CN106179392A - A kind of preparation method of the cobaltous tungstate nanometer rods eelctro-catalyst of iron ion doping - Google Patents
A kind of preparation method of the cobaltous tungstate nanometer rods eelctro-catalyst of iron ion doping Download PDFInfo
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- CN106179392A CN106179392A CN201610576130.9A CN201610576130A CN106179392A CN 106179392 A CN106179392 A CN 106179392A CN 201610576130 A CN201610576130 A CN 201610576130A CN 106179392 A CN106179392 A CN 106179392A
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- Prior art keywords
- nanometer rods
- cobaltous
- catalyst
- ion doping
- eelctro
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- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 title claims abstract description 49
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 title claims abstract description 49
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 25
- -1 iron ion Chemical class 0.000 title claims abstract description 24
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 20
- 239000003054 catalyst Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims abstract description 11
- 229940097267 cobaltous chloride Drugs 0.000 claims abstract description 11
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 10
- 229960002089 ferrous chloride Drugs 0.000 claims abstract description 8
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims abstract description 8
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 230000004044 response Effects 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 6
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 229960003284 iron Drugs 0.000 abstract 2
- 239000000047 product Substances 0.000 description 17
- 150000002500 ions Chemical class 0.000 description 12
- 238000006555 catalytic reaction Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000002105 nanoparticle Substances 0.000 description 6
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 229910001447 ferric ion Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 239000010970 precious metal Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- 230000005611 electricity Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- ZXOKVTWPEIAYAB-UHFFFAOYSA-N dioxido(oxo)tungsten Chemical compound [O-][W]([O-])=O ZXOKVTWPEIAYAB-UHFFFAOYSA-N 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
-
- B01J35/33—
-
- B01J35/40—
-
- 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
-
- 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 invention discloses the preparation method of the cobaltous tungstate nanometer rods eelctro-catalyst of a kind of iron ion doping, with cobaltous chloride, ferrous chloride or iron chloride, sodium tungstate, ammonia as Material synthesis.The present invention is simple to operate, and raw material green, abundance, low cost, product manufacturing cycle is short, and reproducible.The cobaltous tungstate nanometer rods eelctro-catalyst of the preparation-obtained iron ion doping of the present invention has good electrocatalytic decomposition Aquatic product oxygen activity, can be widely applied to energy conversion field.
Description
Technical field
The present invention relates to inorganic nano electrocatalysis material technical field, particularly relate to the tungsten of a kind of efficient iron ion doping
The preparation method of acid cobalt nanorod eelctro-catalyst.
Background technology
Electro-catalysis is to occur at the heterocatalysis of electrode and electrolyte interface, relates to electrochemistry, Surface Science, material science
Cross discipline etc. numerous subsciences.Electro-catalysis is widely present and is applied to energy conversion and stores (fuel cell, chemical-electrical
Pond, ultracapacitor, Hydrogen Energy), environmental conservation (sewage disposal, electrochemical sensor, degraded organic waste materials, ozone generation etc.),
Novel substance synthesis and prepared by material, Electrochemical Engineering (chlorine industry, intermetallic composite coating, shaping, finish etc.) and biology, analysis etc.
In the electrochemical process in field.
Electrolysis water mainly includes cathode hydrogen evolution and Oxygen anodic evolution two parts, and the efficiency being wherein electrolysed water is reacted by Oxygen anodic evolution
Determine.Oxygen anodic evolution reaction relates to 4 electronic transfer process, is a complexity dynamic process slowly, a high efficiency electricity
Chemistry oxygen evolution reaction catalysts can solve decomposition water kinetics process slowly.
Although noble metal and metal oxide containing precious metals show good performance on electro-catalysis oxygen evolution reaction, but these
Noble metal price comparison is expensive, and metal oxide containing precious metals is easier corrosion in alkaline medium, and this hinders to a certain extent
They are as the extensive application of analysis oxygen anelectrode.Therefore, various non-precious metal catalysts have developed into noble metal and oxidation thereof
The succedaneum of thing.Generally non-precious metal catalyst mainly include spinel oxides and Ca-Ti ore type transition metal oxide with
And their derivant, layered double hydroxide, carbon back non-metallic catalyst, and some transition metal complexes etc..
Cobaltous tungstate belongs to divalent transition metal tungstates, and cobaltous tungstate crystal is typical wolframite P2/c monoclinic space group knot
Structure.In current research work, main employing hydrothermal/solvent full-boiled process synthesizes.Relevant result of study shows, cobaltous tungstate micro-nano
Material in terms of magnetic material, microwave dielectric ceramic, photoelectric display material, catalytic decomposition organic pollution rhodamine, methyl orange,
The aspects such as phenol have important effect.Document is also reported cobaltous tungstate can with electrocatalytic decomposition Aquatic product oxygen, but its activity is relatively
Low.
The adsorption of hydroxide ion is closely related by the analysis oxygen performance of material with it.The most weak with hydroxide ion or too
Strong interaction is all unfavorable for the raising of its electro catalytic activity.The analysis oxygen performance of cobaltous tungstate is more weak, on the one hand comes from it to hydrogen
Oxygen radical ion has weak active force.
Summary of the invention
For the deficiencies in the prior art, it is desirable to provide the cobaltous tungstate nanometer rods eelctro-catalyst of a kind of iron ion doping
Preparation method, by iron ion doping to cobaltous tungstate nanometer rods optimizing its adsorption to hydroxide ion, thus
Improving its electro catalytic activity, and the present invention is simple to operate, abundant raw material source, low cost, product manufacturing cycle is short, and repeats
Property is good.
To achieve these goals, the present invention adopts the following technical scheme that
The preparation method of the cobaltous tungstate nanometer rods eelctro-catalyst of a kind of iron ion doping, comprises the steps:
Under agitation, by ferrous chloride or iron chloride, and cobaltous chloride and sodium tungstate are dissolved in water, so S1 jointly
Rear addition ammonia, obtains mixed solution after stirring and evenly mixing；
The mixed solution that step S1 obtains is transferred in teflon-lined reactor by S2, does in air blast after sealing
Dry case reacts；Question response is cooled to gained powder centrifugation after room temperature, with deionized water and dehydrated alcohol alternately
Washing for several times, is placed in vacuum drying oven and is dried, obtain solid product, be the cobaltous tungstate nanometer rods electro-catalysis of iron ion doping
Agent.
It should be noted that in step S1, the amount of cobaltous chloride is 1mmoL, the amount of sodium tungstate is 1mmoL, ferrous chloride or
The amount of iron chloride is 0.05mmoL, and the amount of water is 40mL, and the amount of ammonia is 0.5mL.
It should be noted that in step S2, in air dry oven, the temperature of reaction is 180 DEG C, and the response time is 12 little
Time.
It should be noted that in step S2, the temperature being dried in vacuum drying oven is 60 DEG C, and the time is 4 hours.
The beneficial effects of the present invention is: by by iron ion doping to cobaltous tungstate nanometer rods optimizes its to hydroxyl from
The adsorption of son, thus improve its electro catalytic activity, and the present invention is simple to operate, abundant raw material source, low cost, product system
The standby cycle is short and reproducible.
Accompanying drawing explanation
Fig. 1 a is the scanning electron microscope picture of the pure phase cobaltous tungstate nanometer rods of comparative example one preparation, and Fig. 1 b is the XRD of corresponding product
Diffraction pattern.
Fig. 2 a and 2b is the scanning of the cobaltous tungstate nano-particle of preparation under not using aqueous ammonia conditions in comparative example two respectively
Electronic Speculum picture and corresponding XRD style.
Fig. 3 a is the Fe of embodiment 1 preparation2+The scanning electron microscope picture of the cobaltous tungstate nanometer rods of ion doping, Fig. 3 b is corresponding producing
The XRD diffraction pattern of thing.
Fig. 4 a and 4b is that the embodiment of the present invention two is using Fe respectively3+Ion is that the iron ion of preparation is mixed under the conditions of adulterant
The scanning electron microscope picture of miscellaneous cobaltous tungstate nanometer rods and corresponding XRD style.
Fig. 5 is the linear volt-ampere curve of pure phase cobaltous tungstate nanometer rods and nano-particle.
Fig. 6 is the nitrogen adsorption-desorption curve of pure phase cobaltous tungstate nanometer rods and nano-particle.
Fig. 7 is the Fe that adulterates respectively2+With Fe3+The linear volt-ampere curve of the cobaltous tungstate nanometer rods of ion.
Fig. 8 is cobaltous tungstate nanometer rods and Fe2+The linear volt-ampere curve of the cobaltous tungstate nanometer rods of ion doping.
Detailed description of the invention
Below with reference to accompanying drawing, the invention will be further described, it should be noted that the present embodiment is with this technical side
Premised on case, give detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to this reality
Execute example.
The preparation method of the cobaltous tungstate nanometer rods eelctro-catalyst of a kind of iron ion doping, comprises the steps:
Under agitation, by ferrous chloride or iron chloride, and cobaltous chloride and sodium tungstate are dissolved in water, so S1 jointly
Rear addition ammonia, obtains mixed solution after stirring and evenly mixing；
The mixed solution that step S1 obtains is transferred in teflon-lined reactor by S2, does in air blast after sealing
Dry case reacts；Question response is cooled to gained powder centrifugation after room temperature, with deionized water and dehydrated alcohol alternately
Washing for several times, is placed in vacuum drying oven and is dried, obtain solid product, be the cobaltous tungstate nanometer rods electro-catalysis of iron ion doping
Agent,
It should be noted that in step S1, the amount of cobaltous chloride is 1mmoL, the amount of sodium tungstate is 1mmoL, ferrous chloride or
The amount of iron chloride is 0.05mmol, and the amount of water is 40mL, and the amount of ammonia is 0.5mL.
It should be noted that in step S2, in air dry oven, the temperature of reaction is 180 DEG C, and the response time is 12 little
Time.
It should be noted that in step S2, the temperature being dried in vacuum drying oven is 60 DEG C, and the time is 4 hours.
The performance of the present invention is proved below by way of experiment.
Comparative example one:
The building-up process of pure phase cobaltous tungstate nanometer rods is as follows:
1mmol cobaltous chloride and 1mmol sodium tungstate are dissolved in 40mL water the most jointly.In above-mentioned mixed solution
Add 0.5mL ammonia, stirring and evenly mixing.This mixed solution is transferred to (V in the middle of the autoclave of inner liner polytetrafluoroethylene inner bag
=50mL), 180 DEG C of reaction 12h.Reaction naturally cools to room temperature after terminating, and is taken out by product, respectively by high purity water and anhydrous second
Alcohol washs for several times, the product of centrifugal wash clean is placed in vacuum drying oven and is dried.
Be can be seen that product is nanorod structure by Fig. 1 a scanning electron microscope picture.From Fig. 1 b, product main diffraction peak is equal
Index can turn to monoclinic phase cobaltous tungstate, consistent with standard card (JCPDS No.15-0687).
Comparative example two:
Do not use under aqueous ammonia conditions the building-up process of the cobaltous tungstate nano-particle of preparation:
1mmol cobaltous chloride and 1mmol sodium tungstate are dissolved in 40mL water, stirring and evenly mixing.This solution is put into liner gather
In the middle of the autoclave of tetrafluoroethene inner bag (V=50mL), 180 DEG C of reaction 12h.Reaction naturally cools to room temperature after terminating,
Product is taken out, uses high purity water and absolute ethanol washing for several times respectively, the product of centrifugal wash clean is placed in vacuum drying oven and does
Dry.
Scanning electron microscope picture (Fig. 2 a) observation indicate that, this product is nano-particle.XRD analysis result shows (Fig. 2 b),
Consistent with cobaltous tungstate nanometer rods, product is the cobaltous tungstate of pure phase.
Embodiment one
Fe2+The building-up process of the cobaltous tungstate nanometer rods of ion doping is as follows:
It is separately added into 1mmol cobaltous chloride, 1mmol in the autoclave (V=50mL) of inner liner polytetrafluoroethylene inner bag
Sodium tungstate, the ferrous chloride of 0.05mmol, stirring and dissolving.The ammonia of 0.5mL, stirring and evenly mixing is added the most again in reactor.
Put in electric heating constant-temperature blowing drying box after good for reactor screwing hermetic, react 12 hours at 180 DEG C.Reaction terminates the most certainly
So it is cooled to room temperature, product is taken out.Use high purity water and absolute ethanol washing for several times respectively, the product of centrifugal wash clean is placed in
Vacuum drying oven is dried.
As shown in Figure 3 a, a small amount of Fe2+The doping of ion does not affect the pattern of cobaltous tungstate nanometer rods.The XRD style of product with
Consistent (Fig. 3 b) of unadulterated cobaltous tungstate nanometer rods, does not has new diffraction maximum to occur, this result shows Fe2+Ion doping enters
Cobaltous tungstate nanometer rods lattice.
Embodiment two
Fe3+The building-up process of the cobaltous tungstate nanometer rods of ion doping:
1mmol cobaltous chloride, 1mmol sodium tungstate, 0.05mmol ferric chloride are dissolved in 40mL water, stirring and evenly mixing.To
Above-mentioned mixed solution adds 0.5mL ammonia, stirring and evenly mixing.This mixed solution is transferred to the height of inner liner polytetrafluoroethylene inner bag
In the middle of pressure reactor (V=50mL), electric heating constant-temperature blowing drying box reacts put into after good for reactor screwing hermetic to 180 DEG C instead
Answer 12h.Reaction naturally cools to room temperature after terminating, and is taken out by product, respectively with high purity water and absolute ethanol washing for several times, and will be from
The product of heart wash clean is placed in vacuum drying oven and is dried.
Scanning electron microscope picture (Fig. 4 a) observation indicate that, this product is nanometer rods.XRD analysis result shows (Fig. 4 b) product
Cobaltous tungstate for pure phase.
The catalyst of preparation in comparative example one, comparative example two, embodiment one and embodiment two is carried out electro-catalysis and produces oxygen in fact
Testing, reaction condition is as follows:
The catalytic performance of eelctro-catalyst uses linear volt-ampere (LSV) to test.The test of chemical property is all in Beijing
Carry out on the CHI660D electrochemical workstation of China Tech Pu Tian scientific & technical corporation, do electrode with platinum filament, do reference electricity with saturated calomel
Pole.Weigh 5mg catalyst dissolution in the solution of 1mL (V isopropanol: V water=2: 1), ultrasonic 30min, it is subsequently adding 40 μ L's
Naphthols, continues ultrasonic 30min.Pipette the amount of 5 μ L on the glass-carbon electrode prepared with liquid-transfering gun, after overnight placing, measure its electricity
Chemical property.The electrolyte of test system is the KOH of 0.5M, and LSV sweeps speed for 10mV/s.Electrode potential uses RHE standard, E
(RHE)=E (SCE)+0.242+0.059 × pH.
Analyze the linear volt-ampere curve (figure of pure phase cobaltous tungstate nanometer rods and nano-particle in comparative example one and comparative example two
5), result shows, cobaltous tungstate nanometer rods has more preferable electro-catalysis and produces oxygen performance.The electro-catalysis work that cobaltous tungstate nanometer rods is good
Property, can attribution be its one-dimensional nano structure with beneficially carrier transport and big specific surface area (Fig. 6).
Analyze the Fe that adulterates in embodiment one and embodiment two2+With Fe3+The linear volt-ampere of the cobaltous tungstate nanometer rods of ion doping
Curve (Fig. 7), result shows Fe2+With Fe3+The cobaltous tungstate nanometer rods of ion doping has close electro catalytic activity, doping two
It is little that the electro-catalysis of cobaltous tungstate nanometer rods is analysed oxygen performance impact by valency iron ion or ferric ion.
Analyze the cobaltous tungstate nanometer rods of comparative example one and the Fe of embodiment one2+The cobaltous tungstate nanometer rods of ion doping linear
Volt-ampere curve (Fig. 8), result shows, Fe2+The cobaltous tungstate nanometer rods of ion doping has the electro catalytic activity being remarkably reinforced.
During 1.95V (vs RHE), electric current density can reach 72mA cm-2It it is more than 5 times of unadulterated cobaltous tungstate nanometer rods.Well
Electro catalytic activity, the doping coming from iron ion has regulated and controled the absorption of the electronic structure of cobaltous tungstate, beneficially hydroxide ion, thus
Enhance its electro-catalysis analysis oxygen performance.
For a person skilled in the art, can according to above technical scheme and design, make various accordingly
Change and deformation, and within all these change and deformation should be construed as being included in the protection domain of the claims in the present invention.
For a person skilled in the art, can according to above technical scheme and design, make various accordingly
Change and deformation, and within all these change and deformation should be construed as being included in the protection domain of the claims in the present invention.
Claims (4)
1. the preparation method of the cobaltous tungstate nanometer rods eelctro-catalyst of an iron ion doping, it is characterised in that comprise the steps:
S1 under agitation, by ferrous chloride or iron chloride, is jointly dissolved in water together with cobaltous chloride and sodium tungstate, then adds
Enter ammonia, after stirring and evenly mixing, obtain mixed solution；
The mixed solution that step S1 obtains is transferred in teflon-lined reactor by S2, in air dry oven after sealing
In react；Question response is cooled to by gained powder centrifugation after room temperature, with deionized water and dehydrated alcohol alternately washing
For several times, it is placed in vacuum drying oven and is dried, obtain solid product, be the cobaltous tungstate nanometer rods eelctro-catalyst of iron ion doping.
The preparation method of the wolframic acid nanometer rods eelctro-catalyst of a kind of iron ion doping the most according to claim 1, its feature
Being, in step S1, the amount of cobaltous chloride is 1mmoL, and the amount of sodium tungstate is that the amount of 1mmoL, ferrous chloride or iron chloride is
0.05mmoL, the amount of water is 40mL, and the amount of ammonia is 0.5mL.
The preparation method of the wolframic acid nanometer rods eelctro-catalyst of a kind of iron ion doping the most according to claim 1, its feature
Being, in step S2, in air dry oven, the temperature of reaction is 180 DEG C, and the response time is 12 hours.
The preparation method of the wolframic acid nanometer rods eelctro-catalyst of a kind of iron ion doping the most according to claim 1, its feature
Being, in step S2, the temperature being dried in vacuum drying oven is 60 DEG C, and the time is 4 hours.
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| CN108033492A (en) * | 2017-12-19 | 2018-05-15 | 扬州大学 | The CoWO of amorphous4The preparation method of cage-shaped nano material and its application in electro-catalysis |
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| CN108033492A (en) * | 2017-12-19 | 2018-05-15 | 扬州大学 | The CoWO of amorphous4The preparation method of cage-shaped nano material and its application in electro-catalysis |
| CN109019533A (en) * | 2018-07-18 | 2018-12-18 | 南京航空航天大学 | A kind of bimetallic nitride Co3W3N and the preparation method and application thereof |
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| CN110038599A (en) * | 2019-04-28 | 2019-07-23 | 浙江大学台州研究院 | Efficient two cobaltous selenides/cobaltous tungstate composite electrocatalyst of one kind and preparation method thereof |
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| CN113774403A (en) * | 2021-09-22 | 2021-12-10 | 辽宁师范大学 | Water decomposition electrocatalyst Ag8W4O16/CoWO4Preparation method of (1) |
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