CN109126844A - A kind of molybdenum carbide nanometer sheet and its preparation method and application - Google Patents
A kind of molybdenum carbide nanometer sheet and its preparation method and application Download PDFInfo
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- CN109126844A CN109126844A CN201811009185.7A CN201811009185A CN109126844A CN 109126844 A CN109126844 A CN 109126844A CN 201811009185 A CN201811009185 A CN 201811009185A CN 109126844 A CN109126844 A CN 109126844A
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- Prior art keywords
- molybdenum
- molybdenum carbide
- carbide nanometer
- nanometer sheet
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- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910039444 MoC Inorganic materials 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000001257 hydrogen Substances 0.000 claims abstract description 52
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 52
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 46
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000007787 solid Substances 0.000 claims abstract description 36
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 34
- 239000008103 glucose Substances 0.000 claims abstract description 34
- 238000010438 heat treatment Methods 0.000 claims abstract description 29
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 28
- 239000011733 molybdenum Substances 0.000 claims abstract description 28
- 239000004471 Glycine Substances 0.000 claims abstract description 22
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 230000001788 irregular Effects 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- XUFUCDNVOXXQQC-UHFFFAOYSA-L azane;hydroxy-(hydroxy(dioxo)molybdenio)oxy-dioxomolybdenum Chemical compound N.N.O[Mo](=O)(=O)O[Mo](O)(=O)=O XUFUCDNVOXXQQC-UHFFFAOYSA-L 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims 1
- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
- 238000004321 preservation Methods 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 14
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 30
- 239000011259 mixed solution Substances 0.000 description 26
- 238000006722 reduction reaction Methods 0.000 description 21
- 239000004215 Carbon black (E152) Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 20
- 229930195733 hydrocarbon Natural products 0.000 description 20
- 150000002430 hydrocarbons Chemical class 0.000 description 20
- 239000007789 gas Substances 0.000 description 14
- 239000000843 powder Substances 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000001000 micrograph Methods 0.000 description 10
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 10
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000011049 filling Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 229910003178 Mo2C Inorganic materials 0.000 description 5
- 229910021392 nanocarbon Inorganic materials 0.000 description 5
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- PRORZGWHZXZQMV-UHFFFAOYSA-N azane;nitric acid Chemical compound N.O[N+]([O-])=O PRORZGWHZXZQMV-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- B01J35/33—
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The present invention relates to a kind of molybdenum carbide nanometer sheets and its preparation method and application, the method is to be uniformly mixed molybdenum source, ammonium nitrate, glycine, it is heated to 160~180 DEG C later, obtain mixture 1, glucose is added, is heated to 230~280 DEG C later, obtains fluffy solid, it is put under atmosphere of hydrogen and is heated to 450~550 DEG C, cooling obtains molybdenum carbide nanometer sheet.The molybdenum carbide nanometer piece preparation method heating temperature is low, convenient for operation and promotes, and obtained molybdenum carbide will not reunite, and irregular sheet is presented, and large specific surface area has outstanding catalytic performance in electro-catalysis hydrogen manufacturing in.
Description
Technical field
The present invention relates to molybdenum carbide preparation method, especially a kind of molybdenum carbide nanometer sheet and its preparation method and application.
Background technique
It is good alternative green energy resource that the utilization of Hydrogen Energy, which is traditional fossil energy, and the utilization of Hydrogen Energy depends on hydrogen manufacturing skill
The development of art.Water electrolysis hydrogen production technology is that industry is described as " optimal Process of Hydrogen Production ", and the most crucial problem of the technology is
Efficiently, stablize, the honest exploitation for preparing elctro-catalyst.Currently, platinum based catalyst is maximally efficient elctro-catalyst, but it is high
High cost and low amount of storage seriously constrain the extensive use of such catalyst.
Molybdenum carbide (Mo2C it) due to having many advantages, such as class noble metal property, resistance to roasting, the resistance to nitrogen of resistant to sulfur, high-melting-point, is being catalyzed
Extensive concern has been obtained in field, becomes most potential instead of one of precious metals pt, the catalysis material of Pd.Currently, carbonization
The preparation method of molybdenum mainly has chemical vapour deposition technique, temperature-programmed reduction method and the hot hydrogen reduction method of carbon.Chemical vapour deposition technique
The film Mo of high-ratio surface, high quality can be prepared2C catalyst, but the deposition efficiency of this method is relatively low.Temperature programmed reduction
Method can prepare a nanometer Mo2C catalyst, while activity with higher, but this method needs complicated and stringent synthesis condition, it can
Control property is poor.The hot hydrogen reduction method of carbon can the controllable height of synthesizing high specific surface area, grain size by control active component and temperature
Performance Mo2C catalyst.In terms of raw material, carbon source is synthesized high-performance Mo2One of key of C, different carbon sources can synthesize the not isomorphous
The Mo of body structure2C catalyst.Currently, the carbon source mainly used has the gases such as ethane, methane, normal heptane and normal butane, carbon source is logical
It often needs to mix with hydrogen to realize that carbonization obtains Mo2C catalyst, synthesis technology are complex.Meanwhile Mo at this stage2The conjunction of C
It is carried out at a higher temperature at passing through, such as with 20%CH4~80%H2Gaseous mixture is carbon source, and reaction is needed 700~900
DEG C, when reaction temperature is lower at that time, it is incomplete to will lead to carbonization.Higher synthesis temperature can unavoidably cause Mo2The sintering of C
With reunion, causes the specific surface area of catalyst to reduce, seriously affected the performance of catalyst activity.
Summary of the invention
The purpose of the invention is to overcome the problems, such as that existing molybdenum carbide synthesis temperature height, product are reunited, one kind is provided
Molybdenum carbide nanometer sheet and its preparation method and application.
Concrete scheme is as follows:
A kind of preparation method of molybdenum carbide nanometer sheet, comprising the following steps:
Step 1: molybdenum source, ammonium nitrate, glycine being uniformly mixed, are heated to 160~180 DEG C later, obtains mixture 1；
Step 2: glucose is added into the mixture 1 that step 1 obtains, is heated to 230~280 DEG C later, obtains fluffy
Solid；
Step 3: the fluffy solid that step 2 is obtained, which is put under atmosphere of hydrogen, is heated to 450~550 DEG C, and cooling obtains carbon
Change molybdenum nanometer sheet.
Further, molybdenum source described in step 1 is at least one of ammonium paramolybdate, ammonium tetramolybdate or ammonium dimolybdate；
It is optional, in molybdenum source described in step 1 molybdenum mole amount: the ammonium nitrate mole amount+glycine rub
Your amount=0.5~1.0:2.2~3.2；
Optional, the quality of ammonium nitrate described in step 1: quality=0.8~3.2 of the glycine.
Further, step 1 includes: that deionized water is added after 1a mixes molybdenum source, ammonium nitrate, glycine, is stirred to molten
Solution；1b heated solution keeps the temperature 3~6 minutes, obtains mixture 1 to 165~175 DEG C.
Further, the mass ratio of the molybdenum in glucose described in step 2 and the molybdenum source be 0.8~1.0:1.6~
2.8；
Optional, it is 0.1~0.3g/mL glucose solution that glucose, which is configured to concentration, in step 2, is obtained to step 1
Mixture 1 in be added 10~50mL the glucose solution.
Further, the temperature of heating described in step 2 is 240~270 DEG C, and soaking time is 10~20 minutes.
Further, H in atmosphere of hydrogen described in step 32Flow be 100~500mL/min.
Further, the temperature of heating described in step 3 is 460~500 DEG C, and soaking time is 1~3 hour.
The molybdenum carbide nanometer sheet that the present invention also protects the preparation method of the molybdenum carbide nanometer sheet to be prepared.
Further, the molybdenum carbide nanometer sheet has crystalline structure, is in irregular sheet, with a thickness of 10~30nm.
The present invention also protects application of the molybdenum carbide nanometer sheet in electro-catalysis hydrogen manufacturing.
The utility model has the advantages that
In the present invention, the molybdenum carbide nanometer sheet is using glucose as carbon source, and during the reaction, glucose disperses
It is to determine that molybdenum carbide is presented sheet and receives as the stay in place form that molybdenum carbide is formed and by the nanometer carbon plate of thermosetting unformed shape
One of the key of rice structure.
Moreover the present invention is reaction promoter using ammonium nitrate and glycine, not only effectively reduces molybdenum carbide generating process
In temperature, realize (450~550 DEG C) of medium temperature and complete hydrocarbon reduction synthesis molybdenum carbide nanometer sheets, but also by ammonium nitrate
With a large amount of reducibility gas discharged during glycine reactant, being formed includes amorphous state molybdenum oxide and armorphous nano carbon plate
Presoma.
In short, molybdenum carbide nanometer piece preparation method heating temperature of the present invention is low, convenient for operation and promote, it is obtained
Molybdenum carbide will not reunite, be presented irregular sheet, large specific surface area has outstanding urging in the application in electro-catalysis hydrogen manufacturing
Change performance.
Detailed description of the invention
In order to illustrate more clearly of technical solution of the present invention, attached drawing will be briefly described below, it should be apparent that,
The accompanying drawings in the following description merely relates to some embodiments of the present invention, rather than limitation of the present invention.
Fig. 1 is the XRD diffraction spectra for the presoma that the embodiment of the present invention 1 provides；
Fig. 2 is the electron scanning micrograph for the presoma that the embodiment of the present invention 1 provides；
Fig. 3 is the XRD diffraction spectra for the molybdenum carbide nanometer sheet that the embodiment of the present invention 1 provides；
Fig. 4 is the electron scanning micrograph for the molybdenum carbide nanometer sheet that the embodiment of the present invention 1 provides；
Fig. 5 is the XRD diffraction spectra for the compact solid that comparative example 1 of the present invention provides；
Fig. 6 is the XRD diffraction spectra for the comparative sample 1 that comparative example 1 of the present invention provides；
Fig. 7 is the electron scanning micrograph for the comparative sample 1 that comparative example 1 of the present invention provides；
Fig. 8 is the XRD diffraction spectra for the fluffy solid that comparative example 2 of the present invention provides；
Fig. 9 is the electron scanning micrograph for the fluffy solid that comparative example 2 of the present invention provides；
Figure 10 is the XRD diffraction spectra for the comparative sample 2 that comparative example 2 of the present invention provides；
Figure 11 is the electron scanning micrograph for the comparative sample 2 that comparative example 2 of the present invention provides.
Specific embodiment
The definition of term used in the present invention has definition known in the field and meaning.
In molybdenum carbide nanometer piece preparation method provided by the invention, molybdenum source is preferably ammonium paramolybdate, mixed with deionized water
Conjunction forms solution, and dispersion is uniform, is conducive to the speed for controlling subsequent reactions, forms the uniform product of thickness.
In molybdenum carbide nanometer piece preparation method provided by the invention, molybdenum in the molybdenum source mole amount: (the nitric acid
Ammonium mole amount+glycine mole amount)=0.5~1.0:2.2~3.2, preferably 0.7:2.5~2.9, such as 0.7:
2.7, it is less than the ratio (0.5~1.0:2.2~3.2), ammonium nitrate+glycine is too many, reacts acutely, the temperature mistake of generation
Height is easy the presoma for making to generate into sintering adhesion state, can not form amorphous structure and flaky nanometer structure completely, together
When, opposite molybdenum source is very little, and the yield of product is also low.Greater than the ratio, ammonium nitrate+glycine is very little, can not decompose molybdenum source
For oxide.The wherein quality of the ammonium nitrate: quality=0.8~3.2 of the glycine, preferably 1.3~2.5:, more preferably
1.8~2.3, such as 2.2, stoichiometric ratio principle is abided by the two reaction, is unable to reach decomposition molybdenum less than or greater than the ratio
Temperature needed for source, meanwhile, the gas flow for reacting release also not enough forms nanometer chip architecture.Ammonium nitrate is aoxidized with glycine
Reduction reaction, exothermic heat of reaction generate a large amount of reducibility gas, act not only on the reduction process of glucose, and promote molybdenum source
Form the presoma comprising amorphous state molybdenum oxide.The mass ratio of molybdenum is 0.8~1.0:1.6~2.8 in glucose and the molybdenum source,
If glucose is excessive, excessive armorphous nano carbon plate will form, can not react elimination completely in hydrocarbon reduction process,
It will lead to product Mo2More carbon is remained in C.
In molybdenum carbide nanometer piece preparation method provided by the invention, step 1 is heated to 160~180 DEG C, obtains mixture 1,
It is preferred that 165~175 DEG C, 3~6 minutes are kept the temperature, more preferably 170 DEG C, keeps the temperature 5 minutes, by heating so that molybdenum source formation includes
The presoma of amorphous state molybdenum oxide.
In molybdenum carbide nanometer piece preparation method provided by the invention, step 2 is heated to 230~280 DEG C, obtains fluffy solid
Body, preferably 240~270 DEG C, soaking time are 10~20 minutes, more preferably 250 DEG C, keep the temperature 15 minutes, which obtains fluffy
Loose solid is the mixture of amorphous molybdenum oxide and armorphous nano carbon plate, passes through its XRD diffraction spectra, it is known that, in diffraction
Angle is 23 ° of diffraction maximums for forming apparent unformed shape, shows it to be made of amorphous substance.
In molybdenum carbide nanometer piece preparation method provided by the invention, step 3 is heated to 450~550 DEG C, preferably 480~
530 DEG C, soaking time be 1~3 hour, more preferably 500 DEG C, keep the temperature 2 hours, the reaction need flow be 100~
It is carried out under the atmosphere of hydrogen of 500mL/min, to guarantee the progress of hydrocarbon reaction, flow is too small, and hydrocarbon underaction can not be complete
Form Mo2C, flow reaches then to be caused to waste greatly.It should be noted that the atmosphere of hydrogen can be pure hydrogen, it is also possible to hydrogen
Gas and other gas mixings, for example, hydrogen and nitrogen mixing or hydrogen and inert gas mixing, as long as containing in principle
There is the gas of hydrogen to be ok, temperature is not influenced, but has an impact to hydrogen flowing quantity, such as hydrogen/nitrogen mixture gas, gas
Flow must it is sufficiently large to guarantee hydrogen sufficient amount, it is preferable to use pure hydrogen, flow is 100~500mL/min.
Molybdenum carbide nanometer sheet prepared by the present invention can be used for substituting precious metals pt, Pd as catalyst, especially urge in electricity
Change in hydrogen manufacturing.It can be seen that obtained molybdenum carbide nanometer sheet by product ingredient and morphology analysis and will not reunite, present
Irregular sheet, large specific surface area have preferable structural advantage, can play preferable catalytic performance.
There is no particular limitation in source of the present invention to each raw material, can be commercially available, can also be according to existing
Various methods are prepared, and raw material preferably analyzes pure grade.In addition it is also necessary to explanation, realization of the present invention to heating
Mode there is no particular limitation, as long as reaction system can be made to be in stable temperature range.For example, Muffle furnace, pipe
Formula furnace.In addition, keeping body system is under an atmosphere of hydrogen, it can be and be passed through hydrogen, be also possible to the mixed of hydrogen and other inert gases
It closes, such as hydrogen is mixed with nitrogen, can be known to this those skilled in the art, therefore not to repeat here.
The preferred embodiment of the present invention is described in more detail below.Although the following describe preferred implementations of the invention
Mode, however, it is to be appreciated that may be realized in various forms the present invention without that should be limited by the embodiments set forth herein.It is real
It applies and particular technique or condition person is not specified in example, according to the literature in the art described technology or conditions or according to product
Specification carries out.Reagents or instruments used without specified manufacturer, being can be with conventional products that are commercially available.Under
In the embodiment in face, such as it is not known and illustrates, " % " refers both to weight percent, and degree refers both to DEG C.
Test method used below includes:
XRD test: the object phase of product, test condition are measured by X-ray diffractometer (Rigaku D/max-RB12, XRD)
For Cu target, K α (λ=0.1541nm)
Scanning electron microscope: product is carried out using field emission scanning electron microscope (FEI Quanta FEG450)
Microstructure observation.
Embodiment 1
Molybdenum carbide nanometer sheet is prepared according to the following steps:
Step 1: 18.5 grams of ammonium paramolybdates, 20 grams of ammonium nitrate, 12 grams of glycine are put into the beaker of 1000ml simultaneously, and
100ml deionized water is added, is stirred to and is completely dissolved to form mixed solution, the beaker for filling above-mentioned mixed solution is put into Muffle
It in furnace, is heated 5 minutes at 160 DEG C, keeps coming into full contact with air in heating process, while being sufficiently stirred；
Step 2: it is 0.2g/mL glucose solution that glucose addition ionized water, which is configured to concentration, and step 1 heating terminates
The glucose solution of 30mL is added in solution afterwards, and is stirred and to form mixed solution, by mixed solution be put into 240 degree plus
It is heated 12 minutes in hot stove, fluffy solid is obtained after heating；
Step 3: the fluffy solid that step 2 is obtained is put into tube furnace, in the flowing hydrogen that hydrogen flowing quantity is 200mL/min
Under gas, 500 DEG C it is hydrocarbon reduction 1.5 hours, flowing hydrogen state is still kept the temperature after hydrocarbon reduction, to furnace temperature be cooled to room temperature by
Powder takes out, and obtains molybdenum carbide nanometer sheet.
XRD test and Electronic Speculum are carried out respectively to molybdenum carbide nanometer sheet made from fluffy solid obtained in step 2, step 3
Test, the result is shown in Figure 1~Fig. 4.
From fig. 1, it can be seen that fluffy solid is 23 ° of diffraction maximums for forming apparent unformed shape in the angle of diffraction, show fluffy solid
Body is made of amorphous substance, consisting of the mixture of amorphous molybdenum oxide and armorphous nano carbon plate.Fig. 2 is fluffy solid
The electron scanning micrograph of body, as can be seen from Figure 2, fluffy solid do not find apparent crystalline phases at flaky nanometer structure, this
It is consistent with the result of XRD.
Fig. 3 is the XRD diffraction spectra of molybdenum carbide nanometer sheet, and as can be seen from Figure 3, molybdenum carbide nanometer sheet is crystalline structure, and Fig. 4 is carbon
Change the electron scanning micrograph of molybdenum, it can be seen that it is irregular sheet, and lamellar spacing about 15nm has biggish ratio
Surface area.
Embodiment 2
Step 1: 11.2 grams of ammonium tetramolybdates, 18 grams of ammonium nitrate, 9 grams of glycine are put into the beaker of 1000ml simultaneously, and
100ml deionized water is added, is stirred to and is completely dissolved to form mixed solution, the beaker for filling above-mentioned mixed solution is put into Muffle
It in furnace, is heated 4 minutes at 170 DEG C, keeps coming into full contact with air in heating process, while being sufficiently stirred；
Step 2: it is 0.2g/mL glucose solution that glucose addition ionized water, which is configured to concentration, and step 1 heating terminates
The glucose solution of 20mL is added in solution afterwards, and is stirred and to form mixed solution, by mixed solution be put into 250 degree plus
It is heated 10 minutes in hot stove, fluffy solid is obtained after heating；
Step 3: the fluffy solid that step 2 is obtained is put into tube furnace, in the flowing hydrogen that hydrogen flowing quantity is 150mL/min
Under gas, 450 DEG C of hydrocarbon reductase 12 hours, flowing hydrogen state is still kept the temperature after hydrocarbon reduction, is cooled to room temperature to furnace temperature by powder
End is taken out, and molybdenum carbide nanometer sheet is obtained.It is irregular sheet, lamellar spacing size is about through scanning electron microscope test
20nm。
Embodiment 3
Step 1: 23.6 grams of ammonium dimolybdates, 22 grams of ammonium nitrate, 13 grams of glycine are put into the beaker of 1000ml simultaneously, and
100ml deionized water is added, is stirred to and is completely dissolved to form mixed solution, the beaker for filling above-mentioned mixed solution is put into Muffle
It in furnace, is heated 5 minutes at 165 DEG C, keeps coming into full contact with air in heating process, while being sufficiently stirred；
Step 2: it is 0.2g/mL glucose solution that glucose addition ionized water, which is configured to concentration, and step 1 heating terminates
The glucose solution of 20mL is added in solution afterwards, and is stirred and to form mixed solution, by mixed solution be put into 230 degree plus
It is heated 15 minutes in hot stove, fluffy solid is obtained after heating；
Step 3: the fluffy solid that step 2 is obtained is put into tube furnace, in the flowing hydrogen that hydrogen flowing quantity is 150mL/min
Under gas, 550 DEG C it is hydrocarbon reduction 1 hour, flowing hydrogen state is still kept the temperature after hydrocarbon reduction, is cooled to room temperature to furnace temperature by powder
End is taken out, and molybdenum carbide nanometer sheet is obtained.It is irregular sheet, lamellar spacing size is about through scanning electron microscope test
25nm。
Embodiment 4
Step 1: 19.3 grams of ammonium paramolybdates, 20 grams of ammonium nitrate, 25 grams of glycine are put into the beaker of 1000ml simultaneously, and
100ml deionized water is added, is stirred to and is completely dissolved to form mixed solution, the beaker for filling above-mentioned mixed solution is put into Muffle
It in furnace, is heated 3 minutes at 180 DEG C, keeps coming into full contact with air in heating process, while being sufficiently stirred；
Step 2: it is 0.2g/mL glucose solution that glucose addition ionized water, which is configured to concentration, and step 1 heating terminates
The glucose solution of 23mL is added in solution afterwards, and is stirred and to form mixed solution, by mixed solution be put into 240 degree plus
It is heated 10 minutes in hot stove, fluffy solid is obtained after heating；
Step 3: the fluffy solid that step 2 is obtained is put into tube furnace, in the flowing hydrogen that hydrogen flowing quantity is 500mL/min
Under gas, 460 DEG C it is hydrocarbon reduction 3 hours, flowing hydrogen state is still kept the temperature after hydrocarbon reduction, is cooled to room temperature to furnace temperature by powder
End is taken out, and molybdenum carbide nanometer sheet is obtained.
Embodiment 5
Step 1: 26.3 grams of ammonium paramolybdates, 20 grams of ammonium nitrate, 6.3 grams of glycine are put into the beaker of 1000ml simultaneously,
And 100ml deionized water is added, it is stirred to and is completely dissolved to form mixed solution, the beaker for filling above-mentioned mixed solution is put into horse
It not in furnace, is heated 6 minutes at 170 DEG C, keeps coming into full contact with air in heating process, while being sufficiently stirred；
Step 2: it is 0.2g/mL glucose solution that glucose addition ionized water, which is configured to concentration, and step 1 heating terminates
The glucose solution of 26mL is added in solution afterwards, and is stirred and to form mixed solution, by mixed solution be put into 270 degree plus
It is heated 10 minutes in hot stove, fluffy solid is obtained after heating；
Step 3: the fluffy solid that step 2 is obtained is put into tube furnace, in the flowing hydrogen that hydrogen flowing quantity is 100mL/min
Under gas, 500 DEG C it is hydrocarbon reduction 1 hour, flowing hydrogen state is still kept the temperature after hydrocarbon reduction, is cooled to room temperature to furnace temperature by powder
End is taken out, and molybdenum carbide nanometer sheet is obtained.
Comparative example 1
Step 1: 18.5 grams of ammonium paramolybdates being put into the beaker of 1000ml, and 100ml deionized water is added, have been stirred to
Fully dissolved forms solution, and the beaker for filling above-mentioned solution is put into Muffle furnace, heats 5 minutes at 160 DEG C, protects in heating process
It holds and is come into full contact with air, while being sufficiently stirred；
Step 2: it is 0.2g/mL glucose solution that glucose addition ionized water, which is configured to concentration, and step 1 heating terminates
The glucose solution of 30mL is added in solution afterwards, and is stirred and to form mixed solution, by mixed solution be put into 240 degree plus
It is heated 12 minutes in hot stove, what is obtained after heating is compact solid rather than fluffy state powder；
Step 3: the compact solid that step 2 is obtained is put into tube furnace, in the flowing hydrogen that hydrogen flowing quantity is 200mL/min
Under gas, 500 DEG C it is hydrocarbon reduction 1.5 hours, flowing hydrogen state is still kept the temperature after hydrocarbon reduction, to furnace temperature be cooled to room temperature by
Powder takes out, and obtains comparative sample 1.
XRD test and Electronic Speculum test, knot are carried out respectively to comparative sample made from compact solid obtained in step 2, step 3
Fruit sees Fig. 5~Fig. 7.
As can be seen from Figure 5, compact solid still forms the diffraction maximum of apparent unformed shape, but occurs molybdenum oxide (two simultaneously
Molybdenum oxide, molybdenum trioxide) diffraction maximum, show that molybdenum oxide has become crystalline state phase, amorphous molybdenum oxide can not be formed, this will
Cause to can not be successfully synthesis molybdenum carbide in subsequent hydrocarbon reduction step.
Fig. 6 is the XRD diffraction spectra of comparative sample 1 made from step 3, as can be seen from Figure 6, comparative sample 1 by main phase molybdenum dioxide and
A small amount of molybdenum carbide composition, shows successfully synthesize molybdenum carbide phase.Fig. 7 is the electron scanning micrograph for comparing sample 1, can be with
See that its pattern is large-size particle shape, nano-sheet appearance structure can not be formed.
Comparative example 2
Step 1: 18.5 grams of ammonium paramolybdates, 20 grams of ammonium nitrate, 12 grams of glycine are put into the beaker of 1000ml simultaneously, and
100ml deionized water is added, is stirred to and is completely dissolved to form mixed solution, the beaker for filling above-mentioned mixed solution is put into Muffle
It in furnace, is heated 5 minutes at 160 DEG C, keeps coming into full contact with air in heating process, while being sufficiently stirred；
Step 2: in the solution after it is 0.2g/mL citric acid solution that citric acid, which is configured to concentration, and step 1 heats
The citric acid solution of 30mL is added, and is stirred and to form mixed solution, mixed solution is put into 240 degree of heating furnace and is heated
12 minutes, more fluffy solid powder is obtained after heating；
Step 3: the relatively fluffy solid powder that step 2 obtains being put into tube furnace, is 200mL/min's in hydrogen flowing quantity
Under flowing hydrogen, 500 DEG C it is hydrocarbon reduction 1.5 hours, flowing hydrogen state is still kept the temperature after hydrocarbon reduction, is down to room to furnace temperature
Powder is taken out after temperature, obtains comparative sample 2.
XRD test and Electronic Speculum test, knot are carried out respectively to comparative sample made from compact solid obtained in step 2, step 3
Fruit sees Fig. 8~Figure 11.
As it can be observed in the picture that fluffy solid powder forms the diffraction maximum of apparent unformed shape, show fluffy solid by amorphous state
Material composition, consisting of the mixture of amorphous molybdenum oxide and armorphous nano carbon plate.Fig. 9 is compared with fluffy solid powder
Electron scanning micrograph is as can be seen from Figure 9 porous laminated structure compared with fluffy solid powder, about 2~4 microns of thickness, can not
Flaky nanometer structure is formed, this has significant difference with Fig. 2.
Figure 10 is the XRD diffraction spectra for comparing sample 2, and as can be seen from Figure 10, comparative sample 2 is by main phase molybdenum carbide and time phase molybdenum dioxide
Composition, showing can not complete synthesis molybdenum carbide phase.Figure 11 is the electron scanning micrograph for comparing sample 2, as can be seen from Figure 11, right
The pattern before hydrocarbon reduction, i.e. porous laminated structure are still kept than sample 2, flaky nanometer structure can not be formed, this has obviously with Fig. 4
Difference.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (10)
1. a kind of preparation method of molybdenum carbide nanometer sheet, it is characterised in that: the following steps are included:
Step 1: molybdenum source, ammonium nitrate, glycine being uniformly mixed, are heated to 160~180 DEG C later, obtains mixture 1；
Step 2: glucose is added into the mixture 1 that step 1 obtains, is heated to 230~280 DEG C later, obtains fluffy solid；
Step 3: the fluffy solid that step 2 is obtained, which is put under atmosphere of hydrogen, is heated to 450~550 DEG C, and cooling obtains molybdenum carbide
Nanometer sheet.
2. the preparation method of molybdenum carbide nanometer sheet according to claim 1, it is characterised in that: molybdenum source described in step 1 is
At least one of ammonium paramolybdate, ammonium tetramolybdate or ammonium dimolybdate；
It is optional, in molybdenum source described in step 1 molybdenum mole amount: (ammonium nitrate mole amount+glycine mole
Amount)=0.5~1.0:2.2~3.2；
Optional, the quality of ammonium nitrate described in step 1: quality=0.8~3.2 of the glycine.
3. the preparation method of molybdenum carbide nanometer sheet according to claim 2, it is characterised in that: step 1 includes: 1a by molybdenum
Deionized water, stirring to dissolution are added after source, ammonium nitrate, glycine mixing；1b heated solution is to 165~175 DEG C, heat preservation 3~6
Minute, obtain mixture 1.
4. the preparation method of molybdenum carbide nanometer sheet according to claim 1, it is characterised in that: glucose described in step 2
Mass ratio with the molybdenum in the molybdenum source is 0.8~1.0:1.6~2.8；
Optional, it is 0.1~0.3g/mL glucose solution that glucose, which is configured to concentration, in step 2, and what is obtained to step 1 is mixed
Close the glucose solution that 10~50mL is added in object 1.
5. the preparation method of molybdenum carbide nanometer sheet according to claim 1, it is characterised in that: heating described in step 2
Temperature is 240~270 DEG C, and soaking time is 10~20 minutes.
6. the preparation method of molybdenum carbide nanometer sheet according to claim 1, it is characterised in that: nitrogen atmosphere described in step 3
Enclose middle H2Flow be 100~500mL/min.
7. the preparation method of molybdenum carbide nanometer sheet according to claim 1, it is characterised in that: heating described in step 3
Temperature is 460~500 DEG C, and soaking time is 1~3 hour.
8. with the preparation method of the described in any item molybdenum carbide nanometer sheets of claim 1~7, the molybdenum carbide nanometer being prepared
Piece.
9. molybdenum carbide nanometer sheet according to claim 8, it is characterised in that: the molybdenum carbide nanometer sheet has crystalline state knot
Structure is in irregular sheet, with a thickness of 10~30nm.
10. application of the molybdenum carbide nanometer sheet in electro-catalysis hydrogen manufacturing described in claim 8 or 9.
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| CN110422846A (en) * | 2019-08-13 | 2019-11-08 | 哈尔滨工业大学 | A kind of synthetic method of molybdenum carbide nano material |
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| CN111495402B (en) * | 2020-04-20 | 2023-03-24 | 嘉兴学院 | Molybdenum-based composite material prepared by microwave spark and preparation method and application thereof |
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| CN111646504B (en) * | 2020-05-29 | 2022-08-12 | 厦门理工学院 | Nano lanthanum zirconate and preparation method thereof |
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