CN106179392B - A kind of preparation method of the wolframic acid cobalt nanorod elctro-catalyst of iron ion doping - Google Patents
A kind of preparation method of the wolframic acid cobalt nanorod elctro-catalyst of iron ion doping Download PDFInfo
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- CN106179392B CN106179392B CN201610576130.9A CN201610576130A CN106179392B CN 106179392 B CN106179392 B CN 106179392B CN 201610576130 A CN201610576130 A CN 201610576130A CN 106179392 B CN106179392 B CN 106179392B
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- wolframic acid
- catalyst
- ion doping
- acid cobalt
- chloride
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- 239000002253 acid Substances 0.000 title claims abstract description 40
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 40
- 239000010941 cobalt Substances 0.000 title claims abstract description 40
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000002073 nanorod Substances 0.000 title claims abstract description 39
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 19
- 239000003054 catalyst Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- -1 iron ion Chemical class 0.000 claims abstract description 21
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 12
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 8
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims abstract description 8
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 3
- 238000002156 mixing Methods 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
- 238000005406 washing Methods 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 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
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 19
- 150000002500 ions Chemical class 0.000 description 12
- 238000006555 catalytic reaction Methods 0.000 description 10
- 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 description 10
- 238000000034 method Methods 0.000 description 10
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 6
- 229910001447 ferric ion Inorganic materials 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- 239000010970 precious metal Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000012498 ultrapure water Substances 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
- 239000002019 doping agent Substances 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
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 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
- 238000002441 X-ray diffraction Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 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
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 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
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical class CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 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
- 230000015556 catabolic process 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
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 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
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 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
- 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
- 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
- 238000003860 storage Methods 0.000 description 1
- 238000010408 sweeping Methods 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
- 238000002604 ultrasonography Methods 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of preparation methods of the wolframic acid cobalt nanorod elctro-catalyst of iron ion doping, using cobalt chloride, frerrous chloride or iron chloride, sodium tungstate, ammonium hydroxide as Material synthesis.Easy to operate, raw material green, abundance, at low cost, product short preparation period of the invention, and it is reproducible.The wolframic acid cobalt nanorod elctro-catalyst of the preparation-obtained iron ion doping of the present invention has good electrocatalytic decomposition aquatic products oxygen activity, can be widely applied to energy conversion field.
Description
Technical field
The present invention relates to inorganic nano electrocatalysis material technical field more particularly to a kind of tungsten of efficient iron ion doping
The preparation method of sour cobalt nanorod elctro-catalyst.
Background technology
Electro-catalysis is to be happened at the heterocatalysis of electrode and electrolyte interface, is related to electrochemistry, Surface Science, material science
Etc. the cross discipline of numerous subsciences.Electro-catalysis is widely present and is applied to energy conversion and storage (fuel cell, chemical-electrical
Pond, ultracapacitor, Hydrogen Energy), environmental protection (sewage disposal, electrochemical sensor, degradation organic waste materials, ozone generate etc.),
Novel substance synthesizes and material preparation, Electrochemical Engineering (chlorine industry, intermetallic composite coating, forming, finish etc.) and biology, analysis etc.
In the electrochemical process in field.
Electrolysis water includes mainly cathode hydrogen evolution and Oxygen anodic evolution two parts, and the efficiency of wherein electrolysis water is reacted by Oxygen anodic evolution
It determines.Oxygen anodic evolution reaction is related to 4 electronic transfer process, is a slow dynamic process of complexity, an efficient electricity
Chemical oxygen evolution reaction catalysts can solve to decompose the slow process of hydrodynamics.
Although noble metal and metal oxide containing precious metals show good performance on electro-catalysis oxygen evolution reaction, these
Noble metal price is more expensive, and metal oxide containing precious metals are easier to corrode in alkaline medium, this is hindered to a certain extent
Their extensive uses as analysis oxygen positive electrode.Therefore, various non-precious metal catalysts have developed into noble metal and its oxidation
The substitute of object.Usual non-precious metal catalyst include mainly spinel oxides and Ca-Ti ore type transition metal oxide with
And their derivative, layered double hydroxide, carbon-based 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 knots
Structure.It is mainly synthesized using the hot method of hydrothermal/solvent in current research work.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,
Phenol etc. has important role.Also reported in document cobaltous tungstate can with electrocatalytic decomposition aquatic products oxygen, but its activity compared with
It is low.
The analysis oxygen performance of material is closely related to the suction-operated of hydroxide ion with it.It is too weak or too with hydroxide ion
Strong interaction is all unfavorable for the raising of its electro catalytic activity.The analysis oxygen performance of cobaltous tungstate is weaker, is on the one hand derived from it to hydrogen
Oxygen radical ion has weak active force.
Invention content
In view of the deficiencies of the prior art, the present invention is intended to provide a kind of wolframic acid cobalt nanorod elctro-catalyst of iron ion doping
Preparation method, by the way that its suction-operated to hydroxide ion will be optimized in iron ion doping to wolframic acid cobalt nanorod, to
Improve its electro catalytic activity, and the present invention is easy to operate, raw material sources are abundant, at low cost, product short preparation period, and repeat
Property is good.
To achieve the goals above, the present invention adopts the following technical scheme that：
A kind of preparation method of the wolframic acid cobalt nanorod elctro-catalyst of iron ion doping, includes the following steps：
S1 under agitation, in water by frerrous chloride or iron chloride and cobalt chloride and sodium tungstate co-dissolve, so
After ammonium hydroxide is added, after stirring and evenly mixing mixed solution；
The step S1 mixed solutions obtained are transferred in the reaction kettle of polytetrafluoroethyllining lining by S2, dry in air blast after sealing
It is reacted in dry case；Gained powder is centrifuged after reaction is cooled to room temperature, is replaced with deionized water and absolute ethyl alcohol
Washing for several times, is placed in drying in vacuum drying chamber, obtains solid product, as the wolframic acid cobalt nanorod electro-catalysis of iron ion doping
Agent.
It should be noted that in step S1, the amount of cobalt chloride is 1mmoL, and the amount of sodium tungstate is 1mmoL, frerrous chloride or
The amount of iron chloride is 0.05mmoL, and the amount of water is 40mL, and the amount of ammonium hydroxide is 0.5mL.
It it is 180 DEG C in the temperature reacted in air dry oven, the reaction time is 12 small it should be noted that in step S2
When.
It should be noted that in step S2, dry temperature is 60 DEG C in vacuum drying chamber, and the time is 4 hours.
The beneficial effects of the present invention are：By will optimize in iron ion doping to wolframic acid cobalt nanorod its to hydroxyl from
The suction-operated of son, to improve its electro catalytic activity, and the present invention is easy to operate, and raw material sources are abundant, at low cost, product system
The standby period is short and reproducible.
Description of the drawings
Fig. 1 a are the scanning electron microscope pictures of pure phase wolframic acid cobalt nanorod prepared by comparative example one, and Fig. 1 b are the XRD of corresponding product
Diffraction pattern.
Fig. 2 a and 2b are the scanning of the wolframic acid cobalt nano-particle prepared under without using aqueous ammonia conditions in comparative example two respectively
Electronic Speculum picture and corresponding XRD styles.
Fig. 3 a are Fe prepared by embodiment 12+The scanning electron microscope picture of the wolframic acid cobalt nanorod of ion doping, Fig. 3 b are corresponding productions
The XRD diffraction patterns of object.
Fig. 4 a and 4b are the embodiment of the present invention two respectively using Fe3+Ion is mixed for the iron ion prepared under the conditions of dopant
The scanning electron microscope picture of miscellaneous wolframic acid cobalt nanorod and corresponding XRD styles.
Fig. 5 is the linear volt-ampere curve of pure phase wolframic acid cobalt nanorod and nano particle.
Fig. 6 is nitrogen adsorption-desorption curve of pure phase wolframic acid cobalt nanorod and nano particle.
Fig. 7 is to adulterate Fe respectively2+With Fe3+The linear volt-ampere curve of the wolframic acid cobalt nanorod of ion.
Fig. 8 is wolframic acid cobalt nanorod and Fe2+The linear volt-ampere curve of the wolframic acid cobalt nanorod of ion doping.
Specific implementation mode
Below with reference to attached drawing, the invention will be further described, it should be noted that the present embodiment is with this technology side
Premised on case, detailed embodiment and specific operating process are given, but protection scope of the present invention is not limited to this reality
Apply example.
A kind of preparation method of the wolframic acid cobalt nanorod elctro-catalyst of iron ion doping, includes the following steps：
S1 under agitation, in water by frerrous chloride or iron chloride and cobalt chloride and sodium tungstate co-dissolve, so
After ammonium hydroxide is added, after stirring and evenly mixing mixed solution；
The step S1 mixed solutions obtained are transferred in the reaction kettle of polytetrafluoroethyllining lining by S2, dry in air blast after sealing
It is reacted in dry case；Gained powder is centrifuged after reaction is cooled to room temperature, is replaced with deionized water and absolute ethyl alcohol
Washing for several times, is placed in drying in vacuum drying chamber, obtains solid product, as the wolframic acid cobalt nanorod electro-catalysis of iron ion doping
Agent,
It should be noted that in step S1, the amount of cobalt chloride is 1mmoL, and the amount of sodium tungstate is 1mmoL, frerrous chloride or
The amount of iron chloride is 0.05mmol, and the amount of water is 40mL, and the amount of ammonium hydroxide is 0.5mL.
It it is 180 DEG C in the temperature reacted in air dry oven, the reaction time is 12 small it should be noted that in step S2
When.
It should be noted that in step S2, dry temperature is 60 DEG C in vacuum drying chamber, and the time is 4 hours.
Below by way of experiments have shown that the present invention performance.
Comparative example one：
The building-up process of pure phase wolframic acid cobalt nanorod is as follows：
By 1mmol cobalt chlorides and 1mmol sodium tungstates under stiring co-dissolve in 40mL water.Into above-mentioned mixed solution
0.5mL ammonium hydroxide is added, stirs and evenly mixs.The mixed solution is transferred to (V in the autoclave of inner liner polytetrafluoroethylene liner
=50mL), 180 DEG C of reaction 12h.Cooled to room temperature after reaction takes out product, uses high purity water and anhydrous second respectively
Alcohol washs for several times, and the product for centrifuging wash clean is placed in vacuum drying chamber drying.
It can be seen that product is nanorod structure by Fig. 1 a scanning electron microscope pictures.By Fig. 1 b it is found that product main diffraction peak is equal
Can index turn to monoclinic phase cobaltous tungstate, it is consistent with standard card (JCPDS No.15-0687).
Comparative example two：
Without using the building-up process of the wolframic acid cobalt nano-particle prepared under aqueous ammonia conditions：
1mmol cobalt chlorides and 1mmol sodium tungstates are dissolved in 40mL water, stirred and evenly mixed.The solution is put into liner to gather
In the autoclave of tetrafluoroethene liner (V=50mL), 180 DEG C of reaction 12h.Cooled to room temperature after reaction,
Product is taken out, is washed for several times with high purity water and absolute ethyl alcohol respectively, the product for centrifuging wash clean, which is placed in vacuum drying chamber, to be done
It is dry.
Scanning electron microscope picture (Fig. 2 a) observation indicate that, the product be nano particle.XRD analysis the result shows that (Fig. 2 b),
Consistent with wolframic acid cobalt nanorod, product is the cobaltous tungstate of pure phase.
Embodiment one
Fe2+The building-up process of the wolframic acid cobalt nanorod of ion doping is as follows：
It is separately added into 1mmol cobalt chlorides, 1mmol in the autoclave (V=50mL) of inner liner polytetrafluoroethylene liner
The frerrous chloride of sodium tungstate, 0.05mmol, stirring and dissolving.Then the ammonium hydroxide of 0.5mL is added into reaction kettle again, stirs and evenly mixs.
By reaction kettle screwing hermetic it is good after be put into electric heating constant-temperature blowing drying box, reacted 12 hours at 180 DEG C.After reaction certainly
It is so cooled to room temperature, product is taken out.It is washed for several times with high purity water and absolute ethyl alcohol respectively, the product for centrifuging wash clean is placed in
Vacuum drying chamber is dried.
As shown in Figure 3a, a small amount of Fe2+The doping of ion does not influence the pattern of wolframic acid cobalt nanorod.The XRD styles of product with
Consistent (Fig. 3 b) of undoped wolframic acid cobalt nanorod, not new diffraction maximum occur, should be the result shows that Fe2+Ion doping enters
Cobaltous tungstate nanometer rods lattice.
Embodiment two
Fe3+The building-up process of the wolframic acid cobalt nanorod of ion doping：
1mmol cobalt chlorides, 1mmol sodium tungstates, 0.05mmol ferric trichlorides are dissolved in 40mL water, stirred and evenly mixed.To
0.5mL ammonium hydroxide is added in above-mentioned mixed solution, stirs and evenly mixs.The mixed solution is transferred to the height of inner liner polytetrafluoroethylene liner
Press reaction kettle in (V=50mL), by reaction kettle screwing hermetic it is good after be put into electric heating constant-temperature blowing drying box react 180 DEG C instead
Answer 12h.Cooled to room temperature after reaction takes out product, is washed for several times with high purity water and absolute ethyl alcohol respectively, will be from
The product of heart wash clean is placed in vacuum drying chamber drying.
Scanning electron microscope picture (Fig. 4 a) observation indicate that, the product be nanometer rods.XRD analysis is the result shows that (Fig. 4 b) product
For the cobaltous tungstate of pure phase.
It is real that electro-catalysis production oxygen is carried out to the catalyst prepared in comparative example one, comparative example two, embodiment one and embodiment two
It tests, reaction condition is as follows：
The catalytic performance of elctro-catalyst is tested using linear volt-ampere (LSV).The test of chemical property is in Beijing
It carries out on the CHI660D electrochemical workstations of China Tech Pu Tian scientific ＆ technical corporation, is done to electrode with platinum filament, reference electricity is done to be saturated calomel
Pole.It weighs 5mg catalyst and is dissolved in 1mL (V isopropanols: water=2 V: in solution 1), then ultrasonic 30min is added 40 μ L's
Naphthols continues ultrasound 30min.It is electric to measure its on the glass-carbon electrode prepared for the amount for pipetting 5 μ L with liquid-transfering gun after placing overnight
Chemical property.The electrolyte of test system is the KOH of 0.5M, and the speed of sweeping of LSV is 10mV/s.Electrode potential uses RHE standards, E
(RHE)=E (SCE)+0.242+0.059 × pH.
Analyze the linear volt-ampere curve (figure of pure phase wolframic acid cobalt nanorod and nano particle in comparative example one and comparative example two
5), the results showed that, there is wolframic acid cobalt nanorod better electro-catalysis to produce oxygen performance.The good electro-catalysis of wolframic acid cobalt nanorod is lived
Property, can be attributed to it has the one-dimensional nano structure and big specific surface area (Fig. 6) for being conducive to carrier transport.
Fe is adulterated in analysis embodiment one and embodiment two2+With Fe3+The linear volt-ampere of the wolframic acid cobalt nanorod of ion doping
Curve (Fig. 7), the results showed that Fe2+With Fe3+The wolframic acid cobalt nanorod of ion doping has similar electro catalytic activity, doping two
Valence iron ion or ferric ion influence the electro-catalysis of wolframic acid cobalt nanorod analysis oxygen performance little.
Analyze the Fe of the wolframic acid cobalt nanorod and embodiment one of comparative example one2+The wolframic acid cobalt nanorod of ion doping it is linear
Volt-ampere curve (Fig. 8), the results showed that, Fe2+The wolframic acid cobalt nanorod of ion doping has the electro catalytic activity being remarkably reinforced.
Current density can reach 72mAcm when 1.95V (vs RHE)-2It is 5 times or more of undoped wolframic acid cobalt nanorod.Well
Electro catalytic activity, the doping derived from iron ion regulated and controled the electronic structure of cobaltous tungstate, has been conducive to the absorption of hydroxide ion, to
Enhance its electro-catalysis analysis oxygen performance.
For those skilled in the art, it can be made various corresponding according to above technical solution and design
Change and distortion, and all these change and distortions should be construed as being included within the protection domain of the claims in the present invention.
For those skilled in the art, it can be made various corresponding according to above technical solution and design
Change and distortion, and all these change and distortions should be construed as being included within the protection domain of the claims in the present invention.
Claims (2)
1. a kind of preparation method of the wolframic acid cobalt nanorod elctro-catalyst of iron ion doping, which is characterized in that include the following steps：
S1 under agitation, by frerrous chloride or iron chloride, in water together with cobalt chloride and sodium tungstate co-dissolve, then plus
Enter ammonium hydroxide, mixed solution is obtained after stirring and evenly mixing；The amount of cobalt chloride is 1mmol, and the amount of sodium tungstate is 1mmol, frerrous chloride or chlorine
The amount for changing iron is 0.05mmol, and the amount of water is 40ml, and the amount of ammonium hydroxide is 0.5ml；
The step S1 mixed solutions obtained are transferred in the reaction kettle of polytetrafluoroethyllining lining by S2, in air dry oven after sealing
In reacted 12 hours at 180 DEG C；Gained powder is centrifuged after reaction is cooled to room temperature, with deionized water and anhydrous second
Alternately washing for several times, is placed in drying in vacuum drying chamber to alcohol, obtains solid product, as the wolframic acid cobalt nanorod electricity of iron ion doping
Catalyst.
2. a kind of preparation method of the wolframic acid nanometer rods elctro-catalyst of iron ion doping according to claim 1, feature
It is, in step S2, dry temperature is 60 DEG C in vacuum drying chamber, and the time is 4 hours.
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