CN105948052B - A kind of flake nano carbonization tungsten and its preparation and application - Google Patents
A kind of flake nano carbonization tungsten and its preparation and application Download PDFInfo
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- CN105948052B CN105948052B CN201610395526.3A CN201610395526A CN105948052B CN 105948052 B CN105948052 B CN 105948052B CN 201610395526 A CN201610395526 A CN 201610395526A CN 105948052 B CN105948052 B CN 105948052B
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- 238000003763 carbonization Methods 0.000 title claims description 34
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims description 21
- 229910052721 tungsten Inorganic materials 0.000 title claims description 19
- 239000010937 tungsten Substances 0.000 title claims description 19
- 238000002360 preparation method Methods 0.000 title abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 21
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 13
- 235000012501 ammonium carbonate Nutrition 0.000 claims abstract description 13
- 235000019441 ethanol Nutrition 0.000 claims abstract description 13
- 239000004094 surface-active agent Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims abstract description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 4
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 23
- 239000002243 precursor Substances 0.000 claims description 14
- 238000006722 reduction reaction Methods 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 239000010935 stainless steel Substances 0.000 claims description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims description 10
- 239000006228 supernatant Substances 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 claims description 2
- 150000002828 nitro derivatives Chemical class 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 49
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 9
- 238000006555 catalytic reaction Methods 0.000 abstract description 8
- 239000002086 nanomaterial Substances 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 239000000969 carrier Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 13
- 239000002135 nanosheet Substances 0.000 description 11
- 230000009467 reduction Effects 0.000 description 11
- 239000007789 gas Substances 0.000 description 9
- 239000008246 gaseous mixture Substances 0.000 description 9
- PRKQVKDSMLBJBJ-UHFFFAOYSA-N ammonium carbonate Chemical class N.N.OC(O)=O PRKQVKDSMLBJBJ-UHFFFAOYSA-N 0.000 description 8
- 235000011162 ammonium carbonates Nutrition 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- 239000003643 water by type Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- -1 aromatic nitro compound Chemical class 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical group Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012956 testing procedure Methods 0.000 description 1
- 230000001225 therapeutic effect Effects 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
-
- B01J35/40—
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- 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
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
Abstract
The invention discloses a kind of nanometer tungsten carbide and its preparation and application, the preparation method is specific as follows：(1) aqueous solution of ammonium metatungstate and ammonium carbonate is added in the solution made of ethyl alcohol and surfactant, is stirring evenly and then adding into hydroxylamine hydrochloride, be stirring evenly and then adding into HCl or ammonium hydroxide adjusts pH value to 4~8；(2) mixed liquor is subjected to hydro-thermal reaction, sample presoma is obtained after dry；(3) sample presoma is in CH4/H2Atmosphere high temperature is carbonized, and obtains flake nano WC materials.The preparation of flake nano WC, on the one hand effectively prevents the reunion of nanometer WC, so as to give full play to the effective ratio area of nano material；On the other hand, the advantage of nano lamellar material can be made full use of, it is possible to provide a large amount of surface atom and more chain carriers are conducive in catalytic reaction process that load is rapidly from internal transmission to surface, to improve nano material catalytic activity.
Description
(1) technical field
The present invention relates to a kind of tungsten carbide, more particularly to a kind of flake nano carbonization tungsten and its preparation and application.
(2) background technology
Tungsten carbide (WC) is because having many advantages, such as that eka-platinium catalytic activity, high rigidity, high thermal stability and wear-resisting property are good, hard
The fields such as matter alloy, catalysis are widely used.WC is not only shown as catalyst pair plus hydrogen, dehydrogenation reaction have it is good
Good catalytic activity, and to the also selective catalytic action of certain reactions.Further study show that WC also has well
Electric conductivity and very strong acid resistance, these features make WC be expected to become ideal electrocatalysis material be applied to electrochemistry neck
Domain.Have studies have shown that WC is shown in the fields such as methanol direct oxidation, hydrogen anodic oxidation and aromatic nitro compound electroreduction
Go out certain electro catalytic activity, but catalytic activity is not high, there is also larger gaps from practical application, therefore, prepare high activity W C
Material is researcher critical issue urgently to be resolved hurrily.
The structure of catalyst has a great impact to its catalytic performance.Some researches show that the nanometer sheet of two-dimensional structure can carry
It is a kind of ideal catalyst structure for a large amount of surface atom and more chain carriers.The ultra-thin geometry of nanometer sheet
Feature is conducive in catalytic reaction process that load is rapidly from internal transmission to surface, to accelerate reaction process.Early in about
Before 50 years, there is researcher to prepare and synthesized two dimensional surface plate-like gold nanoparticle.Due to the nano-particle of this pattern
With special surface plasma resonance performance, show and completely different optical of spheroidal particle and body phase material
Matter.Thus recent years, again by the further concern of people, they will be in surface-enhanced Raman for the research of two-dimension nano materials
Fields such as spectrum, metal-enhanced fluorescence spectrum, catalysis, infrared therapeutic and in photon, photoelectron, optical sensor and biology
The fields such as label have great potential using value.Currently, some research groups have synthesized shape with liquid-phase synthesis process
The monocrystalline gold micron film of looks rule and near infrared absorption characteristic [Chem.Mater.2005, (17) for having studied it:566.],
Later, researcher introduced cetyl trimethylammonium bromide, and passed through the tune to growth course by the improvement to experiment condition
Control has reached the control to nano-particle pattern, obtains other shapes of gold nano-plates by restoring gold chloride, and improve
The monodispersity of nano-particle and catalytic performance [Langmuir, 2005 (21):4710].Therefore, the present invention by hydro-thermal from group
Dress synthesis is combined with in-situ reducing carbonization technology, is prepared for nano-sheet WC, on the one hand the preparation of nano-sheet WC is effectively kept away
The reunion for having exempted from nanometer WC, so as to wave the effective ratio area of nano material from distribution；On the other hand, it can make full use of
The advantage of nano lamellar material, it is possible to provide a large amount of surface atom and more chain carriers are conducive to catalysis and reacted
Load is rapidly from internal transmission to surface in journey, to improve nano material catalytic activity.
(3) invention content
The first invention purpose of the present invention is to provide a kind of nano-sheet WC materials of high dispersive, and nano-sheet WC can be made to protect
It is fixed to keep steady, and secondary agglomeration does not occur.
Second object of the present invention is to provide the nano-sheet WC materials as elctro-catalyst in electro-catalysis nitration
Close the application in object reduction reaction.
The technical solution adopted by the present invention is：
The present invention provides a kind of flake nano carbonization tungsten, and the flake nano carbonization tungsten is prepared as follows：
(1) at room temperature, ammonium metatungstate and ammonium carbonate are configured to presoma culture solution with deionized water, presoma is trained
Nutrient solution is added in the solution of surfactant and ethyl alcohol, is stirring evenly and then adding into hydroxylamine hydrochloride, is stirred evenly, and is adjusted pH value and is arrived
4~8, obtain precursor solution；The ammonium metatungstate is 1 with ammonium carbonate mass ratio:0.5~2, the surfactant and inclined tungsten
Sour ammonium mass ratio is 0.01~0.05：1, the hydroxylamine hydrochloride is 0.04~0.1 with ammonium metatungstate mass ratio：1；
(2) precursor solution for obtaining step (1) carries out hydro-thermal reaction 10~for 24 hours at 150~250 DEG C, stands to room
Temperature discards supernatant liquid, sample presoma is obtained after dry；
(3) the sample presoma for obtaining step (2) is in CH4And H2In atmosphere, be carbonized in 600~900 DEG C to get
To flake nano carbonization tungsten.
Further, step (1) described surfactant is neopelex or cetyl trimethylammonium bromide.
Further, the mass ratio of step (1) ammonium metatungstate and ammonium carbonate is 1:0.8~1.5, the surfactant
It is 0.03~0.05 with ammonium metatungstate mass ratio：1, the hydroxylamine hydrochloride is 0.04~0.06 with ammonium metatungstate mass ratio：1.
Further, step (1) the deionized water volumetric usage is calculated as 2~200mL/g, preferably 2 with ammonium metatungstate quality
~50mL/g, the ethyl alcohol are 0.3~0.5 with deionized water volume ratio:1, preferably 0.4~0.5:1.
Further, step (1) hydrochloric acid or ammonium hydroxide adjust pH value to 5~6.
Further, step (2) precursor solution is transferred in the stainless steel autoclave of polytetrafluoroethyllining lining, seals high pressure
Kettle carries out hydro-thermal reaction.
Further, step (2) hydrothermal temperature is 150~200 DEG C, and the hydro-thermal reaction time is 10~16h.
Further, step (3) CH4And H2Volume ratio be 1:0.2~1.5, preferably 1:0.8~1.5.
Further, step (3) carbonization method is：Sample presoma is placed in tube furnace, with 1~5 DEG C/min's
Heating rate from room temperature be increased to 600~900 DEG C carbonization 1~10h (heating rate of more preferable 2~3 DEG C/min from room temperature increase
To 750~900 DEG C of 5~7h of carbonization), after the completion of heating reaction, lead to N2It is cooled to room temperature to get flake nano carbonization tungsten.
The present invention also provides a kind of flake nano carbonization tungsten as elctro-catalyst in nitro compound electro-reduction reaction
Middle application.
The method of the present invention is prepared for flake nano WC using surface active agent assisting alcohol-hydrothermal method, than existing method directly with inclined
Ammonium tungstate prepares WC with the high advantage of large specific surface area, catalytic activity.
Compared with prior art, advantageous effect of the present invention is mainly reflected in：Flake nano prepared by the method for the invention
Tungsten carbide nanometer sheet is well dispersed, nanometer sheet 3~15nm of thickness, on the one hand the method for the present invention effectively prevents the reunion of nanometer WC,
So as to give full play to the effective ratio area of nano material；On the other hand, the excellent of nano lamellar material can be made full use of
Gesture, it is possible to provide a large amount of surface atom and more chain carriers are conducive in catalytic reaction process load rapidly
From internal transmission to surface, to improve nano material catalytic activity.
(4) it illustrates
Fig. 1 is the SEM figures that 2 nano-sheet WC of embodiment amplifies 10000 times.
Fig. 2 is the SEM figures that 2 nano-sheet WC of embodiment amplifies 60000 times.
Fig. 3 is that embodiment 8 (comparative example 1) obtains sample SEM figures.
Fig. 4 is the cyclic voltammetry curve of the electro-catalysis nitrobenzene reduction of 8 sample of 2 sample of embodiment and embodiment, wherein (a)
It is (b) cyclic voltammetry curve of 8 sample of embodiment for the cyclic voltammetry curve of 2 sample of embodiment.
(5) specific implementation mode
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This：
Embodiment 1
At room temperature, 2mL deionized waters are added in 1g ammonium metatungstates and 0.5g ammonium carbonates and are configured to ammonium metatungstate and carbonic acid
Presoma culture solution is added to made of 0.6mL ethyl alcohol and 0.01g neopelexes by the presoma culture solution of ammonium
In solution, 0.04g hydroxylamine hydrochlorides are stirring evenly and then adding into, HCl is stirring evenly and then adding into and adjusts pH value to 4, it is molten to obtain presoma
Liquid；Above-mentioned precursor solution is transferred in the stainless steel autoclave of polytetrafluoroethyllining lining again, sealing autoclave, by it in number
It maintains 150 DEG C of reaction 10h, reaction solution to stand to room temperature in word perseverance temperature control box, discards supernatant liquid, sample is obtained after 40 DEG C of vacuum drying
Sample presoma is placed in tube furnace by product presoma, with volume ratio for 1:1 CH4、H2Gaseous mixture is reduction and carbonization gas, with
The heating rate of 5 DEG C/min is increased to 900 DEG C of carbonization 5h from room temperature and leads to N after the completion of heating reaction2Be cooled to room temperature to get to
Flake nano WC.WC nanometer sheets are well dispersed, 12~15nm of nanometer sheet thickness.
Embodiment 2
At room temperature, 20mL deionized waters are added in 1g ammonium metatungstates and 1g ammonium carbonates and are configured to ammonium metatungstate and ammonium carbonate
Presoma culture solution, presoma culture solution is added to the solution made of 8mL ethyl alcohol and 0.04g neopelexes
In, 0.05g hydroxylamine hydrochlorides are stirring evenly and then adding into, HCl is stirring evenly and then adding into and adjusts pH value to 5.6, obtain precursor solution；
Above-mentioned precursor solution is transferred in the stainless steel autoclave of polytetrafluoroethyllining lining again, sealing autoclave, by it in number
It maintains 180 DEG C of reaction 12h, reaction solution to stand to room temperature in permanent temperature control box, discards supernatant liquid, sample is obtained after 40 DEG C of vacuum drying
Sample presoma is placed in tube furnace by presoma, with volume ratio for 1:1 CH4、H2Gaseous mixture is reduction and carbonization gas, with 5
DEG C/heating rate of min is increased to 900 DEG C of carbonization 5h from room temperature and leads to N after the completion of heating reaction2Be cooled to room temperature to get to
Flake nano WC.Its pattern such as Fig. 1 and Fig. 2.Scanning electron microscope (SEM) photograph shows that WC nanometer sheets are well dispersed, 5~8nm of nanometer sheet thickness.
Embodiment 3
At room temperature, 200mL deionized waters are added in 1g ammonium metatungstates and 2g ammonium carbonates and are configured to ammonium metatungstate and carbonic acid
Presoma culture solution is added to made of 100mL ethyl alcohol and 0.05g neopelexes by the presoma culture solution of ammonium
In solution, 0.1g hydroxylamine hydrochlorides are stirring evenly and then adding into, ammonium hydroxide is stirring evenly and then adding into and adjusts pH value to 8, it is molten to obtain presoma
Liquid；Above-mentioned precursor solution is transferred in the stainless steel autoclave of polytetrafluoroethyllining lining again, sealing autoclave, by it in number
250 DEG C of reactions are maintained in word perseverance temperature control box for 24 hours, reaction solution is stood to room temperature, discards supernatant liquid, sample is obtained after 40 DEG C of vacuum drying
Sample presoma is placed in tube furnace by product presoma, with volume ratio for 1:1 CH4、H2Gaseous mixture is reduction and carbonization gas, with
The heating rate of 5 DEG C/min is increased to 900 DEG C of carbonization 5h from room temperature and leads to N after the completion of heating reaction2Be cooled to room temperature to get to
Flake nano WC.SEM figures show that WC nanometer sheets are well dispersed, nanometer sheet thickness 12nm or so.
Embodiment 4
At room temperature, 20mL deionized waters are added in 1g ammonium metatungstates and 1g ammonium carbonates and are configured to ammonium metatungstate and ammonium carbonate
Presoma culture solution, presoma culture solution is added to made of 8mL ethyl alcohol and 0.04g cetyl trimethylammonium bromides
In solution, 0.05g hydroxylamine hydrochlorides are stirring evenly and then adding into, HCl is stirring evenly and then adding into and adjusts pH value to 5.6, obtain presoma
Solution；Above-mentioned precursor solution is transferred in the stainless steel autoclave of polytetrafluoroethyllining lining again, sealing autoclave, by its
It maintains 180 DEG C of reaction 12h, reaction solution to stand to room temperature in digital perseverance temperature control box, discards supernatant liquid, obtained after 40 DEG C of vacuum drying
Sample presoma is placed in tube furnace by sample presoma, with volume ratio for 1:0.2 CH4、H2Gaseous mixture is reduction and carbonization gas
Body is increased to 600 DEG C of carbonization 4h from room temperature with the heating rate of 1 DEG C/min and leads to N after the completion of heating reaction2It is cooled to room temperature,
Obtain flake nano WC.SEM figures show that WC nanometer sheets are well dispersed, nanometer sheet thickness 10nm or so.
Embodiment 5
At room temperature, 20mL deionized waters are added in 1g ammonium metatungstates and 1g ammonium carbonates and are configured to ammonium metatungstate and ammonium carbonate
Presoma culture solution, presoma culture solution is added to made of 8mL ethyl alcohol and 0.04g cetyl trimethylammonium bromides
In solution, 0.05g hydroxylamine hydrochlorides are stirring evenly and then adding into, HCl is stirring evenly and then adding into and adjusts pH value to 5.8, obtain presoma
Solution；Above-mentioned precursor solution is transferred in the stainless steel autoclave of polytetrafluoroethyllining lining again, sealing autoclave, by its
It maintains 180 DEG C of reaction 12h, reaction solution to stand to room temperature in digital perseverance temperature control box, discards supernatant liquid, obtained after 40 DEG C of vacuum drying
Sample presoma is placed in tube furnace by sample presoma, with volume ratio for 1:0.5 CH4、H2Gaseous mixture is reduction and carbonization gas
Body is increased to 750 DEG C of carbonization 6h from room temperature with the heating rate of 2.5 DEG C/min and leads to N after the completion of heating reaction2It is cooled to room
Temperature is to get to flake nano WC.SEM figures show that WC nanometer sheets are well dispersed, 5~10nm of nanometer sheet thickness.
Embodiment 6
At room temperature, 20mL deionized waters are added in 1g ammonium metatungstates and 1g ammonium carbonates and are configured to ammonium metatungstate and ammonium carbonate
Presoma culture solution, presoma culture solution is added to made of 8mL ethyl alcohol and 0.04g cetyl trimethylammonium bromides
In solution, 0.05g hydroxylamine hydrochlorides are stirring evenly and then adding into, HCl is stirring evenly and then adding into and adjusts pH value to 6, it is molten to obtain presoma
Liquid；Above-mentioned precursor solution is transferred in the stainless steel autoclave of polytetrafluoroethyllining lining again, sealing autoclave, by it in number
It maintains 180 DEG C of reaction 12h, reaction solution to stand to room temperature in word perseverance temperature control box, discards supernatant liquid, sample is obtained after 40 DEG C of vacuum drying
Sample presoma is placed in tube furnace by product presoma, with volume ratio for 1:1 CH4、H2Gaseous mixture is reduction and carbonization gas, with
The heating rate of 2.5 DEG C/min is increased to 800 DEG C of carbonization 6h from room temperature and leads to N after the completion of heating reaction2Be cooled to room temperature to get
To flake nano WC.SEM figures show that WC nanometer sheets are well dispersed, 3~6nm of nanometer sheet thickness.
Embodiment 7
At room temperature, 20mL deionized waters are added in 1g ammonium metatungstates and 1g ammonium carbonates and are configured to ammonium metatungstate and ammonium carbonate
Presoma culture solution, presoma culture solution is added to made of 8mL ethyl alcohol and 0.04g cetyl trimethylammonium bromides
In solution, 0.05g hydroxylamine hydrochlorides are stirring evenly and then adding into, HCl is stirring evenly and then adding into and adjusts pH value to 6, it is molten to obtain presoma
Liquid；Above-mentioned precursor solution is transferred in the stainless steel autoclave of polytetrafluoroethyllining lining again, sealing autoclave, by it in number
It maintains 180 DEG C of reaction 12h, reaction solution to stand to room temperature in word perseverance temperature control box, discards supernatant liquid, sample is obtained after 40 DEG C of vacuum drying
Sample presoma is placed in tube furnace by product presoma, with volume ratio for 1:1 CH4、H2Gaseous mixture is reduction and carbonization gas, with
The heating rate of 5 DEG C/min is increased to 900 DEG C of carbonization 10h from room temperature and leads to N after the completion of heating reaction2Be cooled to room temperature to get
To flake nano WC.SEM figures show that WC nanometer sheets are well dispersed, 12~15nm of nanometer sheet thickness.
Embodiment 8：Comparative example 1 (is not added with surfactant)
At room temperature, 20mL deionized waters are added in 1g ammonium metatungstates and 1g ammonium carbonates and are configured to ammonium metatungstate and ammonium carbonate
Presoma culture solution, presoma culture solution is added in 8mL ethyl alcohol, 0.05g hydroxylamine hydrochlorides are stirring evenly and then adding into, stir
HCl is added after uniformly and adjusts pH value to 6；Above-mentioned mixed solution is transferred to the stainless steel autoclave of polytetrafluoroethyllining lining again
In, it is maintained 180 DEG C of reaction 12h, reaction solution to stand to room temperature, discard supernatant by sealing autoclave in digital permanent temperature control box
Liquid obtains sample presoma after 40 DEG C of vacuum drying, sample presoma is placed in tube furnace, with volume ratio for 1:1 CH4、H2
Gaseous mixture is reduction and carbonization gas, is increased to 800 DEG C of carbonization 6h from room temperature with the heating rate of 2.5 DEG C/min, heating has been reacted
Cheng Hou leads to N2It is cooled to room temperature, gained WC particle is bulk, and thickness is greatly to 600nm, and WC particle is reunited more serious, SEM
Figure is shown in Fig. 3.
Embodiment 9：Ammonium metatungstate presoma (is not carried out any processing) by comparative example 2
At room temperature, ammonium metatungstate is placed in tube furnace, with volume ratio for 1:1 CH4、H2Gaseous mixture is reduction and carbonization
Gas is increased to 800 DEG C of carbonization 6h from room temperature with the heating rate of 2.5 DEG C/min and leads to N after the completion of heating reaction2It is cooled to room
Temperature, SEM figures show that gained WC particle is bulk, and thickness is greatly to 2~3 microns, and WC particle reunion is more serious.
Embodiment 10：Using
Flake nano WC made from embodiment 2 is prepared into powder microelectrode, using cyclic voltammetry to nano-sheet WC
Powder microelectrode carries out electroreduction catalytic activity test, as a result sees a curves in Fig. 4.Instrument is CHI660C electrochemical analysis
Instrument, experiment use three electrode test systems, electrolyte 0.5molL-1NaOH+0.01mol·L-1P-nitrophenol, reference
Electrode is saturated calomel electrode, and auxiliary electrode is large area light platinum electrode.Experimental temperature is 25 DEG C, sweep speed 50mV/
s。
Embodiment 11：Comparative example 3
The blocky WC that embodiment 8 obtains is prepared into powder microelectrode, repeats the testing procedure described in embodiment 10, as a result
See b curves in Fig. 4.
From fig. 4, it can be seen that reduction peak current of the p-nitrophenol on nano-sheet WC powder microelectrode is apparently higher than
Blocky WC powder microelectrode.This illustrates that nano-sheet WC catalytic performances made from embodiment 2 are apparently higher than block made from embodiment 8
Shape WC.Reactivity area increases caused by the high degree of dispersion and very thin flaky nanometer structure that its main cause is nano-sheet WC
The promotion of unit catalytic activity caused by big and generated nanometer size effect.
Claims (9)
- The tungsten 1. a kind of flake nano is carbonized, it is characterised in that the flake nano carbonization tungsten is prepared as follows：(1) at room temperature, ammonium metatungstate and ammonium carbonate are configured to presoma culture solution with deionized water, by presoma culture solution It is added in the solution of surfactant and ethyl alcohol, is stirring evenly and then adding into hydroxylamine hydrochloride, stir evenly, adjusting pH value to 4~ 8, obtain precursor solution；The surfactant is neopelex or cetyl trimethylammonium bromide；It is described Ammonium metatungstate is 1 with ammonium carbonate mass ratio:0.5~2, the surfactant is 0.01~0.05 with ammonium metatungstate mass ratio： 1, the hydroxylamine hydrochloride is 0.04~0.1 with ammonium metatungstate mass ratio：1；(2) precursor solution for obtaining step (1) carries out hydro-thermal reaction 10~for 24 hours at 150~250 DEG C, stands to room temperature, abandons Supernatant is removed, sample presoma is obtained after dry；(3) the sample presoma for obtaining step (2) is in CH4And H2In atmosphere, it is carbonized in 600~900 DEG C to get to piece Shape nanometer tungsten carbide.
- The tungsten 2. flake nano as described in claim 1 is carbonized, it is characterised in that the matter of step (1) ammonium metatungstate and ammonium carbonate Amount is than being 1:0.8~1.5, the surfactant is 0.03~0.05 with ammonium metatungstate mass ratio:1, the hydroxylamine hydrochloride with Ammonium metatungstate mass ratio is 0.04~0.06:1.
- The tungsten 3. flake nano as described in claim 1 is carbonized, it is characterised in that step (1) the deionized water volumetric usage is with inclined Ammonium tungstate quality is calculated as 2~200mL/g, and the ethyl alcohol is 0.3~0.5 with deionized water volume ratio:1.
- The tungsten 4. flake nano as described in claim 1 is carbonized, it is characterised in that step (1) hydrochloric acid or ammonium hydroxide adjust pH value to 5 ~6.
- The tungsten 5. flake nano as described in claim 1 is carbonized, it is characterised in that step (2) precursor solution is transferred to polytetrafluoroethyl-ne In the stainless steel autoclave of alkene liner, sealing autoclave carries out hydro-thermal reaction.
- The tungsten 6. flake nano as described in claim 1 is carbonized, it is characterised in that hydrothermal temperature is 150~200 DEG C, and hydro-thermal is anti- It is 10~16h between seasonable.
- The tungsten 7. flake nano as described in claim 1 is carbonized, it is characterised in that step (3) described CH4And H2Volume ratio be 1: 0.2~1.5.
- The tungsten 8. flake nano as described in claim 1 is carbonized, it is characterised in that step (3) carbonization method is：Before sample It drives body to be placed in tube furnace, 600~900 DEG C of 1~10h of carbonization, heating is increased to from room temperature with the heating rate of 1~5 DEG C/min After the completion of reaction, lead to N2It is cooled to room temperature to get nanometer tungsten carbide.
- 9. flake nano carbonization tungsten described in a kind of claim 1 is answered as elctro-catalyst in nitro compound electro-reduction reaction With.
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