CN105948052A - Flaky nano tungsten carbide and preparation method and application thereof - Google Patents
Flaky nano tungsten carbide and preparation method and application thereof Download PDFInfo
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- CN105948052A CN105948052A CN201610395526.3A CN201610395526A CN105948052A CN 105948052 A CN105948052 A CN 105948052A CN 201610395526 A CN201610395526 A CN 201610395526A CN 105948052 A CN105948052 A CN 105948052A
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- flake nano
- presoma
- ammonium metatungstate
- room temperature
- ammonium
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- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000003763 carbonization Methods 0.000 claims abstract description 44
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 23
- 235000012501 ammonium carbonate Nutrition 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 22
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000004094 surface-active agent Substances 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 20
- 239000012531 culture fluid Substances 0.000 claims description 19
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 18
- 229910052721 tungsten Inorganic materials 0.000 claims description 18
- 239000010937 tungsten Substances 0.000 claims description 18
- 238000006722 reduction reaction Methods 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000006228 supernatant Substances 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- -1 Sodium alkyl benzene Chemical class 0.000 claims description 2
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 claims description 2
- 150000002828 nitro derivatives Chemical class 0.000 claims description 2
- 230000004044 response Effects 0.000 claims description 2
- 229940077388 benzenesulfonate Drugs 0.000 claims 1
- 235000015097 nutrients Nutrition 0.000 claims 1
- 239000000047 product Substances 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 8
- 239000002086 nanomaterial Substances 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 239000000908 ammonium hydroxide Substances 0.000 abstract 1
- 239000000969 carrier Substances 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 26
- 230000009467 reduction Effects 0.000 description 12
- 239000002135 nanosheet Substances 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000008246 gaseous mixture Substances 0.000 description 9
- 239000000376 reactant Substances 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 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
- 229910052697 platinum Inorganic materials 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000000090 biomarker Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical group Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 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
- 238000005984 hydrogenation reaction Methods 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
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- JHJUUEHSAZXEEO-UHFFFAOYSA-M sodium;4-dodecylbenzenesulfonate Chemical group [Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 JHJUUEHSAZXEEO-UHFFFAOYSA-M 0.000 description 1
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 description 1
- 238000003786 synthesis reaction 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 flaky nano tungsten carbide and a preparation method and application thereof. The preparation method comprises the following specific steps that 1, a water solution of ammonium metatungstate and ammonium carbonate is added into a solution prepared from ethyl alcohol and a surface active agent, hydroxylamine hydrochloride is added after the mixture is stirred to be uniform, and HCl or ammonium hydroxide is added to adjust the pH value to range from 4 to 8 after the mixture is stirred to be uniform; 2, the mixture liquid is subjected to a hydrothermal reaction, and a sample precursor is obtained after drying; 3, the sample precursor is subjected to high-temperature carbonization in the CH4/H2 atmosphere, and the flaky nano WC material is obtained. According to preparation of flaky nano WC, on the one hand, agglomeration of nano WC is avoided, and therefore the effective specific area of the nano material can be fully achieved; on the other hand, the advantages of the flaky nano material can be fully utilized, a large number of surface atoms and more reaction active centers can be provided, carriers can be fast conveyed to the surface from the interior in the catalytic reaction process, and therefore the catalytic activity of the nano material is improved.
Description
(1) technical field
The present invention relates to a kind of tungsten carbide, particularly to a kind of flake nano carbonization tungsten and preparation and application thereof.
(2) background technology
Tungsten carbide (WC) because having the advantages such as class platinum catalysis activity, high rigidity, high thermal stability and anti-wear performance are good,
It is widely used in the field such as hard alloy, catalysis.WC not only shows as catalyst hydrogenation, takes off
Hydrogen reaction has good catalysis activity, and some reaction is also had selective catalytic action.Research further
Finding, WC also has good electric conductivity and the strongest acid resistance, and these features make WC be expected to become preferable
Electrocatalysis material is applied to electrochemical field.There are some researches show, WC methanol direct oxidation, hydrogen anodic oxidation and
The fields such as aromatic nitro compound electroreduction demonstrate certain electro catalytic activity, but catalysis activity is the highest, from reality
Application there is also bigger gap, and therefore, preparing high activity W C-material is researcher key issue urgently to be resolved hurrily.
Its catalytic performance is had a great impact by the structure of catalyst.There are some researches show, the nanometer sheet of two-dimensional structure can carry
For substantial amounts of surface atom and more chain carrier, it it is a kind of preferably catalyst structure.Nanometer sheet is ultra-thin
Geometric properties be conducive in catalytic reaction process load rapidly from internal transmission to surface, thus add fast response and enter
Journey.Before about 50 years, there is researcher to prepare and synthesized two dimensional surface plate-like golden nanometer particle.Due to this
The nanoparticle planting pattern has special surface plasma resonance performance, shows and spheroidal particle and body phase material
Expect distinct optical property.Thus recent years, the research of two-dimension nano materials is again by the further pass of people
Note, they will the fields such as surface enhanced raman spectroscopy, metal-enhanced fluorescence spectrum, catalysis, infrared therapeutic and
The fields such as photon, photoelectron, optical pickocff and biomarker have great potential using value.At present, one
A little research groups have synthesized the monocrystalline gold micron film of pattern rule with liquid-phase synthesis process and have studied the near of it
Infrared absorption characteristic [Chem.Mater.2005, (17): 566.], later, research worker by the improvement to experiment condition,
Introduce cetyl trimethylammonium bromide, by the regulation and control of growth course having been reached the control to nanoparticle pattern,
Obtain other shapes of gold nano-plates by reduction gold chloride, and improve monodispersity and the catalysis of nanoparticle
Performance [Langmuir, 2005 (21): 4710].Therefore, the present invention is by hydro-thermal self assembly and in-situ reducing carbonization skill
Art combines, and is prepared for nano-sheet WC, the preparation of this nano-sheet WC, on the one hand effectively prevent nanometer WC
Reunion, such that it is able to wave the effective ratio area of nano material from distribution；On the other hand, nanometer can be made full use of
The advantage of flaky material, it is possible to provide substantial amounts of surface atom and more chain carrier, beneficially catalytic reaction mistake
In journey load rapidly from internal transmission to surface, thus improve nano material catalysis activity.
(3) summary of the invention
The present invention the first goal of the invention is to provide the nano-sheet WC material of a kind of high dispersive, it is possible to make nano-sheet
WC keeps stable, and secondary agglomeration does not occur.
Second object of the present invention is to provide described nano-sheet WC material as eelctro-catalyst at electro-catalysis nitro
Application in compound reduction reaction.
The technical solution used in the present invention is:
The present invention provides a kind of flake nano carbonization tungsten, and described flake nano carbonization tungsten is prepared as follows:
(1) at room temperature, ammonium metatungstate and ammonium carbonate deionized water are configured to presoma culture fluid, by forerunner
Body culture fluid joins in the solution of surfactant and ethanol, is stirring evenly and then adding into oxammonium hydrochloride., stirs,
Regulation pH value is to 4～8, it is thus achieved that precursor solution；Described ammonium metatungstate and ammonium carbonate mass ratio are 1:0.5～2, described
Surfactant and ammonium metatungstate mass ratio are 0.01～0.05:1, and described oxammonium hydrochloride. with ammonium metatungstate mass ratio is
0.04～0.1:1；
(2) precursor solution step (1) obtained carries out hydro-thermal reaction 10～24h at 150～250 DEG C, stands
To room temperature, abandoning supernatant, obtain sample presoma after drying；
(3) sample presoma step (2) obtained is at CH4And H2In atmosphere, carry out carbon in 600～900 DEG C
Change, i.e. obtain described flake nano carbonization tungsten.
Further, step (1) described surfactant is dodecylbenzene sodium sulfonate or cetyl trimethyl bromination
Ammonium.
Further, step (1) described ammonium metatungstate is 1:0.8～1.5 with the mass ratio of ammonium carbonate, described surface activity
Agent and ammonium metatungstate mass ratio are 0.03～0.05:1, and described oxammonium hydrochloride. and ammonium metatungstate mass ratio are 0.04～0.06:
1。
Further, step (1) described deionized water volumetric usage is calculated as 2～200mL/g with ammonium metatungstate quality, excellent
Selecting 2～50mL/g, described ethanol and deionized water volume ratio are 0.3～0.5:1, preferably 0.4～0.5:1.
Further, step (1) hydrochloric acid or ammonia regulates pH value to 5～6.
Further, step (2) precursor solution is transferred in teflon-lined stainless steel autoclave, seals
Autoclave 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) described CH4And H2Volume ratio be 1:0.2～1.5, preferably 1:0.8～1.5.
Further, described step (3) carbonization method is: be placed in tube furnace by sample presoma, with 1～5 DEG C/min
Programming rate from room temperature be increased to 600～900 DEG C of carbonizations 1～10h (more preferably the programming rate of 2～3 DEG C/min from
Room temperature is increased to 750～900 DEG C of carbonizations 5～7h), after reacting by heating completes, logical N2It is cooled to room temperature, obtains lamellar
Nanometer tungsten carbide.
The present invention also provides for a kind of described flake nano carbonization tungsten as eelctro-catalyst at nitro compound electro-reduction reaction
Middle application.
The inventive method uses surface active agent assisting alcohol-hydrothermal method to be prepared for flake nano WC, directly uses than existing method
Ammonium metatungstate is prepared WC and is had the advantage that specific surface area is big, catalysis activity is high.
Compared with prior art, the present invention has the advantages that: flake nano prepared by the method for the invention
Preferably, nanometer sheet thick 3～15nm, on the one hand the inventive method effectively prevent nanometer WC to the dispersion of tungsten carbide nanometer sheet
Reunion, such that it is able to give full play to the effective ratio area of nano material；On the other hand, nanometer can be made full use of
The advantage of flaky material, it is possible to provide substantial amounts of surface atom and more chain carrier, beneficially catalytic reaction mistake
In journey load rapidly from internal transmission to surface, thus improve nano material catalysis activity.
(4) accompanying drawing explanation
Fig. 1 is the SEM figure that embodiment 2 nano-sheet WC amplifies 10000 times.
Fig. 2 is the SEM figure that embodiment 2 nano-sheet WC amplifies 60000 times.
Fig. 3 is that embodiment 8 (comparative example 1) obtains sample SEM figure.
Fig. 4 is the cyclic voltammetry curve of the electro-catalysis nitrobenzene reduction of embodiment 2 sample and embodiment 8 sample, wherein
A () is the cyclic voltammetry curve of embodiment 2 sample, (b) is the cyclic voltammetry curve of embodiment 8 sample.
(5) detailed description of the invention
Below in conjunction with 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, 1g ammonium metatungstate and 0.5g ammonium carbonate are added 2mL deionized water be configured to ammonium metatungstate with
The presoma culture fluid of ammonium carbonate, joins presoma culture fluid by 0.6mL ethanol and 0.01g detergent alkylate
In the solution that sodium sulfonate is made, it is stirring evenly and then adding into 0.04g oxammonium hydrochloride., is stirring evenly and then adding into HCl regulation
PH value is to 4, it is thus achieved that precursor solution；Above-mentioned precursor solution is transferred to teflon-lined rustless steel again high
In pressure still, sealing autoclave, it is maintained in the permanent temperature control box of numeral 150 DEG C of reaction 10h, reactant liquor stands extremely
Room temperature, abandoning supernatant, obtain sample presoma after 40 DEG C of vacuum drying, sample presoma is placed in tube furnace,
CH with volume ratio as 1:14、H2Gaseous mixture is reduction and carbonization gas, with the programming rate of 5 DEG C/min from room temperature
It is increased to 900 DEG C of carbonization 5h, after reacting by heating completes, logical N2It is cooled to room temperature, i.e. obtains flake nano WC.
The dispersion of WC nanometer sheet is preferable, nanometer sheet thick 12～15nm.
Embodiment 2
At room temperature, 1g ammonium metatungstate and 1g ammonium carbonate are added 20mL deionized water be configured to ammonium metatungstate with
The presoma culture fluid of ammonium carbonate, joins presoma culture fluid by 8mL ethanol and 0.04g detergent alkylate sulphur
In the solution that acid sodium is made, it is stirring evenly and then adding into 0.05g oxammonium hydrochloride., is stirring evenly and then adding into HCl and regulates pH
Value is to 5.6, it is thus achieved that precursor solution；Above-mentioned precursor solution is transferred to teflon-lined rustless steel again high
In pressure still, sealing autoclave, it is maintained in the permanent temperature control box of numeral 180 DEG C of reaction 12h, reactant liquor stands extremely
Room temperature, abandoning supernatant, obtain sample presoma after 40 DEG C of vacuum drying, sample presoma is placed in tube furnace,
CH with volume ratio as 1:14、H2Gaseous mixture is reduction and carbonization gas, with the programming rate of 5 DEG C/min from room temperature
It is increased to 900 DEG C of carbonization 5h, after reacting by heating completes, logical N2It is cooled to room temperature, i.e. obtains flake nano WC.
Its pattern such as Fig. 1 and Fig. 2.Scanning electron microscope (SEM) photograph display WC nanometer sheet dispersion is preferable, nanometer sheet thick 5～8nm.
Embodiment 3
At room temperature, 1g ammonium metatungstate and 2g ammonium carbonate are added 200mL deionized water be configured to ammonium metatungstate with
The presoma culture fluid of ammonium carbonate, joins presoma culture fluid by 100mL ethanol and 0.05g detergent alkylate
In the solution that sodium sulfonate is made, it is stirring evenly and then adding into 0.1g oxammonium hydrochloride., is stirring evenly and then adding into ammonia regulation pH
Value is to 8, it is thus achieved that precursor solution；Above-mentioned precursor solution is transferred to teflon-lined rustless steel high pressure again
In still, sealing autoclave, it is maintained in the permanent temperature control box of numeral 250 DEG C of reaction 24h, reactant liquor stands to room
Temperature, abandoning supernatant, obtain sample presoma after 40 DEG C of vacuum drying, sample presoma is placed in tube furnace,
CH with volume ratio as 1:14、H2Gaseous mixture is reduction and carbonization gas, with the programming rate of 5 DEG C/min from room temperature
It is increased to 900 DEG C of carbonization 5h, after reacting by heating completes, logical N2It is cooled to room temperature, i.e. obtains flake nano WC.
SEM figure shows the dispersion of WC nanometer sheet preferably, about nanometer sheet thickness 12nm.
Embodiment 4
At room temperature, 1g ammonium metatungstate and 1g ammonium carbonate are added 20mL deionized water be configured to ammonium metatungstate with
The presoma culture fluid of ammonium carbonate, joins presoma culture fluid by 8mL ethanol and 0.04g cetyl front three
In the solution that base ammonium bromide is made, it is stirring evenly and then adding into 0.05g oxammonium hydrochloride., is stirring evenly and then adding into HCl regulation
PH value is to 5.6, it is thus achieved that precursor solution；Again above-mentioned precursor solution is transferred to teflon-lined rustless steel
In autoclave, sealing autoclave, it is maintained in the permanent temperature control box of numeral 180 DEG C of reaction 12h, reactant liquor stands
To room temperature, abandoning supernatant, obtain sample presoma after 40 DEG C of vacuum drying, sample presoma is placed in tube furnace
In, the CH with volume ratio as 1:0.24、H2Gaseous mixture is reduction and carbonization gas, with the programming rate of 1 DEG C/min from
Room temperature is increased to 600 DEG C of carbonization 4h, after reacting by heating completes, and logical N2It is cooled to room temperature, i.e. obtains flake nano
WC.SEM figure shows the dispersion of WC nanometer sheet preferably, about nanometer sheet thickness 10nm.
Embodiment 5
At room temperature, 1g ammonium metatungstate and 1g ammonium carbonate are added 20mL deionized water be configured to ammonium metatungstate with
The presoma culture fluid of ammonium carbonate, joins presoma culture fluid by 8mL ethanol and 0.04g cetyl front three
In the solution that base ammonium bromide is made, it is stirring evenly and then adding into 0.05g oxammonium hydrochloride., is stirring evenly and then adding into HCl regulation
PH value is to 5.8, it is thus achieved that precursor solution；Again above-mentioned precursor solution is transferred to teflon-lined rustless steel
In autoclave, sealing autoclave, it is maintained in the permanent temperature control box of numeral 180 DEG C of reaction 12h, reactant liquor stands
To room temperature, abandoning supernatant, obtain sample presoma after 40 DEG C of vacuum drying, sample presoma is placed in tube furnace
In, the CH with volume ratio as 1:0.54、H2Gaseous mixture is reduction and carbonization gas, with the programming rate of 2.5 DEG C/min
It is increased to 750 DEG C of carbonization 6h from room temperature, after reacting by heating completes, logical N2It is cooled to room temperature, i.e. obtains flake nano
WC.SEM figure shows the dispersion of WC nanometer sheet preferably, nanometer sheet thick 5～10nm.
Embodiment 6
At room temperature, 1g ammonium metatungstate and 1g ammonium carbonate are added 20mL deionized water be configured to ammonium metatungstate with
The presoma culture fluid of ammonium carbonate, joins presoma culture fluid by 8mL ethanol and 0.04g cetyl front three
In the solution that base ammonium bromide is made, it is stirring evenly and then adding into 0.05g oxammonium hydrochloride., is stirring evenly and then adding into HCl regulation
PH value is to 6, it is thus achieved that precursor solution；Above-mentioned precursor solution is transferred to teflon-lined rustless steel again high
In pressure still, sealing autoclave, it is maintained in the permanent temperature control box of numeral 180 DEG C of reaction 12h, reactant liquor stands extremely
Room temperature, abandoning supernatant, obtain sample presoma after 40 DEG C of vacuum drying, sample presoma is placed in tube furnace,
CH with volume ratio as 1:14、H2Gaseous mixture is reduction and carbonization gas, with the programming rate of 2.5 DEG C/min from room temperature
It is increased to 800 DEG C of carbonization 6h, after reacting by heating completes, logical N2It is cooled to room temperature, i.e. obtains flake nano WC.
SEM figure shows the dispersion of WC nanometer sheet preferably, nanometer sheet thick 3～6nm.
Embodiment 7
At room temperature, 1g ammonium metatungstate and 1g ammonium carbonate are added 20mL deionized water be configured to ammonium metatungstate with
The presoma culture fluid of ammonium carbonate, joins presoma culture fluid by 8mL ethanol and 0.04g cetyl front three
In the solution that base ammonium bromide is made, it is stirring evenly and then adding into 0.05g oxammonium hydrochloride., is stirring evenly and then adding into HCl regulation
PH value is to 6, it is thus achieved that precursor solution；Above-mentioned precursor solution is transferred to teflon-lined rustless steel again high
In pressure still, sealing autoclave, it is maintained in the permanent temperature control box of numeral 180 DEG C of reaction 12h, reactant liquor stands extremely
Room temperature, abandoning supernatant, obtain sample presoma after 40 DEG C of vacuum drying, sample presoma is placed in tube furnace,
CH with volume ratio as 1:14、H2Gaseous mixture is reduction and carbonization gas, with the programming rate of 5 DEG C/min from room temperature
It is increased to 900 DEG C of carbonization 10h, after reacting by heating completes, logical N2It is cooled to room temperature, i.e. obtains flake nano WC.
SEM figure shows the dispersion of WC nanometer sheet preferably, nanometer sheet thick 12～15nm.
Embodiment 8: comparative example 1 (being not added with surfactant)
At room temperature, 1g ammonium metatungstate and 1g ammonium carbonate are added 20mL deionized water be configured to ammonium metatungstate with
The presoma culture fluid of ammonium carbonate, joins presoma culture fluid in 8mL ethanol, is stirring evenly and then adding into 0.05g
Oxammonium hydrochloride., is stirring evenly and then adding into HCl regulation pH value to 6；Again above-mentioned mixed solution is transferred to polytetrafluoroethyl-ne
In the stainless steel autoclave of alkene liner, sealing autoclave, it is maintained 180 DEG C of reactions 12 in the permanent temperature control box of numeral
H, reactant liquor stands to room temperature, abandoning supernatant, obtains sample presoma, by sample forerunner after 40 DEG C of vacuum drying
Body is placed in tube furnace, the CH with volume ratio as 1:14、H2Gaseous mixture is reduction and carbonization gas, with 2.5 DEG C/min
Programming rate be increased to 800 DEG C of carbonization 6h from room temperature, after reacting by heating completes, logical N2It is cooled to room temperature, gained
WC particle is block, and thickness is greatly to 600nm, and WC particle is reunited more serious, and SEM figure is shown in Fig. 3.
Embodiment 9: comparative example 2 (ammonium metatungstate presoma not being carried out any process)
At room temperature, ammonium metatungstate is placed in tube furnace, the CH with volume ratio as 1:14、H2Gaseous mixture is reduction
Carbonization gas, is increased to 800 DEG C of carbonization 6h with the programming rate of 2.5 DEG C/min from room temperature, after reacting by heating completes,
Logical N2Being cooled to room temperature, SEM figure shows that gained WC particle is for bulk, thickness greatly to 2～3 microns, and WC
Particle agglomeration is the most serious.
Embodiment 10: application
The flake nano WC that embodiment 2 prepares is prepared as powder microelectrode, uses cyclic voltammetry to nano-sheet
WC powder microelectrode carries out electroreduction catalysis active testing, and result is shown in a curve in Fig. 4.Instrument is CHI660C
Electrochemical analyser, experiment uses three electrode test systems, and electrolyte is 0.5mol L-1NaOH+0.01mol·L-1Right
Nitrophenol, reference electrode is saturated calomel electrode, and auxiliary electrode is large area light platinum electrode.Experimental temperature is
25 DEG C, scanning speed is 50mV/s.
Embodiment 11: comparative example 3
Block WC embodiment 8 obtained is prepared as powder microelectrode, repeats the testing procedure described in embodiment 10, knot
Fruit sees b curve in Fig. 4.
From fig. 4, it can be seen that the reduction peak current that paranitrophenol is on nano-sheet WC powder microelectrode apparently higher than
Block WC powder microelectrode.The nano-sheet WC catalytic performance that this explanation embodiment 2 prepares is apparently higher than embodiment 8
The block WC prepared.High degree of dispersion that its main cause is nano-sheet WC and very thin flaky nanometer structure are brought
The lifting of the unit catalysis activity that reactivity area increases and produced nanometer size effect is brought.
Claims (10)
1. a flake nano carbonization tungsten, it is characterised in that described flake nano carbonization tungsten is prepared as follows:
(1) at room temperature, ammonium metatungstate and ammonium carbonate deionized water are configured to presoma culture fluid, presoma is trained
Nutrient solution joins in the solution of surfactant and ethanol, is stirring evenly and then adding into oxammonium hydrochloride., stirs, and regulates pH
Value is to 4～8, it is thus achieved that precursor solution；Described ammonium metatungstate and ammonium carbonate mass ratio are 1:0.5～2, described surfactant with
Ammonium metatungstate mass ratio is 0.01～0.05:1, and described oxammonium hydrochloride. and ammonium metatungstate mass ratio are 0.04～0.1:1；
(2) precursor solution step (1) obtained carries out hydro-thermal reaction 10～24h at 150～250 DEG C, stands to room
Temperature, abandoning supernatant, obtain sample presoma after drying；
(3) sample presoma step (2) obtained is at CH4And H2In atmosphere, carry out carbonization in 600～900 DEG C,
I.e. obtain flake nano carbonization tungsten.
2. flake nano carbonization tungsten as claimed in claim 1, it is characterised in that step (1) described surfactant is 12
Sodium alkyl benzene sulfonate or cetyl trimethylammonium bromide.
3. flake nano carbonization tungsten as claimed in claim 1, it is characterised in that step (1) described ammonium metatungstate and ammonium carbonate
Mass ratio be 1:0.8～1.5, described surfactant and ammonium metatungstate mass ratio are 0.03～0.05:1, described oxammonium hydrochloride. with
Ammonium metatungstate mass ratio is 0.04～0.06:1.
4. flake nano carbonization tungsten as claimed in claim 1, it is characterised in that step (1) described deionized water volumetric usage
Being calculated as 2～200mL/g with ammonium metatungstate quality, described ethanol and deionized water volume ratio are 0.3～0.5:1.
5. flake nano carbonization tungsten as claimed in claim 1, it is characterised in that step (1) hydrochloric acid or ammonia regulate pH
Value is to 5～6.
6. flake nano carbonization tungsten as claimed in claim 1, it is characterised in that step (2) precursor solution is transferred to poly-four
In the stainless steel autoclave of fluorothene liner, sealing autoclave carries out hydro-thermal reaction.
7. flake nano carbonization tungsten as claimed in claim 1, it is characterised in that hydrothermal temperature is 150～200 DEG C, water
The thermal response time is 10～16h.
8. flake nano carbonization tungsten as claimed in claim 1, it is characterised in that step (3) described CH4And H2Volume
Ratio is 1:0.2～1.5.
9. flake nano carbonization tungsten as claimed in claim 1, it is characterised in that described step (3) carbonization method is: by sample
Product presoma is placed in tube furnace, is increased to 600～900 DEG C of carbonizations 1～10h with the programming rate of 1～5 DEG C/min from room temperature,
After reacting by heating completes, logical N2It is cooled to room temperature, obtains nanometer tungsten carbide.
10. flake nano carbonization tungsten described in a claim 1 should in nitro compound electro-reduction reaction as eelctro-catalyst
With.
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