scandium-aluminum nitride single crystal material, and preparation method and application thereof |
| CN113502543B (en) * | 2020-12-28 | 2022-10-11 | 中国科学院福建物质结构研究所 | Porous scandium-aluminum nitride single crystal material, and preparation method and application thereof |
| CN114892271A (en) * | 2022-04-26 | 2022-08-12 | 中国科学院福建物质结构研究所 | Porous MoO 3 Single crystal material and preparation method and application thereof |
| CN114892271B (en) * | 2022-04-26 | 2023-07-25 | 中国科学院福建物质结构研究所 | Porous MoO 3 Single crystal material and preparation method and application thereof |
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